USOO8882862B2

(12) United States Patent (10) Patent No.: US 8,882,862 B2

Stiller et al. (45) Date of Patent: Nov. 11, 2014

(54) METHOD OF FORMING AMESOPHASE USPC .................................................... 44/628, 620

PTCH FROMA COAL EXTRACT SUITABLE See application file for complete search history.
FOR PROCESSING TO A HIGHVALUE COKE
(56) References Cited
(75) Inventors: Alfred H. Stiller, Morgantown, WV
(US); Peter G. Stansberry, North U.S. PATENT DOCUMENTS
Olmstead, OH (US) 2,681,300 A 6/1954 Ruidisch et al.
(73) Assignee: West Virginia University, Morgantown, 3,505,203 A 4, 1970 Nelson
WV (US) (Continued)
(*) Notice: Subject to any disclaimer, the term of this FOREIGN PATENT DOCUMENTS
patent is extended or adjusted under 35 JP 56-072O79 6, 1981
U.S.C. 154(b) by 133 days. JP 05-230469 9, 1993
(21) Appl. No.: 13/166,139 OTHER PUBLICATIONS
(22) Filed: Jun. 22, 2011 Allevato et al., , Assessing the Structural Integrity and Remaining
Life of Coke Drums with Acoustic Emission Testing, Strain Gaging,
(65) Prior Publication Data and Finite Element Analysis, 1999, Engineering Sources Tech Con
US 2012/0097579 A1 Apr. 26, 2012 ference and Exhibition, pp. 1-18.
Related U.S. Application Data (Continued)
(63) Continuation of application No. 13/165.857, filed on Primary Examiner — Cephia DToomer
Jun. 22, 2011, now Pat. No. 8,597,503, and a (74) Attorney, Agent, or Firm — The Webb Law Firm
(Continued) (57) ABSTRACT
(51) Int. Cl. The present disclosure provides methods and systems for coal
CIOL 5/00 (2006.01) liquefaction and obtaining a mesophase pitch. A method of
CIGI/00 (2006.01) obtaining a quinoline insoluble-free and ash-free mesophase
pitch may include exposing a coal to a hydrogenated veg
(Continued) etable oil in the presence of a coal-derived solvent to form a
(52) U.S. Cl. slurry, elevating the temperature of the slurry to facilitate
CPC, C10G I/002 (2013.01); CIOL5/00 (2013.01); liquefying the coal and liberating a volatile matter, separating
CI0G I/065 (2013.01); C10G 2300/1014 the insoluble components from the slurry to obtain a de-ashed
(2013.01); CIOB I/04 (2013.01); CIOB 55/00 coal extract that is quinoline insoluble-free, and distilling the
(2013.01); CIOB 57/045 (2013.01); CIOG coal extract under vacuum to obtain a mesophase pitch with a
2300/708 (2013.01) softening point in the range of 25 degrees Celsius to 160
USPC ............................................... 44/620; 44/628 degrees Celsius, wherein the mesophase pitch can be coked to
(58) Field of Classification Search obtain an anisotropic coke. A quinoline insoluble-free and
CPC ............. C10L 5700; C10B 1/04; C10B 55/00; ash-free pitch may be obtained by the method.
C10B 57/045; C10G 1/002: C10G 2300/1014:
C1 OG 23 OOf708 10 Claims, 18 Drawing Sheets

O
ATWE
N COA-104 CTDC8

WIFR
112
e

CONDENSED XTRACT 18
114

COLLECTED CNTRUGE
WOLATILES 128 120

TAILS 22 celle

COKER
138 e-PITCH132 K- DESTILLATION
COLUMN3.
WATES CONDENSE
142 COKE140 WOATILES 134
 US 8,882.862 B2
Page 2

Related U.S. Application Data 5,961,814 A 10, 1999 Kearns

6,129,773. A 10/2000 Killicket al.
continuation-in-part of application No. 1 1/897,059. 6,241,957 B1 6/2001 Stiller et al.
filed on Aug. 29, 2007, and a continuation-in-part of 3. R g38. e
t
application No. 1 1/805,737, filed on May 24, 2007, 6,387.343 B1 5, 2002 Klett
now Pat. No. 8,226,816. 6,399,149 B1 6/2002 Klett et al.
(60) Provisional application No. 61/357,323, filed on Jun. 35 R 38. Site al
22, 2010, provisional application No. 61/357,332, 6,576, 168 B2 6/2003 Hardcastle et al.
filed on Jun. 22, 2010. 6,656,443 B2 12/2003 Klett
6,663,842 B2 12/2003 Klett
(51) Int. C. SRK. 4
33 al
poet al.
CIGL/06 (2006.01) 6,797.251 B1 9, 2004 Bennett et al.
CIOB I/04 (2006.01) 6,833,012 B2 12/2004 Rogers
CIOB 55/00 (2006.01) 6,860,910 B2 3/2005 Rogers et al.
CIOB 57/04 (2006.01) 6,869,455 B2 3/2005 Rogers et al.
7,014,668 B2 3/2006 Golubkov et al.
7,070,755 B2 7/2006 Klett et al.
(56) References Cited 8, 101,812 B2 1/2012 Fan et al.
8,226,816 B2 7/2012 Kennel et al.
U.S. PATENT DOCUMENTS 2005/0097814 A1 5/2005 Sugita et al.
2007. O144944 A1 6/2007 Del Bianco et al.
$59,38 A . .197 Stewart, Jr. et al.
3,919,387 A * 1 1/1975 Singer ........................... 264,344
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2009, O250381 A1
3/2008 Kennel et al.
10, 2009 Fan et al.
3,954,544. A 5/1976 Hooker 2011/0230688 A1 9, 2011 Charon et al.
3,966,585 A 6/1976 Gray et al.
4,045,328 A 8, 1977 Green et al. OTHER PUBLICATIONS
4,052,291 A 10/1977 Espenscheid et al.
4,081,361 A 3, 1978 Hildebrand et al. J. J. Fernandez et al., “Modification of Coal-Tar Pitch by Air-Blow
4,092,236 A 5/1978 Heredy ing-I. Variation of Pitch Composition and Properties'. Pergamon,
4,177,079 A 12/1979 Espenscheid Carbon, vol. 33, No. 3, pp. 295-307.
4,179,352 A 12, 1979 Effron D &8
4211,576 A 7, 1980 Yan adyburjor et al., “Production of Carbon Products Using a Coal
427112 A 8, 1980 Johanson Extraction Process. NETL Contract No. DE-FC26-02NT41596,
4.24995 1 A 2f1981 Leonard National Energy Technology Laboratories Final Report Sep. 11,
4,259,171 A 3/1981 Stadelhofer et al. 2002-Aug. 31, 2004, Published Dec. 12, 2005, pp. 1-233, U.S.
4,272.356 A 6, 1981 Stiller et al. Department of Energy, Pittsburgh, Pennsylvania.
4,277.324 A * 7/1981 Greenwood .................... 208/45 Fernández et al., “Modification of Coal-Tar Pitch by Air-Blowing I.
4,303,496 A 12/1981 Rudnick Variation of Pitch Composition and Properties.” Carbon, 1995, pp.
4,334,977 A 6, 1982 Derbyshire et al. 295-307, vol. 33, No. 3, Elsevier Science Ltd., Great Britain.
4,369,171 A 1/1983 Grindstaffet al. Taylor et al., “Future Synthetic Fuels: A Scientific and Technical
3. A
W-
3. She Applications Forecast-1975.” Sep. 1975, US Army Contract DAAC)5-
T3-C-0559.

E. A 88: E. “Increased Automobile Fuel Efficiency and Synthetic Fuels: Alter

455 1234 A 11, 1985 Kuhlmann natives for Reducing Oil Imports.” NTIS Order No. PB83-126094,
4,610,776 A 9/1986 Urban et al. 1982, 157 pages.
4,617,105 A 10, 1986 Miller Stansberry et al., “Development of binder pitches from coal extract
4,671,801 A 6/1987 Burgess et al. and coal-tar pitch blends.” 2001, pp. 581-585, Light Metals.
4,762,527 A 8, 1988 Beshore et al. “The Carbon Products Industry Vision for the Future'. Sep.1998, pp.
4.959,139 A 9/1990 Blakeburn, II et al. i-vii; 1-27, Carbon Products Consortium.
4,997.548 A 3/1991 Rantell et al. Wombles, Robert H., “Experience with Petroleum Enhanced Coal
5,061,363 A 10, 1991 Farcasiu et al. Tar Pitch', 2000, pp. 1-11. http://www.koppers.com/htm/PandS
5, 182,011 A 1, 1993 Tsuchitani et al. RanD WhitePhtml.
5,208,003 A 5, 1993 Simandlet al. Elliott, J.D., “Fine-Tune Your Delayed Coker: Obstacles and Objec
5,248,413 A
5,262,043 A 1 9,1/1993
1993 Stencel et al.
Boenigket al. tives. S
Ives, Sep. 2004 1SSue, pp. 83-90. . www.flydrocarbon
Hvor bonP
Processing.
5,300,272 A 4, 1994 Simandlet al. CO.
5,746,906 A 5/1998 McHenry et al. "Tar and Pitch', pp. 1-31, Kirk-Othmer Encyclopedia of Chemical
5,868,974 A 2f1999 Kearns Technology.
5,888,469 A 3, 1999 Stiller et al.
5,955,375 A 9, 1999 Zondlo et al. * cited by examiner
U.S. Patent US 8,882,862 B2
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1. 2
METHOD OF FORMING AMESOPHASE enhance the dissolution ability of heavy aromatic oils by the
PTCH FROMA COAL EXTRACT SUITABLE addition of a hydrogenated liquid. In an embodiment, the
FOR PROCESSING TO A HIGHVALUE COKE hydrogenated liquid may be partially or fully hydrogenated
Vegetable oil. The present invention may also provide a pro
CROSS-REFERENCE TO RELATED cess that may liquefy coal without the need to hydrogenate the
APPLICATIONS Solvent. In embodiments, this may occur by the use of an
additive that may contain hydrogen, which may result in
This application claims the benefit of the following provi de-polymerizing large coal molecules, while also suppress
sional applications, each of which is hereby incorporated by ing recombination; thus, resulting in Smaller overall molecu
reference in its entirety: 10 lar distribution and creating a liquid.
U.S. Provisional Application No. 61/357,323, filed Jun. 22, In an aspect, a method of obtaining a de-ashed coal extract
2010; and U.S. Provisional Application No. 61/357,332, filed includes exposing a coal to a hydrogenated vegetable oil in
Jun. 22, 2010. the presence of a coal-derived solvent to form a slurry, elevat
This application is a continuation-in-part of the following ing the temperature of the slurry to facilitate liquefying the
U.S. patent applications, each of which is incorporated by 15 coal and liberating a volatile matter, and separating the
reference in its entirety: insoluble components from the slurry to obtain a de-ashed
U.S. Non-Provisional application Ser. No. 1 1/897,059, coal extract, wherein the coal extract is suitable for down
filed Aug. 29, 2007; and U.S. Non-Provisional application stream processing. Water liberated as a result of the elevated
Ser. No. 1 1/805,737, filed May 24, 2007. temperature may be captured and stored. Volatile matter may
This application is a continuation of the following U.S. be condensed and recycled. The method may further include
patent applications, each of which is incorporated by refer distilling the coal extract to obtain a pitch. The coal-derived
ence in its entirety: Solvent may be selected from a group comprising recycled
U.S. Non-Provisional application Ser. No. 13/165.857, liquefied coal, coaltar distillate, and coal tarpitch. The hydro
filed Jun. 22, 2011. genated vegetable oil may have a vapor pressure of less than
25 1500 psi attemperatures less than 400 degrees Celsius. Sepa
BACKGROUND OF THE INVENTION rating may include at least one of centrifugation, filtration,
decanting, and float separation. The hydrogenated vegetable
1. Field of the Invention oil may be at least one of soybean oil, peanut oil, canola oil,
The present invention relates to coal-to-liquid technology, olive oil, other vegetable oil or combination of at least two of
and specifically to a system and method for liquefying coal 30 these oils. The temperature may be elevated to between 300
using solvents that hydrogenate under mild conditions. degrees Celsius and 600 degrees Celsius. The method may
2. Description of the Related Art further include agitating the slurry to facilitate liquefying the
Coal-to-liquid technology refers to chemical processes that coal. The coal may be selected from one or more of a sub
convert solid coal into liquid fuels and chemicals. The hydro bituminous coal, lignite coal and an anthracite coal. The
gen to carbon ratio (H/C, molar) of coal is about 0.8 while that 35 method may further include heating the insoluble compo
of liquid fuels is about 2.0. The main functions of the coal nents to liberate a volatile matter and an entrained solvent,
to-liquid processes are breakage of the coal's molecular size blending the insoluble components with a calcareous material
and addition of hydrogen into coal, or in otherwords, destruc and roasting the blend in a kiln at a temperature greater than
tive hydrogenation of coal. These processes are generally 1000 degrees Celsius to obtain a clinker, and grinding the
termed as coal liquefaction. 40 clinker to obtain a cement. The method may further include
Coal liquefaction may occur by two different pathways: distilling the coal extract under vacuum to obtain a
indirect liquefaction and direct liquefaction. The indirect mesophase pitch with a softening point in the range of 25
method converts coal to hydrogen and carbon monoxide, and degrees Celsius to 160 degrees Celsius, wherein the
syngas by reacting coal with steam at high temperatures in an mesophase pitch can be coked to obtain an anisotropic coke.
oxygen-starved combustion process. Direct liquefaction 45 The method may further include coking the pitch to obtain a
includes reaction of coal with hydrogen in a manner that coal coke. The coke may be at least one of an anisotropic coke, a
becomes liquid. However, direct coal liquefaction has been metallurgical coke, a graphite coke, an anode coke, and a
historically carried out with hydrogen gas, which requires needle coke. The method may further include air blowing the
high temperature and pressure. In an example, direct coal pitch to crosslink molecules in the pitch, the air blowing of
liquefaction may involve temperatures in excess of 450° C. 50 synthetic pitch used for at least modifying a softening point
and 2000 psig pressure. and increasing coke yield.
Tetralin has been used as a donor Solvent. However, a large In an aspect, a method of obtaining a de-ashed coal extract
overpressure of hydrogen and high temperature is needed to may include exposing a coal to a petroleum crude to form a
transfer the hydrogen from the gas phase to naphthalene, slurry, elevating the temperature of the slurry to facilitate
which is produced when tetralin is dehydrogenated as it trans 55 liquefying the coal and liberating a volatile matter, and sepa
fers hydrogen to coal molecules. Thus, in situ re-hydrogena rating the insoluble components from the slurry to obtain a
tion during liquefaction can be rather costly. de-ashed coal extract, wherein the coal extract is suitable for
In view of the limitations discussed above, there exists a downstream processing. Petroleum crude may be at least one
need for a method of coal liquefaction utilizing an inexpen of crude bitumen, oil sands crude and liquids containing at
sively produced, effective hydrogen donor Solvent to digest 60 least 20% of oil sands crude. The de-ashed coal extract may
coal. be added to a pipeline of petroleum crude for delivery to a
petroleum refinery.
SUMMARY OF THE INVENTION In an aspect, a method of obtaining a de-ashed coal extract
may include exposing a coal to a rubber material in the pres
In an aspect, the present invention provides methods and 65 ence of a coal-derived solvent to form a slurry, elevating the
systems for inexpensively producing an effective solvent to temperature of the slurry to facilitate liquefying the coal and
digest coal. Alternatively, the methods and systems may liberating a volatile matter, and separating the insoluble com
 US 8,882,862 B2
3 4
ponents from the slurry to obtain a de-ashed coal extract, as it is being coked, and a coke formed in the apparatus is
wherein the coal extract is suitable for downstream process removed by the force of the Archimedes spiral.
ing. The rubber material may be from a rubber tire. In yet another aspect, an apparatus for coking may include
In an aspect, a method of obtaining a de-ashed coal extract a coated coking drum that receives a pitch material, wherein
may include exposing a coal to a sewage material in the the coking drum is coated with a coating comprising at least
presence of a coal-derived solvent to form a slurry, elevating one of a chromium, an aluminum, a nickel, oran alloy thereof,
the temperature of the slurry to facilitate liquefying the coal aheater that heats the pitch material to a coking temperature,
and liberating a volatile matter, and separating the insoluble a flash vessel that condenses liberated volatile matter, and a
components from the slurry to obtain a de-ashed coal extract, coated plunger, wherein the plunger is coated with a coating
wherein the coal extract is suitable for downstream process 10 comprising at least one of a chromium, an aluminum, a
ing. nickel, or an alloy thereof wherein a coke formed in the
In an aspect, a method of obtaining a cement by-product of apparatus is removed by the force of the plunger being pushed
coal liquefaction may include exposing a coal to a hydroge or pulled through the coking drum.
nated vegetable oil in the presence of a coal-derived solvent to In an aspect, a modular coal liquefaction system may
form a slurry, elevating the temperature of the slurry to facili 15 include a reactor for exposing a coal to a hydrogenated veg
tate liquefying the coal and liberating a volatile matter, sepa etable oil in the presence of a coal-derived solvent to form a
rating the insoluble components from the slurry, heating the slurry, a heater that elevates the temperature of the slurry in
insoluble components to liberate a Volatile matter and an the reactor to facilitate liquefying the coal and liberating a
entrained solvent, blending the insoluble components with a Volatile matter, and a centrifuge that separates the insoluble
calcareous material and roasting the blend in a kiln at a components from the slurry to obtain a de-ashed coal extract,
temperature greater than 1000 degrees Celsius to obtain a wherein the coal extract is suitable for downstream process
clinker, and grinding the clinker to obtain a cement. ing, wherein the reactor, heater, and centrifuge are adapted to
In an aspect, a method of obtaining a quinoline insoluble be modular. The system may further include a distillation
free and ash-free mesophase pitch may include exposing a column that distills the de-ashed coal extract to obtain a pitch.
coal to a hydrogenated vegetable oil in the presence of a 25 The system may further include a coker that cokes at least one
coalderived solvent to form a slurry, elevating the temperature of the de-ashed coal extract and the pitch to obtain a coke. The
of the slurry to facilitate liquefying the coal and liberating a system may be adapted to be modularly disposed on a rail car.
Volatile matter, separating the insoluble components from the The system may be adapted to be modularly disposed on a
slurry to obtain a de-ashed coal extract that is quinoline semi-truck trailer.
insoluble-free, and distilling the coal extract under vacuum to 30 In another aspect, a modular coal liquefaction system may
obtain a mesophase pitch with a softening point in the range include a reactor for exposing a coal to a hydrogenated veg
of 25 degrees Celsius to 160 degrees Celsius, wherein the etable oil in the presence of a coal-derived solvent to form a
mesophase pitch can be coked to obtain an anisotropic coke. slurry, a heater that elevates the temperature of the slurry in
A quinoline insoluble-free and ash-free pitch may be the reactor to facilitate liquefying the coal and liberating a
obtained by the method. 35 Volatile matter, a centrifuge that separates the insoluble com
In an aspect, a method of obtaining a high quality coke ponents from the slurry to obtain a de-ashed coal extract,
from a low rank coal extract may include exposing a coal to a wherein the coal extract is suitable for downstream process
hydrogenated vegetable oil in the presence of a coal-derived ing, a distillation column that distills the de-ashed coal extract
solvent to form a slurry, elevating the temperature of the to obtain a pitch, and a coker that cokes at least one of the
slurry to facilitate liquefying the coal and liberating a volatile 40 de-ashed coal extract and the pitch to obtain a coke, wherein
matter, separating the insoluble components from the slurry the coker comprises a coated coking drum that receives the
to obtain a de-ashed coal extract that is quinoline insoluble de-ashed coal extract or the pitch, wherein the coking drum is
free, distilling the coal extract under vacuum to obtain a pitch coated with a coating comprising at least one of a chromium,
with a suitable softening point, and coking the pitch to obtain an aluminum, a nickel, or an alloy thereof, wherein the reac
a coke. The coke may be at least one of an anisotropic coke, a 45 tor, heater, centrifuge, distillation column, and coker are
metallurgical coke, a graphite coke, an anode coke, and a adapted to be modular. The system may be adapted to be
needle coke. The method may further include air blowing the modularly disposed on a rail car. The system may be adapted
pitch to crosslink molecules in the pitch, the air blowing of to be modularly disposed on a semi-truck trailer.
synthetic pitch used for at least modifying a softening point In an aspect, a coal liquefaction system includes a reactor
and increasing coke yield. 50 for exposing a coal, to a hydrogenated vegetable oil in the
In an aspect, an apparatus for coking includes a coated presence of a coal-derived solvent to form a slurry, a heater
coking drum that receives a pitch material, wherein the cok that elevates the temperature of the slurry in the reactor to
ing drum is coated with a coating comprising at least one of a facilitate liquefying the coal and liberating a volatile matter,
chromium, an aluminum, a nickel, oran alloy thereof, aheater and a centrifuge that separates the insoluble components from
that heats the pitch material to a coking temperature, and a 55 the slurry to obtain a de-ashed coal extract, wherein the coal
flash vessel that condenses a liberated volatile matter, extract is Suitable for downstream processing. The system
wherein a coke formed in the apparatus is readily removable. may further include a distillation column that distills the
In another aspect, an apparatus for coking includes a coated de-ashed coal extract to obtain a pitch. The system may fur
coking drum that receives a pitch material, wherein the cok ther includeacoker that cokes at least one of the de-ashed coal
ing drum is coated with a coating comprising at least one of a 60 extract and the pitch to obtain a coke. The coker includes a
chromium, an aluminum, a nickel, oran alloy thereof, aheater coated coking drum that receives the de-ashed coal extract or
that heats the pitch material to a coking temperature, a flash the pitch, wherein the coking drum is coated with a coating
vessel that condenses liberated volatile matter, and a coated comprising at least one of a chromium, an aluminum, a
Archimedes screw, wherein the Archimedes screw is coated nickel, or an alloy thereof. The system may be adapted to be
with a coating comprising at least one of a chromium, an 65 modular. The system may be adapted to be modularly dis
aluminum, a nickel, or an alloy thereof, wherein the posed on a rail car. The system may be adapted to be modu
Archimedes screw pushes the pitch through the coking drum larly disposed on a semi-truck trailer.
 US 8,882,862 B2
5 6
In an aspect, a coal liquefaction system includes a reactor Those of ordinary skill in the art will appreciate that the
for exposing a coal to a hydrogenated vegetable oil in the elements in the figures are illustrated for simplicity and clar
presence of a coal-derived solvent to form a slurry, a heater ity and are not necessarily drawn to scale. For example, the
that elevates the temperature of the slurry in the reactor to dimensions of Some of the elements in the figures may be
facilitate liquefying the coal and liberating a volatile matter, a exaggerated, relative to other elements, in order to improve an
centrifuge that separates the insoluble components from the understanding of the present invention.
slurry to obtain a de-ashed coal extract, wherein the coal
extract is suitable for downstream processing, a distillation DESCRIPTION OF THE PREFERRED
column that distills the de-ashed coal extract to obtain a pitch, EMBODIMENTS
10
and a coker that cokes at least one of the de-ashed coal extract
and the pitch to obtain a coke, wherein the coker comprises a Detailed embodiments of the present invention are dis
coated coking drum that receives the de-ashed coal extract or closed herein; however, it is to be understood that the dis
the pitch, wherein the coking drum is coated with a coating closed embodiments are merely exemplary of the invention,
comprising at least one of a chromium, an aluminum, a 15 which may be embodied in various forms. Therefore, specific
nickel, or an alloy thereof. structural and functional details disclosed herein are not to be
In another aspect of the invention, the methods and systems interpreted as limiting, but merely as a basis for the claims and
may produce a slurry of coal liquids and undissolved coal as a representative basis for teaching one skilled in the art to
particles. The slurry may be further refined to produce a pitch, variously employ the present invention in virtually any appro
which may be considered a final productor alternatively may priately detailed structure. Further, the terms and phrases
be upgraded to produce lighter hydrocarbon synthetic crude used herein are not intended to be limiting, but rather to
for fuels and chemicals. The present invention may also seek provide an understandable description of the invention.
to remove Sulfur from Sulfur-containing hydrocarbon liquids The terms 'a' or “an, as used herein, are defined as one or
Such as crude petroleum. more than one. The term “another as used herein, is defined
These and other systems, methods, objects, features, and 25 as at least a second or more. The terms “including” and/or
advantages of the present invention will be apparent to those "having, as used herein, are defined as comprising (i.e., open
skilled in the art from the following detailed description of the transition).
preferred embodiment and the drawings. All documents men The present invention relates to coal solvents and more
tioned herein are hereby incorporated in their entirety by specifically to a method for inexpensively producing an effec
reference. 30 tive partially or fully hydrogenated solvent to digest coal,
BRIEF DESCRIPTION OF THE DRAWINGS
thereby producing a slurry of coal liquids and undissolved
coal particles. In an embodiment, the present invention may
include three phases. The first phase may include formation
The invention and the following detailed description of of a coal slurry and that may be treated in a reactor and may
certain embodiments thereof may be understood with refer 35 then be centrifuged to obtain a centrate. The second phase
ence to the following figures: may include distillation of the centrate produced in the first
FIG. 1 illustrates an overview of a system for carrying out phase. The distillation may result in formation of pitch that
a coal liquefaction process, in accordance with an embodi may be introduced to a coker in the third phase. In this phase,
ment of the present invention. the pitch may be coked to obtain coke with different proper
FIG. 2 illustrates a flowchart illustrating a method of 40 ties.
increasing the average molecular weight of a pitch product, in
accordance with an embodiment of the present invention. The present disclosure describes a process for coal lique
FIG. 3 illustrates a block flow diagram of an example of a faction that involves the mixing of ground coal, a coal tar
processing system that may be used to produce synthetic distillate that has been purchased from a coke oven operator
pitch, in accordance with an embodiment of the present or distributor or collected from prior runs of the process, and
invention. 45 a hydrogen donor Solvent to form a slurry. Most coal lique
FIG. 4 is a chart depicting an example of coal conversion faction was done previously with bituminous coal, but in
using various solvents in accordance with one embodiment. contrast, the present disclosure describes the advantageous
FIG. 5 is a chart depicting an example of the benefits of use of Sub-bituminous and lignite coals and other low rank
hydrogenation of the feedstock solvent on coal conversion, in coals not previously considered Suitable for liquefaction. It
accordance with one embodiment. 50 should be understood that the process described herein may
FIG. 6 depicts a process flow diagram for coal liquefaction. be employed with any kind of coal. Coal liquefaction has
FIG. 7 depicts an embodiment of the coal liquefaction previously been carried out with hydrogen gas, requiring high
system. temperature and pressure, commonly at 450 C and 2000 psig
FIG. 8 depicts an embodiment of a process flow of a dis pressure. In the EXXon donor process, hydrogenated naphtha
tillation column. 55 lene is used as a proton donor. Naphthalene hydrogenation,
FIG.9 depicts an embodiment of a process flow of a coker. and in situ re-hydrogenation, requires high temperatures and
FIG. 10 depicts a method of a coal liquefaction process. high pressures. The present disclosure describes the unex
FIG. 11 depicts a method of a coal liquefaction process. pected liquefaction results obtained using hydrogenated veg
FIG. 12 depicts a method of a coal liquefaction process. etable oil or partially hydrogenated vegetable oil in combina
FIG. 13 depicts a method of a coal liquefaction process.
FIG. 14 depicts a method of obtaining a cement by-product 60 tion with a coaltar distillate (CTD). Liquefaction can proceed
of coal liquefaction. without high temperature or applied pressure that is usually
FIG. 15 depicts a method of obtaining a quinoline required for liquefaction, however, any level of temperature
insoluble-free and ash-free mesophase pitch. and pressure may be employed in the process. Also, it is
FIG. 16 depicts a method of obtaining a high quality coke relatively easy and inexpensive to hydrogenate vegetable oil.
from a low rank coal extract. 65 Coal also liquefies without high temperature or pressure in
FIG. 17 depicts a coated coker and coated plunger. pipeline crude oil, since pipeline crude has excess hydrogen.
FIG. 18 depicts a mobile coal liquefaction unit. Coal also liquefies in CTD mixed with ground up rubber tires
 US 8,882,862 B2
7 8
as the H-donor, lignin-containing sewage sludge, and other for mitigating odor. For example, the reactor 102 may be
hydrogen donor solvents further described herein. provided with sodium hydroxide (NaOH) columns for
The slurry is heated at ambient pressure in a reactor to drive absorbing the odor.
off water. At this stage in the process, the temperature may Further, the reactor 102 may enable mixing various reac
only be raised high enough to boil off water. Water is flashed tants such as coal 104, a CTD 108, and an additive 110 to form
off when the pressure builds up in the reactor and can option a slurry in which reactive dissolution of the coal 104 occurs to
ally be collected and stored. Many cycles may be needed to yield a coal extract. After liquefaction, the coal extract may be
remove substantially all of the water. Alternatively, the coal de-ashed. In an embodiment, the coal extract may be de-ashed
may first be dried. After a few cycles of water evaporation, the by employing a separation process, Such as centrifugation,
reactor is brought up to temperature for the thermal break 10 float separation, decanting, filtration, and the like, to separate
down of the coal molecules. The fracturing of the large coal the extract into a heavy phase containing the insoluble coal
molecules commonly occurs through the formation of radi products and a light phase (hereinafter referred as centrate)
containing the soluble coal products. The centrate may be
cals. AS radicals form, the hydrogen donor solvents donate a refined using typical petroleum refining processes to yield
hydrogen to stabilize the radical, thus stabilizing the liquid 15 transportation fuels. Alternatively, the centrate may be dis
form. As aromatic sites get Saturated, the coal liquid becomes tilled to yield a pitch that can be coked to yield high value
more and more aliphatic. While the hydrogen donor solvent coke products. The pitch may also be refined using typical
may be involved in stabilization of thermally generated radi petroleum refining processes to yield transportation fuels.
cals, it may also be involved in bond cleavage. Thus, the In an embodiment, the coal 104 may be a low rank coal
process may actually be improved by having only partially Such as Sub-bituminous coal. Further, the low-rank coal prod
hydrogenated solvents because once all of the radical sites are ucts may be rich in hydrogen, possess higher oil to asphaltene
filled, they will not be re-cleaved. The process liberates vola ratios, and may be more aliphatic than the bituminous coal
tiles, which can be fed back into the process as “CTD starting liquids. The present invention may enable generation of high
material. There are changes that occur in the chemical com quality coke from low rank coals; however, it will be evident
position of the recycled CTD. More dissolved coal molecules 25 to a person skilled in the art that the coal 104 may be bitumi
replace Some of the original molecules so the Solvent nous, lignite, and the like.
becomes more compatible with the dissolving coal as the In an embodiment, the coal 104 may be crushed to -20
CTD is being reused. Indeed, any volatiles liberated through mesh (800 microns) or smaller before combining the coal 104
out the process may be recovered and recycled as starting with other reactants. Further, the CTD 108 may be obtained
material. 30 from a petroleum refinery, a coal tar refinery, purchased from
The resultant coal extract is centrifuged, or otherwise sub a coke oven operator or distributor, or the like. Alternatively,
jected to a separation process, to de-ash it. The solid ash, or the CTD 108 may be collected from prior cycles of the liq
tails, can be recovered from the centrifuge and processed to uefaction processing in the system 100. In an embodiment,
eventually obtain a cement, which will be further described the additive 110 may be a hydrogen donor solvent (H donor
35 solvent). In embodiments, the H donor solvent may be alter
below. The centrate is collected and can immediately be sub natively referred as a proton transfer agent.
jected to petroleum-type refining processes to obtain fuels. In an embodiment, the additive 110 may be a partially or
Alternatively, it can be distilled. Partial distillation results in fully hydrogenated vegetable oil (hereinafter alternatively
a heavy crude-like substance, which can be further refined referred to as HVO). The HVO may include, but is not limited
using petroleum-type refining processes. Further distillation 40 to, corn, canola, Sunflower, safflower, and olive. Since Veg
results in pitch similar to coal tar binder pitch, but without the etable oils may be easily hydrogenated, they may be preferred
quinoline insoluble matter. Annealing at this distillation step as the H donor solvent for use in the system 100. In an
alters the properties of the resultant pitch. Pitch can be further embodiment, the partially hydrogenated vegetable oil may
processed in a coker, such as a delayed coker. Optionally, the include one part of hydrogenated vegetable oil mixed with
pitch can be air blown to obtain coke with different properties. 45 one part of non-hydrogenated vegetable oil, or any other ratio
In some embodiments, the coker may be coated with thereof. Vegetable oils may behydrogenated to a level of up to
chrome, nickel, aluminum or alloys thereof to facilitate ten percent hydrogen by weight using lower pressure, lower
removal of the coke. The plunger or worm gear of the coker temperature and shorter residence time than hydrogensation
may also be similarly coated to facilitate coke removal. The of other solvents, such as naphthalene. For example, soybean
coated coker is smaller than other commercially available 50 oil can be hydrogenated at a pressure of less than 200 psi, at
cokers, thus, CTL processes/plants with coke as the end prod a temperature less than 200° C., and a residence time of 10
uct may be miniaturized or mobilized. Carbon materials such minutes or less. Hence, this process requires less processing
as coke stick to steel. It is difficult to separate coke from steel; energy, since generation of high temperature and pressure is
however, coke does not stick to chrome or chrome alloys energy-intensive. Moreover, hydrogenated vegetable oils are
therefore coating steel with chrome or chrome alloys permits 55 known for their overall economy and high boiling point,
separation of coke from the Surface. making them Suitable for use in processes to dissolve coal.
FIG. 1 illustrates a system 100 for carrying out a coal In embodiments, a plurality of hydrogenated Solvents may
liquefaction process. The system 100 may include a coal be used for the coal liquefaction process. The hydrogenated
liquefaction reactor 102 (hereinafter referred to as reactor Solvents may include, but are not limited to, pipeline crude
102). The reactor 102 may be a closed reactor. In an embodi 60 oil, rubber tires, animal waste, anything with the potential of
ment, the reactor 102 may be run in a continuous mode, i.e., adding a proton to an aromatic or breaking a chemical bond,
reactants may be continuously fed into the reactor 102 and horse manure, chicken manure, sewage sludge, lignin, any
may emerge as a continuous stream of products. Further, the bio-waste with lignin, peanut oil, soybean oil, canola oil,
reactor 102 may be run in a batch mode for carrying out a olive oil or other vegetable oil, decalin, partially hydroge
sequence of different operations such as Solids dissolution, 65 nated coal tar distillate, or partially hydrogenated petroleum
product mixing, batch distillation, and the like. In an embodi distillate or partially hydrogenated decant oil or recycle oil,
ment, the reactor 102 may be configured with alkali columns Fisher-Tropsch liquid, methyl naphthalene, decahydronaph
 US 8,882,862 B2
10
thalene, tetrahydronaphthalene, methyl naphthalene, creo ambient pressure in the reactor 102 to drive off water. At this
Sote oil, coal tarpitch, asphalt pitch, gasification tar, recycled stage in the process, the temperature may only be raised high
motor oil, petroleum distillates, rubber, plastics, recycled enough to boil off water. Many cycles of the process may be
plastics (e.g. polystyrenes), recycled rubber, biomass deriva required for completely removing the water. In an alternative
tives, liquefied coal, liquefied biomass, shale oil, liquefied embodiment, the coal 104 may be dried first. After a few
process gas, cacenaphthenes, di, tetra- and octahydroan cycles of water evaporation, the reactor 102 may be brought
thracenes, tetrahydroacenaphthenes and other derivatives of up to a temperature for liquefaction. The thermal rupture of
partially hydrogenated aromatic compounds, petroleum dis coal molecules may result in the production of unstable free
tillates, petroleum catalytic cracker products, distillates of radicals. In an embodiment, the proton transfer agent may
gasification tars, products from the pyrolysis of recycled 10
prevent re-polymerization in the coal liquefaction process.
hydrocarbons, and aromatic oil products obtained from the The free radicals, as mentioned herein, may react with hydro
distillation of shale oil or tar sands.
As mentioned herein, rubber tires may be used as an H gen donated by the H donor solvent present in the process to
donor solvent. The rubber tires may include about 40% car form stable species. In some embodiments, the H donor sol
bon black by weight. When coal is dissolved using these 15 vent may be capable of engendering bond Scission. Thus, the
rubber tires, this carbon black may become quinoline process may be improved by having only partially hydroge
insoluble and, therefore, the pitch obtained may be tuned to nated Solvents, i.e., one part of the molecules in solution may
commercially used pitches from coke ovens. be hydrogenated while the others are not.
In an embodiment, lignin may be used as an H donor Therefore, once all the radical sites are filled, they may not
Solvent. Lignin is an undigested, propylbenzene polymer be re-cleaved. The process may liberate volatiles, which may
found in mammal waste. Hydrogen lost due to splitting of the be fed (recycled) into the process as a CTD starting material.
polymer may be used as a hydrogen source. In an example, In an embodiment, there may be changes that may occur in the
when bacteria consume oxygen containing compounds from chemical composition of the recycled CTD. As more dis
tertiary sewage sludge, the sludge is left with lignin. Thus, Solved coal molecules replace some of the original molecules,
tertiary sewage sludge may be used in the coal liquefaction 25 the recycle solvent may become more compatible with the
process. dissolving coal. In an embodiment, any volatile liberated
In an embodiment, a blend of hydrogenated and non-hy throughout the process may be recovered and recycled as the
drogenated solvents may result in an improved yield. For starting material. Further, the proton transfer agent, such as
example, during coal liquefaction, once a coal molecule the HVO, may saturate aromatic site and may render the
breaks down into Smaller pieces, proton transfer may take 30 resultant liquid more aliphatic.
place. The Smaller pieces of the coal molecule may get hydro In an embodiment, pipeline crude oil may be used as the
genated and may tend to become non-polar. Accordingly, the additive 110 in the coal liquefaction process. Accordingly, the
non-polar coal molecules may get dissolved in the non-pro pipeline crude oil may act as a solvent as well as a proton
tonated form of the solvent. transfer agent, and in Some embodiments, a hydrogenation
In embodiments, the coal liquefaction process may pro 35 agent may be added to the coal liquefaction mixture for
ceed at a lower pressure than is usually required for coal enhancing the dissolution of coal in the pipeline crude oil. The
liquefaction e.g., 400 psig. In an embodiment of the present hydrogenation agent may facilitate addition of hydrogen mol
invention, the HVO may enable the coal liquefaction process ecules to the pipeline crude oil, thereby enabling molecules of
to be run at lower temperature and lower pressure with less the pipeline crude oil to become less polar. The addition of
hydrogen. In a scenario, the coal liquefaction process may 40 hydrogen molecules may increase solubility of the pipeline
enable hydrogenation through the proton transfer agent at crude oil molecules in the coal liquefaction mixture.
milder conditions when compared with the conditions of After separation of the extract into insoluble material and
conventional proton transfer agents. For example, the coal centrate, the centrate may be added directly into a pipeline of
liquefaction process may require less extreme conditions to a refinery. In an exemplary embodiment, if properties of the
transfer hydrogen to vegetable oils as compared to transfer of 45 centrate and the pipeline crude oil match or nearly match, the
hydrogen to naphthalene. Consequently, it may be easier to centrate may be added directly back into the pipeline.
remove hydrogen from HVO and therefore, it may serve as a In an embodiment, coal 104 may not dissolve in the coal
better transfer agent than tetralin, for example. liquefaction mixture, and thereby make the pipeline crude oil
In an example, hydrogenation of naphthalene may require less aromatic. In an example, Some coals may be more aro
high temperature (more than 300° C.) and high pressure 50 matic and may dissolve in an aromatic solvent mixture more
(1000 psi or more). Further, the hydrogenation of naphthalene readily. For example, based on the aromaticity of the pipeline
may require a long residence time (more than 10 minutes). crude oil, the highly aromatic coal Such as bituminous coal
However, soybean oil may be hydrogenated at a pressure of may not dissolve in the coal liquefaction mixture. Further,
less than 200 psi, at a temperature less than 200° C., and a aliphatic coals such as lignite may dissolve well in an ali
residence time of 10 minutes or less. Hence, this process may 55 phatic solvent.
require less processing energy as generation of high tempera In another embodiment, if the pipeline crude oil is heavily
ture and pressure may be energy-intensive. Further, hydroge aromatic, a plasticizer may be required to reduce the pipeline
nated vegetable oils have high boiling points, thereby making crude oils viscosity. Therefore, the pipeline crude oil may
them suitable for use in processes to dissolve coal. In an flow with less resistance in the pipeline of the refinery. In a
embodiment, the hydrogenation of solvents for the liquefac 60 scenario, if the coal dissolved in the mixture is less mature,
tion process may be achieved and/or enhanced at low tem then it may be expected to produce more aliphatic or Smaller
perature and pressure by introducing hydrotreating catalysts and lighter molecules. In such a scenario, the dissolved coal
Such as cobalt-molybdenum catalyst, nickel-molybdenum may be distilled and returned to a source of the pipeline crude
catalyst, and the like. oil as Substitute plasticizers. The distillate may make trans
The mass ratio of coal to total solvents may be about 1:2.5, 65 portation of heavy pipeline crude oil economic and viable. In
1:2, or the like. In an embodiment, the mass ratio may be an embodiment, two or more feedstock solvents may be
greater. The slurry as mentioned herein may be heated at an blended together for tailoring the properties of the centrate.
 US 8,882,862 B2
11 12
Optionally, the coal liquefaction mixture may be agitated The solvent extraction need not be performed under a hydro
using ultrasound. The ultrasound technique may enable the gen atmosphere, however, a hydrogen atmosphere may
coal 104 to dissolve in the H donor solvent. As mentioned optionally be used in order to enhance the absorption of
herein, the CTD 108 may be purchased or derived from prior hydrogen.
cycles of the liquefaction process. In an example, the CTD 5
The volatile material may be sent to a flash condenser of the
108 may be formed by blending distillates from each step of reactor 102 for converting the volatile material into a con
the liquefaction process. densed material 114. The condensed material 114 may be
In an embodiment, the more recycled the CTD 108, the used as a CTD in the coal liquefaction process. Further, the
better it functions, as continuous recycling helps components condensed material 114 may be light as compared to the coal
of the CTD 108 reach a steady state. In an embodiment, the 10
extract 118. The coal extract 118 may be sent to a holding tank
composition of the liquefaction mixture may be optimized. of the reactor 102 for bringing down the temperature of the
The original source of a CTD is coal tar that may be obtained coal extract 118 to about 150°C. In an embodiment, the coal
from a coke oven. Coals that are coked are generally bitumi
nous coals. Therefore, the molecules in the CTD are typically extract 118 may be allowed to cool down with time. Alterna
from aromatic bituminous coal. In a first example, when this 15 tively, the coal extract 118 may be cooled down by using a
CTD and the bituminous coals are added, molecules may get heat transfer loop.
exchanged between the CTD and the bituminous coals result The following example is meant to illustrate an exemplary
ing in new CTD that may have the same composition. embodiment of the present disclosure, and is not intended to
In a second example, when the CTD (obtained from bitu limit the scope of the embodiments as described herein and as
minous coal) is dissolved in lignite coals, its composition may defined in the claims: Experiments were carried out with
change as the lignite coals arealiphatic compounds. When the different solvents to determine whether hydrogenation
mixture of the lignite coals and the CTD is distilled, the pitch improved the apparent solubility of coal in each solvent.
obtained may be rich in bituminous coals and the distillate Solvents tried include carbon black base oil (“CBB”, a coal
may be rich in the lignite coals. Accordingly, the recycled tar distillate obtained from Koppers), anthracene oil (AO”, a
CTD may change composition. Therefore, as the recycling of 25 coal tar distillate obtained from Reilly Industries),
the CTD is repeated, the CTD may get richer in lignite coals. Maraflex(ROil (“MO, a mixture of petroleum distillates
Finally, a steady state may be reached where the CTD may obtained from Marathon-Ashland), residual catalytic cracker
become an efficient solvent for the lignite coals. Thus, recy slurry oil (“SO”, obtained from Marathon-Ashland), and tet
cling of the CTD may change its dissolution properties. rahydronaphthalene (“tetralin').
The degree of aromaticity and the size of molecules in the 30
FIG. 4 depicts the coal conversion, in mass percent,
CTD may enable it to be used as a solvent. The CTD 108 may obtained using bituminous coal and the above-mentioned
need to have high viscosity for dispersing coal 104 within it. Solvents. The crushed coal was placed into a sealed container
High viscosity of the CTD 108 may not let the coal 104 settle along with the identified solvent at 400°C. for approximately
in the coal liquefaction mixture. The middle distillate cut one hour. Pressure within the sealed container was controlled
from the coal tars from the coke oven may provide an espe 35
cially useful CTD. by the vapor pressure of the solvent used. The coal conversion
In an embodiment, a catalyst may be added to the entire reported in the figure below is simply the fraction of coal mass
process of coal liquefaction. The catalyst may lower the pro that was converted from a solid to a liquid phase. These results
cessing temperature or pressure and may also modify prop indicate that tetralin, a known hydrogen donor solvent, is
erties of the mixture. Examples of the catalyst may include, 40 better than the other solvents in terms of coal conversion.
but are not limited to, salts of iron, molybdenum, tin, and In order to determine whether hydrogenation can enhance
FeS optionally with a hydrogen pressure. the ability to extract coal in the liquid phase, three different
In an embodiment, the temperature of the coal liquefaction hydrogenation conditions were established, as shown in Table
mixture in the reactor may be raised for condensing or flash 1.
ing out the water out of the mixture. In an embodiment, this 45
may be done by using a condenser loop. For example, the TABLE 1
temperature may be raised to about 150° C. for 200 lbs of the Solvent Hydrogenation Results
mixture so that water 112 may be removed from the mixture,
as the water 112 may become Supercritical at higher tempera Wt 9% Hydrogenation Initial Cold H2
ture and may generate pressure that may be too high for the 50 Run Description H2 absorbed reactor T. C. Pressure (psig)
reactor 102. Accordingly, the water 112 may be removed CBB Hydrogenation O.10 275 500
from the mixture before raising the temperature for avoiding Level 1
high pressure generation in the reactor 102. The water 112 CBB Hydrogenation O.14 350 500
may be removed from the mixture through multiple cycles of Level 2
CBB Hydrogenation O.24 375 750
raising the temperature and condensing out the water. Further, 55 Level 3
the water 112 may be recovered. Slurry Oil O.24 375 750
Once the water has been removed, the temperature of the Hydrogenation Level 3
Maraflex Oil O.24 375 750
mixture may be raised to about 425-450° C. in order to facili Hydrogenation Level 3
tate liquefaction. The mixture may be kept at this temperature
in the reactor 102 for about 10 minutes to an hour or longer. 60
The coal molecules may break apart at the heteroatomic link Coal extraction using these hydrogenated Solvents was
ages, and, in embodiments, form radical sites. Further, hydro performed in the same manner as described previously. As
gen released from the proton transfer agent may react with the shown in FIG. 5, coal conversion using hydrogenated Sol
mixture and seal off the radical sites of the broken linkages. vents from coal tar distillates (e.g., carbon black base oil) is
This may reduce the size of coal molecule clusters and may 65 significantly improved as compared to the use of non-hydro
form a liquid extract. The reaction mixture may be agitated, genated forms of those same solvents. In fact, the perfor
Such as by using a stirrer, an ultrasound technique, or the like. mance was similar to that of tetralin.
 US 8,882,862 B2
13 14
Subsequently, experiments with bituminous coal and CBB coal-derived solvent may be selected from a group compris
L3 produced coal conversion of 90% at 425°C. This shows ing recycled liquefied coal, coal tar distillate, and coal tar
that hydrogenation of hydrocarbon materials can produce an pitch. The hydrogenated vegetable oil may have a vapor pres
effective alternative to tetralin, a much more expensive sol sure of less than 1500 psi at temperatures less than 400
vent that generally cannot be economically incorporated into degrees Celsius. Separating may include at least one of cen
the pitch product. trifugation, filtration, decanting, and float separation. The
In an embodiment, the coal extract may be directed to a hydrogenated vegetable oil may be at least one of soybean oil,
separation process via gravity flow. Alternatively, pressure peanut oil, canola oil, olive oil, other vegetable oil or combi
may be applied to the system to drive the extract to the nation of at least two of these oils. The temperature may be
separation process. 10
elevated to between 300 degrees Celsius and 600 degrees
Further, the coal extract 118 may be subjected to a separa Celsius. The method may further include agitating the slurry
tion process to de-ash the coal extract 118. Such as centrifu to facilitate liquefying the coal. The coal may be selected
gation, filtration, decanting, float separation, or the like. The
separation process may separate insoluble material from the from one or more of a Sub-bituminous coal, lignite coal and an
anthracite coal.
extract, Such as ash and quinoline-insoluble materials. In an 15
embodiment, the coal extract 118 may be de-ashed by using a Referring to FIG. 11, a method of obtaining a de-ashed coal
centrifuge 120. The centrifuge may be a bowl centrifuge, a extract may include exposing a coal to a petroleum crude to
scroll decanter centrifuge, or the like. The scroll decanter form a slurry 1102, elevating the temperature of the slurry to
centrifuge may include a conical rotating member that may facilitate liquefying the coal and liberating a Volatile matter
strip the Solids at a given gravitational force. In the above 1104, and separating the insoluble components from the
mentioned processes, the temperature may need to be kept slurry to obtain a de-ashed coal extract, wherein the coal
low such that the viscosity may be less than 100 centipoise. In extract is suitable for downstream processing 1108. Petro
an embodiment, the extract may have a viscosity below 200 leum crude may be at least one of crude bitumen, oil sands
centipoise at an operating temperature of about 140°C. of the crude and liquids containing at least 20% of oil sands crude.
centrifuge 120. Preferably, the viscosity may be below 100 25 The de-ashed coal extract may be added to a pipeline of
centipoise (closer to 40 centipoise) at 200° C. for use in the petroleum crude for delivery to a petroleum refinery.
centrifuge 120. In an embodiment, the centrifuge 120 may Referring to FIG. 12, a method of obtaining a de-ashed coal
include a condenser (not shown) for collecting volatile mate extract may include exposing a coal to a rubber material in the
rials. presence of a coal-derived solvent to form a slurry 1202,
The centrifugation process may result in Solid ash or tails 30 elevating the temperature of the slurry to facilitate liquefying
122 and centrate 124. The tails 122 may contain about the coal and liberating a volatile matter 1204, and separating
25-35% volatile materials. These volatile materials may be the insoluble components from the slurry to obtain a de-ashed
volatiles from the coal 104 or entrained solvent. Further, the coal extract, wherein the coal extract is suitable for down
tails 122 may include about 55% ash and about 15% fixed stream processing 1208. The rubber material may be from a
carbon. As a result of the centrifugation, Some Volatile mate 35 rubber tire.
rial may be obtained, this volatile material may be baked and Referring to FIG. 13, a method of obtaining a de-ashed coal
collected (collected volatile 128) and may be added to the extract may include exposing a coal to a sewage material in
recyclable CTD. Baking the tails may produce a solid cake the presence of a coal-derived solvent to form a slurry 1302,
that may include about 85% ash and about 15% fixed carbon. elevating the temperature of the slurry to facilitate liquefying
In an embodiment, the ash may be a silicate/aluminate blend. 40 the coal and liberating a volatile matter 1304, and separating
The solid cake may be mixed with limestone to achieve a the insoluble components from the slurry to obtain a de-ashed
3:1 calcium to silicate/aluminate ratio. This configuration coal extract, wherein the coal extract is suitable for down
may then be baked in a kiln at about 1400° C. At this tem stream processing 1308.
perature, the mixture may burn off the fixed carbon and may Referring to FIG. 14, a method of obtaining a cement
produce a clinker. In an embodiment, the clinker may be 45 by-product of coal liquefaction may include exposing a coal
produced by combining clays in the ash and calcium in the to a hydrogenated vegetable oil in the presence of a coal
limestone. The clinker may thereafter be ground to make derived solvent to form a slurry 1402, elevating the tempera
Cement. ture of the slurry to facilitate liquefying the coal and liberating
In another embodiment, the ash may include metals and a volatile matter 1404, separating the insoluble components
non-metals that may be separated from the centrate 124 dur 50 from the slurry 1408, heating the insoluble components to
ing centrifugation. These separated metals and non-metals liberate a volatile matter and an entrained solvent 1410,
may be reacted during clinker formation as insoluble salts of blending the insoluble components with a calcareous material
calcium or silicates, and finally may be incorporated into the and roasting the blend in a kiln at a temperature greater than
cements. Accordingly, the present invention may not produce 1000 degrees Celsius to obtain a clinker 1412, and grinding
any solid waste after the coal 104 is reacted. Further, the waste 55 the clinker to obtain a cement 1414.
material may be used for producing a value-added product. Further, the centrate 124 may be collected and immediately
Referring to FIG. 10, a method of obtaining a de-ashed coal Subjected to a petroleum-type refining process for producing
extract includes exposing a coal to a hydrogenated vegetable transportation fuels. In an alternative embodiment, the cen
oil in the presence of a coal-derived solvent to form a slurry trate 124 may be further refined via distillation, coking, or
1002, elevating the temperature of the slurry to facilitate 60 other processes. In an embodiment, the centrate 124 may flow
liquefying the coal and liberating a volatile matter 1004, and or may otherwise be introduced to a distillation column 130
separating the insoluble components from the slurry to obtain such as a multi-tray distillation column, a Wiped Film Evapo
a de-ashed coal extract, wherein the coal extract is suitable for rator (WFE), or the like. For example, the WFE may include
downstream processing 1008. Water liberated as a result of features such as Vacuum distillation, short residence time, and
the elevated temperature may be captured and stored. Volatile 65 a highly agitated thin film offeed product on a heated Surface.
matter may be condensed and recycled. The method may These features may make the WFE suitable for handling
further include distilling the coal extract to obtain a pitch. The heat-sensitive and viscous materials.
 US 8,882,862 B2
15 16
Further, the centrate 124 may be distilled either under boiling point species removed in the solvent separation unit
vacuum or atmospheric pressure. While carrying out the dis may be optionally recycled back to be blended with the sol
tillation under atmospheric pressure, temperature may need vents used for Subsequent coal liquefaction, with or without
to be increased to distill some of the volatiles. However, at an additional hydrogenation cycle.
high temperature, other components of the distillation mix In some embodiments, distillation yields light distillates,
ture may get coked or cross-linked. Therefore, the distillation middle distillates, and heavy distillates. One use of the light
column 130 may carry out the distillation process under distillates may be to obtain transportation fuels after subse
vacuum. Since the centrate 124 contains no quinoline-in quent refining, which can be accomplished using petroleum
soluble matter or ash, it is possible to obtain a pitch after refining techniques and systems. One use of the middle dis
processing the centrate. Distilling the centrate may result in a 10
tillates may be to recycle back as a starting material in the coal
tailoring of the Softening point, a difference in coke yield, or liquefaction process. One use of the heavy distillates may be
changes in other properties. For example, in some embodi to coke them to obtain high quality cokes.
ments, distillation results in the pitch softening at about 109° In embodiments, an annealing process may take place in
C. The pitch 132 may start to coke at higher temperatures, the distillation column 130 that may alter the properties of a
such as above 400° C. 15
resultant pitch. Further, it may be evident to those skilled in
In an embodiment, the centrate 124 may be distilled to the art that annealing may only be effective in pitches that
obtain a pitch 132 similar to coal tar binder pitch. In embodi may not include quinoline insoluble material. The pitch 132
ments, the pitch 132 may be alternatively referred to as syn may include large discotic molecular clusters displaying a
thetic pitch. Further, the pitch 132 may not include any sol fused, flat or polycyclic aromatic ring structure. At low vis
vent or any insoluble material in it. cosity, the clusters flow and are attracted to other clusters by
Additionally, the distillation process may remove some of the electrons in the Pi cloud associated with each of the ring
the volatiles present in the centrate 124. In an embodiment, clusters, thus causing the aromatic rings to stack. As the
partial distillation of the centrate 124 may result in a heavy association becomes stronger, they form ordered structures,
crude-like substance that may further be refined using the and eventually, a large domain of a liquid crystal called
petroleum-type refining process. The heavy crude-like Sub 25
mesophase pitch. The mesophase pitch is denser than the
stance may be either produced directly from the distillate or parent pitch so it settles to the bottom of the distillation
by coking the pitch 132. In addition, the volatiles (that may be column. In one embodiment, upon delayed coking, this liquid
obtained from the distillation column 130) may be condensed crystal phase produces a very anisotropic coke, needle coke,
to form liquids. The condensed volatiles 134 may be used as needed for the manufacture of anisotropic graphite. Other
substitute crude or as solvent for additional executions of the 30
coal liquefaction process. In embodiments, the Volatiles may cokes may likewise be obtained.
In an embodiment, the degree of annealing may change the
be plasticizers that may be added to increase the fluidity of a degree of association between the clusters. The annealing
material. process may facilitate production of an improved pitch. Fur
The pitch 132 may be blended with other binder pitches so ther, annealing process variables may be modified to modify
that the qualities are closer to a coal tar binder pitch. In an 35
the anisotropy. In an exemplary embodiment, annealing may
embodiment, when rubber tires are used as a liquefaction be carried out at different temperatures and anisotropy may
agent, carbon black obtained from the rubber tires may be change based on the annealing. Higheranisotropic cokes with
incorporated into the pitch 132 and the resultant product may better conducting properties may be produced as a result of
be similar to the conventional coal tar pitch binders. modification in the annealing process. For example, anode
It will be evident to a person skilled in the art that binder 40
coke is only slightly anisotropic while needle coke or graphite
pitch may not be a usual product from direct coal liquefaction coke are highly anisotropic. Other process variables include:
because there is typically still quinoline-insoluble material in temperature, pressure, residence time, gas flow rate, and the
coal extract from prior art coal liquefaction processes. How like. In embodiments, the pitch 132 may facilitate production
ever, in the present disclosure, the extract 118 obtained from ofan impregnating pitch, agraphite pitch, an anode pitch, and
the reactor 102 is quinoline insoluble-free because of the 45
the like. In some embodiments, two or more feedstock sol
separation step employed in the process. For example, cen vents may be blended together to tailor the properties of the
trifugation may separate the quinoline insoluble material synthetic pitch 132. By way of example, for binder and
from the extract. In embodiments, the Residual Oil Super impregnating pitch applications, Table 2 below provides
critical Extraction (ROSE) technique may be used for de exemplary properties that may be achieved with embodi
ashing liquefied coals. 50
ments of the methods of the present disclosure.
Distillation may liberate low-boiling point species, includ
ing excess solvent (particularly any additional solvents TABLE 2
employed). A purified, synthetic pitch may be collected (e.g.,
Such as in a collection drum). This pitch may have enhanced Pitch Properties
aromaticity, increased softening point, increased cross-link 55
ing reactivity, and increased carbon coking value compared to Binder Pitch Impregnating Pitch
the pitch properties prior to distillation. Upon cooling to a Softening Pt. 100-120° C. 75-150° C.
temperature below about 110° C., the resultant pitch gener Viscosity <20 poise (a) 160° C. <50 cps (a) 225° C.
ally solidifies. The pitch thus produced can have properties Flash Pt.
Coking value (wt %)
e2OO C.
50-60
s270° C.
40-50
making it suitable for use as a binder pitch. In some embodi 60
ments, the pitch may be used either for carbon anodes for Hall
Heroult cells for aluminum Smelting, for graphite electrodes In an embodiment, the pitch may be hydrogenated, such as
for electric arc furnaces, or for other purposes. The pitch under hydrogen pressure, to produce an improved mesophase
produced in accordance with the embodiments may also be pitch upon annealing. The hydrogenated pitch is less reactive.
used for other purposes, such as, but not limited to, an impreg 65 Such improved mesophase pitches result in improved cokes,
nation pitch used to produce carbon composites, as well as Such as needle coke, with respect to the degree of anisotropy
fiber spinning pitch used to produce carbon fibers. The low upon coking.
 US 8,882,862 B2
17 18
Referring to FIG. 15, a method of obtaining a quinoline to generate heat. The centrate is transported to a distillation
insoluble-free and ash-free mesophase pitch may include column 712. Distillation results in separation of components
exposing a coal to a hydrogenated vegetable oil in the pres of the centrate based on differences in boiling points.
ence of a coal-derived solvent to form a slurry 1502, elevating Depicted here are multiple components separated from the
the temperature of the slurry to facilitate liquefying the coal centrate, including pitches, light distillates, middle distillates,
and liberating a volatile matter 1504, separating the insoluble and gases. In this embodiment, the middle distillate is
components from the slurry to obtain a de-ashed coal extract recycled 714 back into the process. Thus, the system is closed
that is quinoline insoluble-free 1508, and distilling the coal loop. Additionally, no CO is generated. Pitches may be trans
extract under vacuum to obtain a mesophase pitch with a ported to a delayed coker for coking. The centrate and/or the
softening point in the range of 25 degrees Celsius to 160 10 distillates may be transported to a petroleum refinery for
degrees Celsius, wherein the mesophase pitch can be coked to processing to fuels, such as transportation fuels or other
obtain an anisotropic coke 1510. A quinoline insoluble-free hydrocarbon products.
and ash-free pitch may be obtained by the method. The coal liquefaction process may be continuous or batch.
In an embodiment, optionally, the synthetic pitch 132 may For example, coal may be continually conveyed into the reac
be air blown. FIG. 2 illustrates a method 200 of increasing the 15 tor, the coal extract may be continuously pumped into the
average molecular weight of a pitch, in accordance with an centrifuge or may flow continuously by gravity, a continuous
embodiment of the present invention. The method 200 may use centrifuge may be used such as a scroll decanter, the
start at step 202. At step 204, the pitch may be distilled for centrate may continuously be pumped from the output of the
separating lighter and heavier molecule fractions. Further, at centrifuge to the distillation column, and the pitches may
step 208, the pitch may be air blown to cross-link the heavier continuously be siphoned off or pumped from the distillation
molecules. In embodiments, air blowing of the synthetic pitch column to a coker. Using a coated coker system described
may be used to cross-link hydrocarbons and solvent mol later herein, the coker may also be operated continuously to
ecules that may result in modifying the softening point and remove coke from the coking drum as it is formed.
increasing the coke yield. The cross-linking may facilitate an In an embodiment, the system for coal liquefaction may be
increase in the average molecular weight of the pitch as 25 located near a coal mine so that transport of the coal is mini
shown in step 210. At step 212, a potential precursor for anode mized. Alternatively, coal may be transported to the system
grade coke, needle coke, and the like may be created. The via boat, truck, rail, or the like. The coal may be pre-treated
anode grade coke may be slightly anisotropic coke and the prior to liquefaction. For example, the coal may be dried
needle coke may be highly anisotropic coke. The method 200 using a hot air furnace, microwave treatment, or the like.
terminates at 214. In an embodiment, a product produced by 30 Other pre-treatments may also be used, such as exposure to
the process includes a highly anisotropic (rod-like) coke, calcium, methanol/HCl, Swelling solvents such as ethanol,
which may be of a particular long range order or crystallinity. THF, and tetrabutyammonium hydroxide (TBAH), steam,
In embodiments, if air blowing is done prior to removing crushing, grinding, pulverization, and others.
the light fractions from the pitch 132, the resultant pitch may In an embodiment, the system for coal liquefaction may be
produce an isotropic coke that may be unsuitable for anode 35 modular and sized to be disposed in a mobile unit, Such as one
grade coke, needle coke, and the like. Further, air blowing of or more rail cars, one or more semi-truck trailers, and the like.
the pitch 132 may be performed at a temperature between For example, and referring to FIG. 18, an exploded view of a
250° C. and 450° C., 70° C. and 500° C., and the like. In an semi-truck trailer carrying the system for coal liquefaction,
example, to accomplish this, air may be bubbled through a including a distillation column, coker, and furnace, is
tube that may be inserted in a tank containing the pitch 132. In 40 depicted. It should be understood that not all embodiments of
an alternative embodiment, a sparger may be used for mixing the modular/mobile unit will include all of the components
air and the pitch 132. In embodiments, the pitch 132 may be depicted in FIG. 18. In an embodiment, a modular coal liq
further treated through various downstream processes such as uefaction system may include a reactor for exposing a coal to
hydrothermal cracking, hydrodealkylation, delayed coking, a hydrogenated vegetable oil in the presence of a coal-derived
hydrodesulphurization, Steam cracking, catalytic cracking, 45 solvent to form a slurry, a heater that elevates the temperature
and other refining techniques. of the slurry in the reactor to facilitate liquefying the coal and
Referring to FIG. 16, a method of obtaining a high quality liberating a volatile matter, and a centrifuge that separates the
coke from a low rank coal extract may include exposing a coal insoluble components from the slurry to obtain a de-ashed
to a hydrogenated vegetable oil in the presence of a coal coal extract, wherein the coal extract is suitable for down
derived solvent to form a slurry 1602, elevating the tempera 50 stream processing, wherein the reactor, heater, and centrifuge
ture of the slurry to facilitate liquefying the coal and liberating are adapted to be modular. The system may further include a
a volatile matter 1604, separating the insoluble components distillation column that distills the de-ashed coal extract to
from the slurry to obtain a de-ashed coal extract that is quino obtain a pitch. The system may further include a coker that
line insoluble-free 1608, distilling the coal extract under cokes at least one of the de-ashed coal extract and the pitch to
vacuum to obtain a pitch with a suitable softening point 1610, 55 obtain a coke. The system may be adapted to be modularly
and coking the pitch to obtain a coke 1612. The coke may be disposed on a rail car. The system may be adapted to be
at least one of an anisotropic coke, a metallurgical coke, a modularly disposed on a semi-truck trailer. In another
graphite coke, an anode coke, and a needle coke. The method embodiment, a modular coal liquefaction system may include
may further include air blowing the pitch to crosslink mol a reactor for exposing a coal to a hydrogenated vegetable oil
ecules in the pitch, the air blowing of synthetic pitch used for 60 in the presence of a coal-derived solvent to form a slurry, a
at least modifying a softening point and increasing cokeyield. heater that elevates the temperature of the slurry in the reactor
Referring to FIG.7, an embodiment of the coal liquefaction to facilitate liquefying the coal and liberating a volatile mat
system is depicted. A hydrogen donor solvent 702 is mixed ter, a centrifuge that separates the insoluble components from
with coal and is transported to a reactor 704 for liquefaction. the slurry to obtain a de-ashed coal extract, wherein the coal
After liquefaction, the coal is either pumped or flows by 65 extract is suitable for downstream processing, a distillation
gravity to a centrifuge 708. One product from centrifugation column that distills the de-ashed coal extract to obtain a pitch,
may be gasifier fuel, which may be utilized 710 in the process and a coker that cokes at least one of the de-ashed coal extract
 US 8,882,862 B2
19 20
and the pitch to obtain a coke, wherein the coker comprises a These non-caking coals are referred to as coal that may char
coated coking drum that receives the de-ashed coal extract or and may not agglomerate to produce coke.
the pitch, wherein the coking drum is coated with a coating In embodiments, the coke 140 may not be crystalline:
comprising at least one of a chromium, an aluminum, a however, the coke 140 may have long-range order of posi
nickel, or an alloy thereof, wherein the reactor, heater, cen tioning of molecules. In an example, graphite is anisotropic as
trifuge, distillation column, and coker are adapted to be opposed to a cube, which is isotropic.
modular. The system may be adapted to be modularly dis The degree of the long-range order may modify the
posed on a rail car. The system may be adapted to be modu reflected light. The more anisotropic the coke is, the more
larly disposed on a semi-truck trailer. rod-like it is. For example, graphite may be hexagonal on one
The pitch 132 obtained from the distillation column 130 10 side and may be needle like on another side. In embodiments,
may be pumped directly into a coke producing device 138 anisotropy of the coke 140 may be proportional to the value of
Such as a coker, a coke battery oven, and the like at a given the coke 140. Referring to graphite, carbon molecules in the
temperature to instantaneously turn the pitch 132 into coke. graphite may arrange themselves into a lattice structure,
This process may also be known as delayed coking. Delayed which may allow free movement of electrons, thereby making
coking may use lower temperatures and a longer residence 15 graphite a good conductor.
time than traditional coking and may produce both solid In embodiments, the pitch 132 may be used for preparing
cokes as well as liquid or gaseous material. isotropic coke. The isotropic coke may be ground to make
In an embodiment, the pitch 132 may be coked or delay isotropic graphite (also referred to as nuclear graphite). As a
coked in a coke battery oven (hereinafter referred to as coke bulk property, the nuclear graphite may be isotropic and may
oven). Coking may drive off volatile gases. Further, the not contain any ash.
chemical function of the pitch 132 may change as a function In an embodiment, the coal 104 and the pitch 132 may be
of time. In embodiments, various parameters of the coker 138 admixed in the coker 138 for delayed coking or may be mixed
may be varied as per the requirement. Examples of the param with petroleum resids.
eters may include, but are not limited to, ramp rate, pressure, In embodiments, the tails 124 obtained from the centrifu
temperature, gases added in Steam, addition of nitrogen, addi 25 gation process may include mineral matter that may be
tion of air, and the like. insoluble. The tails 124 may either be clinkered for conver
For example, during the process, the pressure within the sion into cement or the tails 124 containing the mineral matter
coker 138 may be increased above 50 lbs (the pressure that is may be heated in the presence of air to a temperature exceed
generally used for coking) to change the bulk density of the ing 1000°C. The heat treatment may completely oxidize and
pitch 132. Further, the pitch 132 may be treated at higher 30 melt the mineral matter present in the tails 124 and may form
temperatures such as between 400° C. and 600° C. At such a slag.
higher temperatures, lighter molecules may be liberated from Conventionally, a method for removing sulfur from sulfur
the pitch 132 in the form of gas or condensable vapors. Once containing hydrocarbon liquids such as crude petroleum or
the gases are released from the pitch 132, a solid non-melting coal extract may be described as hydrodesulfurization. This
residue may be obtained. In some embodiments, the residue 35 process may involve exposing the hydrocarbon liquid to a
may mostly contain carbon and may be referred to as green high temperature pressurized hydrogen gas in the presence of
coke. When the pitch 132 is baked at 500° C., discotic mol a catalyst. The result may be the formation of hydrogen Sul
ecules may enable formation of coke as stacked crystals. In fide, which may be removed by dissolving the hydrogen
embodiments, different types of binder pitches may result in Sulfide in water. In embodiments, the present invention may
formation of cokes of different properties. 40 provide a method for producing reduced sulfur hydrocarbon
The coke may contain aromatic hydrocarbons and may liquids. The present disclosure describes the use of a hydro
become more anisotropic upon heating, Such as at a tempera genated liquid such as HVO for removing sulfur from crude
ture of 1000°C.-1400° C. to produce calcined coke, such as petroleum liquids. The HVO may be placed in a reactor and
anode grade coke, needlegrade coke, and metallurgical coke. mixed with the crude petroleum liquids. Further, this blend
Calcination of green coke may reduce the overall weight by 45 may be heated at about 400° C.
about 5%, but at the same time it may make the coke stronger. In embodiments, the reactor is typically not pressurized
In embodiments, gases that may be removed during calcina with a gas. However, the vapor pressure of constituents in the
tion may include about 85% hydrogen gas. blend may result in raising the reactor pressure to about 1000
Coke calcining is a process wherein the coke may be ther psig. As a result, Sulfur from the crude petroleum liquids may
mally upgraded to remove associated moisture and volatile 50 react with HVO to form hydrogen sulfide, which may be
combustion matter (VCM). The calcining process may also removed as a vapor, leaving behind a blend of hydrocarbons
improve critical physical properties, such as electrical con with low sulfur content. The resultant blend of vegetable oil
ductivity, real density, oxidation characteristics, and the like. and petroleum may be further refined with conventional refin
Further, the calcining process may be a time-temperature ing processes.
function with control variables such as heating rate, VCM/air 55 In an exemplary embodiment, graphite may be formed
ratio, calcination temperature, and the like. To obtain the from the coke 140 and the pitch 132. The coke 140 and the
calcined coke properties required by the carbon and graphite pitch 132 may be extruded through holes of an oven along
industries, the coke 140 may be subjected to temperatures of with highly viscous material to enable formation of an elec
1000°C.-1400° C. to refine its crystalline structure. The final trode. The electrode may be treated with gas that may be
quality of the calcined coke may be directly related to the 60 passed through channels for again forming coke. This coke
specific characteristics and quality of the coke fed to the coker may be mixed with impregnation pitch and may be impreg
or calciner. nated into the holes of the electrode. The impregnation may
However, the Supply of good quality coking coal is declin take place under application of pressure. Further, the oven
ing, so much so that coking coals or metallurgical coals may may bake the blend of coke and the impregnation pitch. The
be mined from seams as low as 28 inches. The present inven 65 resulting product may be taken through the same procedure,
tion may enable coking of non-caking coals such as Sub until a required density of the resulting product may be
bituminous and lignite coals, whose availability is immense. achieved. Such a product may be referred to as greenware.
 US 8,882,862 B2
21 22
Further, electrodes may be added to the greenware and it may In embodiments, the coal 104 may be optionally dried prior
be heated to about 2800° C. The heating may facilitate order to the preparation of slurry. Pre-drying the coal 104 may
ing of the discotic molecules to obtain graphite. result in enhanced solubility of the coal 104. In an embodi
In embodiments, the mesophase pitch may be extruded and ment, the coal 104 may be pre-dried by using the waste heat
graphitized by heat treatment, which may result in the forma of the reactor 102. In another embodiment, the coal 104 may
tion of carbon fibers similar to human hair in dimension. The be passed through a pre-drying Zone for removing moisture
heat-treated mesophase-pitch-derived carbon fibers may have content of the coal 104 prior to its addition to the slurry.
high Young's modulus and high thermal conductivity. In an Pre-drying may include microwave treatment.
embodiment, the mesophase pitch may have high Surface In embodiments, the solvent that may be used as the addi
tension that may enable the mesophase pitch to Stick to itself 10 tive 110 may or may not be hydrogenated. For example, the
and thus, may differentiate it from the binder pitch. HVO, when used as a solvent, is already hydrogenated; how
In embodiments, only 40% of crude oil may include ingre ever, other feedstock solvents, which may not be hydroge
dients that may be useful for the production of high-quality nated, may also be used as the additive 110. The feedstock
fuels. The remaining components of crude oil may be heavy, Solvents may include a hydrocarbon material that may have a
poor performing fuels. These heavy fuels may be converted to 15 softening temperature of less than about 200° C. and may
usable transportation fuels through cracking. In an example, contain at least 10% hydrocarbon species having a boiling
hydrogenated vegetable oil and crude oil may be treated at point of over 350° C. When a non-hydrogenated solvent is
high pressure and temperature in the presence of a catalyst. used as the additive 110 in the slurry, the solvent may be
The high pressure and high temperature may facilitate hydro heated to a temperature of between 200° C. and about 500° C.
gen from the HVO to be combined with the crude oil. The in a hydrogen atmosphere. Further, a hydrogen pressure of up
combined influences of the catalyst, pressure, and heat may to about 3000 psig may be applied such that the solvent of the
cause the hydrogen and the hydrocarbon molecules to split. extraction mixture has absorbed hydrogen content (by
The hydrogen atoms may immediately combine with the weight) between 0.1% and 10%.
hydrocarbons and form a light oil. Accordingly, hydrogena FIG. 3 illustrates a block flow diagram of a processing
tion may enable recovery of gasoline from the crude oil. 25 system 300 that may be used to produce pitch, in accordance
The ingredients of the carbon-based fuel type materials with an embodiment of the present disclosure. The processing
may be classified by solubility fractions. For example, oils system 300 may include a tank reactor 302. Hydrogen gas
may be known as that portion of the fluid that may be soluble may be used to hydrogenate a portion of the feedstock sol
in cyclohexane. Asphaltene are those materials that may be vent. Optionally, a catalyst, such as, but not limited to, iron,
insoluble in cyclohexane, but may be soluble in tetrahydro 30 cobalt, nickel, molybdenum, tin, Salts of the foregoing metals,
furan. Further, pre-asphaltenes are materials that may be or mixtures of any of the foregoing, may also be added to the
insoluble in both hexane and tetrahydrofuran. Likewise, tank reactor 302 to enhance the absorption of hydrogen by the
pitches may be classified based on their solubility. In an feedstock solvent. Further, the feedstock solvent may be
example, toluene soluble pitches may be light. Quinoline hydrogenated Such that mass of the feedstock solvent may be
insoluble pitches may prevent formation of mesophase. 35 increased by up to several percent due to the absorption of
These pitches may include fixed carbon or carbon black addi hydrogen.
tives. After hydrogenation of at least a portion of the feedstock
In embodiments, coal liquids may be blended with 10-95% solvent, the hydrogenated solvent may be combined with one
alcohol to create a motor fuel with high octane rating and or more un-hydrogenated feedstock solvents, and/or one or
compatible combustion kinetics. Further, coal liquids are 40 more additional solvents (e.g., tetralin). The solvent that has
highly soluble in alcohol. Moreover, the high energy density been removed from the pitch 132 may be blended with the
of coal liquids may act to increase the energy density of the feedstock solvent prior to being added to a second tank reac
blend. The aromatic content of coal liquids may enable the tor in which the extraction takes place. This solvent recycle
blend to be compatible with polymer seals. In addition, stream may include not only solvent (feedstock and addi
although the coal liquids are inherently slow burning, they are 45 tional solvent) and solvent fractions removed from the pitch,
combusted more rapidly in the presence of a combusting but also other light hydrocarbons extracted from the coal 104.
alcohol. Hence, the combination of coal liquids and ethanol As used herein, “light hydrocarbons' may refer to materials
may be favorable as compared to either component used in its having a boiling point lower than about 200°C., making them
pure state or blended with gasoline. Therefore, CE-85, which difficult to incorporate into the pitch 132 intended to with
may include 85% ethanol and 15% coal liquids, may be 50 stand de-volatilization until over 350° C. Recycling of a por
sought as non-petroleum derived motor fuel. tion of the solvent may permit dissolution of additional quan
In embodiments, Fischer-Tropsch liquids may be used in tities of the coal 104. Alternatively, the portion of solvent
place of the alcohol, while direct-liquefied coal liquids may removed from the pitch 132 may be considered a separate
be used as blending agents. For example, Fischer-TropSch product (e.g., for use as an octane enhancer).
liquids may be blended with coal liquids, including petroleum 55 Further, after hydrogenation, the feedstock solvent,
derivatives optionally. The Fischer-Tropsch process may optional additional solvent, and recycled solvent may be
facilitate reaction of methane or gasified coal with air in the transferred to a tank reactor 304 and may be combined with
presence of a catalyst to create synthesis gas, which may be a coal 104 (or other solids-containing material) to be extracted.
mixture of carbon monoxide and hydrogen. Using another The tank reactor 304 may be operated at ambient pressure.
catalyst, the synthesis gas may then be converted to a mixture 60 The extracts obtained from the tank reactor 304 may be intro
of liquid hydrocarbons. The second catalyst may be an iron or duced to the centrifuge 120. The centrifugation and further
cobalt-based commercial catalyst. The present disclosure distillation of centrate through the distillation column 130 has
may not involve the production of synthesis gas or conversion been explained earlier and is not explained again for the sake
of synthesis to liquids, but instead may involve production of of brevity.
coal liquids via mild direct liquefaction that may then be 65 Generally, a coker may be made up of a steel material. Coke
blended with Fischer-Tropsch liquids to produce a substitute may stick to the sides of the coker and may be removed by
kerosene or jet fuel. scraping off the deposits using water knives or other means.
 US 8,882,862 B2
23 24
In embodiments, the coker may be coated with chrome to CTD, the kind of coal used to generate the CTD, inclusion of
facilitate removal of coke. The chrome coating may be ero catalysts, inclusion of hydrogen gas, inclusion of additional
sion resistant and may be capable of withstanding heavy solvents or blends of hydrogen donor solvents, and the like.
residual deposits. In case of a chrome coating, the coke may Variables related to the reactor include temperature, agitation,
be pushed out using a plunger, a piston, and the like. Further, ultrasound, residence time, continuous processing, batch pro
an auger may be built into coker that may enable transporting cessing, and the like. In the separation process, the speed of
the coke to the upper portions of the coker. Additionally, a separation, duration, and the Viscosity of the slurry may all be
coating of aluminum or nickel may be used instead of chrome altered to yield modified tails and/or modified centrate. Refer
as coke does not dissolve in aluminum or nickel. ring to FIG. 8, in the distillation process, any of temperature,
In embodiments, the coker may be coated with materials 10 pressure, residence time, sparger use, air blowing, and gas
Such as chrome, aluminum, aluminum alloys, and nickel flow rate may be varied to modify the distillation output,
alloys. In an example, the coker may be configured with a gear which can be any of gases, middle distillate, light distillate,
in the center for removing the coke. In another example, the pitches (e.g. binder-type pitch, impregnation pitch, graphite
coker may be configured with a hydraulic aim or plunger for pitch, mesophase pitch, other pitches), and the like. The type
facilitating removal of the coke. The gear and the plunger may 15 of pitch obtained depends on the process variables and the
also be coated with any of the materials mentioned above. In coal extract, such as the kind of coal used to generate the
yet another example, the coker may include an Archimedean extract, the ash content, the solvents used to liquefy the coal,
spiral-based screw (also referred to as an Archimedes' screw) and the like. Referring to FIG.9, cokeyields and types may be
that may be used for drawing out coke from a reservoir of varied by changes in pressure, temperature, ramp rate, air
pitch. The coke may then be sent to a calciner. Further, in case blowing, residence time, coating of the coker, type of coke
of a continuous coker, the Archimedes' screw may be used for oven used (e.g. delayed coker, fluid coker, Flexicoker, bee
continuously providing coke. hive oven, coke battery), and changes in starting pitch mate
Further, the coated coker may be configured in a smaller rial, such as use of the any of the pitches described above in
size than other commercially available cokers. Accordingly, reference to FIG. 8. Depending in the input pitch and the
the coated cokers may facilitate mobilization of coal lique 25 process variables, possible coke outputs include graphite
faction plants. In embodiments, the mobile cokers may be coke, needle coke, anode coke, anisotropic coke, isotropic
implemented on one or more trucks or trailers or one or a coke, shot coke, sponge coke, calcined coke, catalyst coke,
series of rail cars, or the like. fuel grade coke, and green coke.
In embodiments, odor may be produced in the reactor 102 The entire process may be controlled by a computer. The
due to presence of toxic gases such as hydrogen Sulfide, 30 system may include sensors and sensor feedback control to
methylmercaptan, and mercaptan. The reactor 102 may facilitate quality control and measurements. For example,
include a column for mixing alkalis such as NaOH for miti sensors may be used to measure the viscosity and temperature
gating the odor. The alkali column may include Raschig rings of the coal extract. When the sensor determines the viscosity
that may be Supported on a porous bed. The porous bed may and temperature are suitable for separation, the sensors may
provide more surface area to the alkali column. Further, a 35 send a signal to a processor that controls a valve or a pump
showerhead may be configured at a top portion of the alkali that facilitates transport of the coal extract from the reactor or
column to be connected to the alkali reservoir. In an example, holding tank to a separation unit, such as a centrifuge. In
the reservoir may supply NaOH to the showerhead for being another example, sensors may be used to control transport of
shot inside the column. Further, the reservoir may supply coal to the reactor, transport of the centrate to the distillation
NaOH to the alkali column through a pump. The pump may 40 column, transport of volatiles captured throughout the system
allow the NaOH to flow from the reservoir to the showerhead. to a tank, transport of pitches distilled to a coker, and the like.
Further, a pipe for ejecting the odor producing gases into the Sensors may be used to measure the properties of the products
coker may be configured near a bottom Surface of the column. of the process. Sensors may be used to provide real time
In use, the odor producing gases (hydrogen Sulfide and feedback during processing in order for an operator of the
mercaptan) flowing upwards may come in contact with the 45 system to make manual adjustments or for a processor to
NaOH flowing downwards. When NaOH and the gases meet, make an automatic adjustment. Sensors may be used for
hydrogen Sulfide and mercaptain may become salts and may safety purposes.
get captured in a solution. This conversion may continue until The methods and systems described herein may be
the solution may either be used in the process itselfor may be deployed in part or in whole through a machine that executes
discarded later. 50 computer Software, program codes, and/or instructions on a
Although the present disclosure has been described in con processor. The processor may be part of a server, client,
junction with the production of liquid fuels and cokes in a network infrastructure, mobile computing platform, station
delayed coker, other methods and systems may be possible to ary computing platform, or other computing platform. A pro
carry out the present disclosure without limiting the spirit and cessor may be any kind of computational or processing device
Scope of the present invention. 55 capable of executing program instructions, codes, binary
The conditions of the process may change with choice of instructions and the like. The processor may be or include a
coal to liquefy and desired endpoint. For example, and refer signal processor, digital processor, embedded processor,
ring to FIG. 6, various coals may be liquefied by the process, microprocessor or any variant Such as a co-processor (math
Such as regional coal types, dried coal, pulverized coal, co-processor, graphic co-processor, communication co-pro
microwaved coal, ground coal, bituminous, Subbituminous, 60 cessor and the like) and the like that may directly or indirectly
anthracite, lignite, brown coal, and the like. Such coals may facilitate execution of program code or program instructions
vary in size, water content, aromatic content, pre-treatment, stored thereon. In addition, the processor may enable execu
cleaning, drying, and the like. Thus, certain process changes tion of multiple programs, threads, and codes. The threads
may be made to accommodate the different coal types, may be executed simultaneously to enhance the performance
including the kind of hydrogen donor Solvent used, amount of 65 of the processor and to facilitate simultaneous operations of
hydrogenation of the hydrogen donor solvent, increased the application. By way of implementation, methods, pro
hydrogenated material content, the amount of recycling of the gram codes, program instructions and the like described
 US 8,882,862 B2
25 26
herein may be implemented in one or more thread. The thread The client may provide an interface to other devices includ
may spawn other threads that may have assigned priorities ing, without limitation, servers, other clients, printers, data
associated with them; the processor may execute these base servers, print servers, file servers, communication serv
threads based on priority or any other order based on instruc ers, distributed servers and the like. Additionally, this
tions provided in the program code. The processor may coupling and/or connection may facilitate remote execution
include memory that stores methods, codes, instructions and of program across the network. The networking of some orall
programs as described herein and elsewhere. The processor of these devices may facilitate parallel processing of a pro
may access a storage medium through an interface that may gram or method at one or more location without deviating
store methods, codes, and instructions as described herein from the scope of the invention. In addition, any of the devices
and elsewhere. The storage medium associated with the pro 10 attached to the client through an interface may include at least
cessor for storing methods, programs, codes, program one storage medium capable of storing methods, programs,
instructions or other type of instructions capable of being applications, code and/or instructions. A central repository
executed by the computing or processing device may include may provide program instructions to be executed on different
but may not be limited to one or more of a CD-ROM, DVD, devices. In this implementation, the remote repository may
memory, hard disk, flash drive, RAM, ROM, cache and the 15 act as a storage medium for program code, instructions, and
like. programs.
A processor may include one or more cores that may The methods and systems described herein may be
enhance speed and performance of a multiprocessor. In deployed in part or in whole through network infrastructures.
embodiments, the process may be a dual core processor, quad The network infrastructure may include elements such as
core processors, other chip-level multiprocessor and the like computing devices, servers, routers, hubs, firewalls, clients,
that combine two or more independent cores (called a die). personal computers, communication devices, routing devices
The methods and systems described herein may be and other active and passive devices, modules and/or compo
deployed in part or in whole through a machine that executes nents as known in the art. The computing and/or non-com
computer Software on a server, client, firewall, gateway, hub, puting device(s) associated with the network infrastructure
router, or other Such computer and/or networking hardware. 25 may include, apart from other components, a storage medium
The Software program may be associated with a server that such as flash memory, buffer, stack, RAM, ROM and the like.
may include a file server, print server, domain server, internet The processes, methods, program codes, instructions
server, intranet server and other variants such as secondary described herein and elsewhere may be executed by one or
server, host server, distributed server and the like. The server more of the network infrastructural elements.
may include one or more of memories, processors, computer 30 The methods, program codes, and instructions described
readable media, Storage media, ports (physical and virtual), herein and elsewhere may be implemented on a cellular net
communication devices, and interfaces capable of accessing work having multiple cells. The cellular network may either
other servers, clients, machines, and devices through a wired be frequency division multiple access (FDMA) network or
or a wireless medium, and the like. The methods, programs or code division multiple access (CDMA) network. The cellular
codes as described herein and elsewhere may be executed by 35 network may include mobile devices, cell sites, base stations,
the server. In addition, other devices required for execution of repeaters, antennas, towers, and the like. The cell network
methods as described in this application may be considered as may be a GSM, GPRS, 3G, EVDO, mesh, or other networks
a part of the infrastructure associated with the server. types.
The server may provide an interface to other devices The methods, programs codes, and instructions described
including, without limitation, clients, other servers, printers, 40 herein and elsewhere may be implemented on or through
database servers, print servers, file servers, communication mobile devices. The mobile devices may include navigation
servers, distributed servers, social networks, and the like. devices, cell phones, mobile phones, mobile personal digital
Additionally, this coupling and/or connection may facilitate assistants, laptops, palmtops, netbooks, pagers, electronic
remote execution of program across the network. The net books readers, music players and the like. These devices may
working of some or all of these devices may facilitate parallel 45 include, apart from other components, a storage medium Such
processing of a program or method at one or more location as a flash memory, buffer, RAM, ROM and one or more
without deviating from the scope of the invention. In addition, computing devices. The computing devices associated with
any of the devices attached to the server through an interface mobile devices may be enabled to execute program codes,
may include at least one storage medium capable of storing methods, and instructions stored thereon. Alternatively, the
methods, programs, code and/or instructions. A central 50 mobile devices may be configured to execute instructions in
repository may provide program instructions to be executed collaboration with other devices. The mobile devices may
on different devices. In this implementation, the remote communicate with base stations interfaced with servers and
repository may act as a storage medium for program code, configured to execute program codes. The mobile devices
instructions, and programs. may communicate on a peer to peer network, mesh network,
The Software program may be associated with a client that 55 or other communications network. The program code may be
may include a file client, print client, domain client, internet stored on the storage medium associated with the server and
client, intranet client and other variants such as secondary executed by a computing device embedded within the server.
client, host client, distributed client and the like. The client The base station may include a computing device and a stor
may include one or more of memories, processors, computer age medium. The storage device may store program codes
readable media, Storage media, ports (physical and virtual), 60 and instructions executed by the computing devices associ
communication devices, and interfaces capable of accessing ated with the base station.
other clients, servers, machines, and devices through a wired The computer Software, program codes, and/or instruc
or a wireless medium, and the like. The methods, programs or tions may be stored and/or accessed on machine readable
codes as described herein and elsewhere may be executed by media that may include: computer components, devices, and
the client. In addition, other devices required for execution of 65 recording media that retain digital data used for computing
methods as described in this application may be considered as for some interval of time; semiconductor storage known as
a part of the infrastructure associated with the client. random access memory (RAM); mass storage typically for
 US 8,882,862 B2
27 28
more permanent storage, such as optical discs, forms of mag gate array, programmable array logic, or any other device or
netic storage like hard disks, tapes, drums, cards and other combination of devices that may be configured to process
types; processor registers, cache memory, Volatile memory, electronic signals. It will further be appreciated that one or
non-volatile memory; optical storage such as CD, DVD: more of the processes may be realized as a computer execut
removable media such as flash memory (e.g. USB sticks or able code capable of being executed on a machine readable
keys), floppy disks, magnetic tape, paper tape, punch cards, medium.
standalone RAM disks, Zip drives, removable mass storage, The computer executable code may be created using a
off-line, and the like; other computer memory Such as structured programming language such as C, an object ori
dynamic memory, static memory, read/write storage, mutable ented programming language Such as C++, or any other high
storage, read only, random access, sequential access, location 10 level or low-level programming language (including assem
addressable, file addressable, content addressable, network bly languages, hardware description languages, and database
attached storage, storage area network, bar codes, magnetic programming languages and technologies) that may be
ink, and the like. stored, compiled or interpreted to run on one of the above
The methods and systems described herein may transform devices, as well as heterogeneous combinations of proces
physical and/or or intangible items from one state to another. 15 sors, processor architectures, or combinations of different
The methods and systems described herein may also trans hardware and Software, or any other machine capable of
form data representing physical and/or intangible items from executing program instructions.
one state to another. Thus, in one aspect, each method described above and
The elements described and depicted herein, including in combinations thereof may be embodied in computer execut
flow charts and block diagrams throughout the figures, imply able code that, when executing on one or more computing
logical boundaries between the elements. However, accord devices, performs the steps thereof. In another aspect, the
ing to software or hardware engineering practices, the methods may be embodied in Systems that perform the steps
depicted elements and the functions thereof may be imple thereof, and may be distributed across devices in a number of
mented on machines through computer executable media ways, or all of the functionality may be integrated into a
having a processor capable of executing program instructions 25 dedicated, standalone device or other hardware. In another
stored thereon as a monolithic Software structure, as standa aspect, the means for performing the steps associated with the
lone software modules, or as modules that employ external processes described above may include any of the hardware
routines, code, services, and so forth, or any combination of and/or software described above. All such permutations and
these, and all Such implementations may be within the scope combinations are intended to fall within the scope of the
of the present disclosure. Examples of Such machines may 30 present disclosure.
include, but may not be limited to, personal digital assistants, While the invention has been disclosed in connection with
laptops, personal computers, mobile phones, other handheld the preferred embodiments shown and described in detail,
computing devices, medical equipment, wired or wireless various modifications and improvements thereon will
communication devices, transducers, chips, calculators, sat become readily apparent to those skilled in the art. Accord
ellites, tablet PCs, electronic books, gadgets, electronic 35 ingly, the spirit and Scope of the present invention is not to be
devices, devices having artificial intelligence, computing limited by the foregoing examples, but is to be understood in
devices, networking equipments, servers, routers and the like. the broadest sense allowable by law.
Furthermore, the elements depicted in the flow chart and All documents cited herein are hereby incorporated by
block diagrams or any other logical component may be imple reference.
mented on a machine capable of executing program instruc 40
tions. Thus, while the foregoing drawings and descriptions set What is claimed is:
forth functional aspects of the disclosed systems, no particu 1. A method of obtaining a quinoline insoluble-free and
lar arrangement of Software for implementing these func ash-free mesophase pitch, comprising:
tional aspects should be inferred from these descriptions exposing a coal to a hydrogenated vegetable oil in the
unless explicitly stated or otherwise clear from the context. 45 presence of a coal-derived solvent to form a slurry;
Similarly, it will be appreciated that the various steps identi elevating the temperature of the slurry to facilitate lique
fied and described above may be varied, and that the order of fying the coal and liberating a volatile matter,
steps may be adapted to particular applications of the tech separating the insoluble components from the slurry to
niques disclosed herein. All Such variations and modifications obtain a de-ashed coal extract that is quinoline
are intended to fall within the scope of this disclosure. As 50 insoluble-free; and
Such, the depiction and/or description of an order for various distilling the coal extract under vacuum to obtain a
steps should not be understood to require a particular order of mesophase pitch with a softening point in the range of 25
execution for those steps, unless required by a particular degrees Celsius to 160 degrees Celsius, wherein the
application, or explicitly stated or otherwise clear from the mesophase pitch can be coked to obtain an anisotropic
COInteXt. 55 coke.
The methods and/or processes described above, and steps 2. The method of claim 1, further comprising hydrogenat
thereof, may be realized in hardware, Software or any com ing the coal extract before distilling.
bination of hardware and software suitable for a particular 3. The method of claim 1, wherein water liberated as a
application. The hardware may include a general purpose result of the elevated temperature is captured and stored.
computer and/or dedicated computing device or specific 60 4. The method of claim 1, wherein the volatile matter is
computing device or particular aspect or component of a condensed and recycled.
specific computing device. The processes may be realized in 5. The method of claim 1, wherein separating comprises at
one or more microprocessors, microcontrollers, embedded least one of centrifugation, filtration, decanting, and float
microcontrollers, programmable digital signal processors or separation.
other programmable device, along with internal and/or exter 65 6. The method of claim 1, wherein the temperature is
nal memory. The processes may also, or instead, be embodied elevated to between 300 degrees Celsius and 600 degrees
in an application specific integrated circuit, a programmable Celsius.
 US 8,882,862 B2
29 30
7. The method of claim 1, further comprising agitating the
slurry to facilitate liquefying the coal.
8. The method of claim 1, wherein the coal is selected from
one or more of a Sub-bituminous coal, a bituminous coal, a
lignite coal, and an anthracite coal. 5
9. The method of claim 1, further comprising air blowing
the pitch to cross-link the heavier molecules in the pitch and
modify the softening point to increase the coke yield.
10. The method of claim 1, wherein the coal-derived sol
vent comprises at least one of recycled liquefied coal, coal tar 10
distillate, and coal tar pitch.
k k k k k