United States Patent (19) 11 Patent Number: 4,701,183

Riley et al. (45. Date of Patent: Oct. 20, 1987

(54) PROCESS FOR REMOVING SULFUR FROM 4,047,898 9/1977 Cole et al. .......................... 44/1 SR
COAL 4,054,421 10/1977 Robinson et al. .................. 44/1 SR
(76) Inventors: John T. Riley, 1511 Woodhurst Dr., 4,260,471 4/1981 Miller ................. ... 44/1 SR
4,400, 176 8/1983 Kutta .................................... 44/1 R
Bowling Green, Ky. 42101; Dwight 4,424,062 1/1984 Kamino et al. ..................... 44/1 SR
D. Watson, 5408 Apple La., West
Deptford, N.J. 08066
Primary Examiner-Carl F. Dees
(21) Appl. No.: 776,467 Attorney, Agent, or Firm-Jon C. Winger
22 Filed: Sep. 16, 1985
51 - - - - - - - - - C10L 9/06
(57) ABSTRACT
52) a 40 44/1 SR; 201/17 A process for removing sulfur from coal comprising the
58) Field of Search ................. 44/1 SR, 1 R, 201/17; steps of forming a slurry of coal, a carrier liquid, and a
423/461 compound selected from the group consisting of car
(56) References Cited boxylic acid, percarboxylic acid, salts of carboxylic
U.S. PATENT DOCUMENTS acid, and salts of percarboxylic acid, and any combina
tion thereof.
3,214,346 10/1965 Mason et al. ......................... 201/17
3,393,978 7/1968 Murphy et al........................ 201/17 8 Claims, No Drawings
 1
4,701, 183
2
PROCESS FORREMOVING SULFUR FROM COAL
ent and 350 degrees Celsius would be effective in re
moving sulfur. Air is used to oxidize the sulfur and aid
BACKGROUND OF THE INVENTION in its removal. The use of pure oxygen seems to enhance
this reaction without degrading the coal. Of the carbox
1. Field of the Invention ylic acids and their salts, formic acid and formate salts
The invention relates to desulfurizing coal, and more appear to perform best in the removal of organic sulfur,
particularly to a process for removing sulfate, pyritic whereas iso-valeric acid and iso-valerate salts are effec
and especially organic sulfur from coal. tive in removing pyritic sulfur. It is anticipated that
2. Discussion of Prior Art other carboxylic acids, their salts, and combinations of
There are three forms of sulfur in coal, pyritic, or 10
carboxylic acids and their salts would be effective in the
ganic, and sulfate sulfur. Typically, the pyritic and or removal of sulfur from coal and coal-derived products.
ganic sulfur contents are about the same in most Illinois Polycarboxylic acids such as nitrilotriacetic acid and
Basin coals, while the sulfate sulfur content in most ethylenediaminetetraacetic acid and their salts would
coals is very low. Present day commercial coal washing also be effective in the removal of sulfur.
operations involve a separation of sulfur containing 15
A systematic study of the removal of sulfur using
minerals as a function of their density. Inorganic sulfur various carboxylic acids and carboxylic acid salts was
compounds, mostly pyrites and marcasite, are more
dense than the organic materials in coal. The density of carried out. The pH of the reaction mixture was also
a washing medium is adjusted so that the organic por varied. Various acids and salts were effective in remov
tion floats and the mineral components containing py 20 ing the sulfur and a portion of the mineral matter from
rite and marcasite sink to the bottom of the washing cell -8 mesh (2.4 mm) coal.
and are moved. This removes a portion of the pyritic DETAILED DESCRIPTION OF THE
sulfur, some of the sulfate sulfur and very, very little of PREFERRED EMBODIMENT
the organic sulfur in coal.
A chemical cleaning process is needed to remove the 25 Various tests were conducted as follows:
organic sulfur from coal. Several methods of chemical Materials
cleaning of coal have been investigated. The Ledge
mont Oxygen Leaching (LOL) Process uses 10-20 atm All reagents used were of reagent grade. All reaction
partial pressure oxygen, 130 degrees Celsius for 2 hours mixtures were prepared with water that had been deion
to remove up to 90% of the pyritic sulfur from pulver 30 ized using an exchange column. The water used for
ized coal. The organic sulfur is not affected. Under rinsing had been deionized also. The air used to pressur
alkaline conditions 80-85% of the pyritic sulfur and ize some of the reactions was designated breatheable
30-40% of the organic sulfur is removed. A known quality.
Oxydesulfurization Process is similar to the LOL Pro
cess but an iron-complexing agent such as oxalic acid or 35 Apparatus
its salt is added to act as a promoter. Pyritic sulfur re The reactions were carried out in a 325 ml. stainless
moval approaches 95% and organic sulfur removal steel autoclave, capable of maintaining a maximum pres
approaches 35% for pulverized coals. This process sure of 3000 psi. The autoclave was manufactured by
typically employs alkaline solutions at 150 degrees Cel American Instruments (Model 40 12150SP, Series G6
sius and oxygen at 14 atmospheres to leach over 95% of 40 3129). The vessel was heated by a thermostat controlled
the pyritic sulfur within 1 hour from certain coals. Or sleeve and is agitated by a pivoting rocker cam.
ganic sulfur removal varies from coal to coal but can
approach 50%. In the oxidation by Nitrogen Oxides Procedure
Process the active oxidizing agent is nitrogen dioxide.
Pulverized coal is heated for 1 hour at 100 degrees 45 Reactions were carried out using -8 mesh coal.
Celsius under atmospheric pressure with a gas mixture These reactions represent a systematic attempt to opti
mize reaction conditions and reagents for removing
of oxygen, nitrogen, nitrogen dioxide, and nitrogen sulfur. Carboxylic and Peracids were reacted under
oxide. The coal is then treated with hot caustic solution
to remove the oxidized organic sulfur compounds. The varying conditions.
pyritic sulfur and up to 40% of the organic sulfur can be 50 The carboxylic acids were the first reactants to be
removed. studied. The acids used were: formic, acetic, propionic,
None of the above processes have been developed butyric, In a
valeric, iso-butyric, and iso-valeric.
first set of reactions each acid was reacted with
commercially, due to the reaction requirements for the
processes and the economics of implementing them. ten grams of -8 mesh coal. One hundred milliliters of
55 2.0M acid was used in each case. The reaction mixture
SUMMARY OF THE INVENTION was placed in the autoclave and allowed to come to
The process of the present invention uses carboxylic 150° C. The reaction time for all the experiments was
acids and their salts which are relatively inexpensive one hour after a heat-up period of thirty minutes. The
materials (sodium formate, sodium acetate, etc.) and pressure in the reactor increased during the reaction
relatively mild reaction conditions. This chemical de 60 because of reaction temperature. Reaction temperature
sulfurization process could be coupled with the present of the autoclave was held at 150 degrees celsius. At the
day coal washing operations, which removes a signifi end of the reaction time, the pressure built up during the
cant portion of the pyritic sulfur, to remove additional reaction was released. The reaction mixture was then
sulfur (primarily organic sulfur) from the coal. immediately filtered.
A significant amount of the sulfur in coal is removed 65 The filtering procedure was Schleicher & Schuell
by treating the coal with carboxylic acids and/or salts. #588 prefolded filter paper. This paper is 0.008 inches
In experimentation, the sulfur occurs at 150 degrees in thickness and is considered a fast filter paper. After
Celsius, but is is likely that temperatures between ambi the reactor had been rinsed into the filter, 100 ml, of
 4,701, 183 4
3
boiling water was poured over the reaction coal mix Analysis of the Test Results
ture.
After the reaction coal mixture had drained, the filter An analysis of the reaction products and initial start
paper was scraped with a spatial to remove the coal ing coals were made to determine moisture, ash, volatile
from the paper. The reaction coal was then transferred matter, fixed carbon by difference, and total sulfur. A
to a beaker and placed in a vacuum oven. The tempera LECO micro-processor controlled instrumentation was
ture of the oven was 110 degrees C. The reaction coal used in the analysis.
sample remained under vacuum for eighteen hours. Forms of sulfur of all reacted coal samples was deter
After drying the sample was then pulverized in a high O mined by ASTM procedure D 2492. A two to five gram
speed grinder. The sample had to be ground to a smaller sample was extracted with boiling hydrochloric acid
particle size so that full analysis could be completed.
A second set of reaction mixtures containing 10 (2:3 dilution). This removes sulfate sulfur and non
grams of coal and buffered solutions of the carboxylic pyritic iron. The coal residue was filtered and ashed.
acids were prepared by adding sodium hydroxide pel The extracted sulfate sulfur is precipitated with barium
lets to the acid solutions to neutralize one-half of the 15 chloride solution. Sulfate sulfur was then determined by
available acid, resulting in a reaction mixture that was gravimetric analysis of barium sulfate. The ashed coal
1M in the acid and the salt. residue was extracted with hydrochloric acid (2:3 dilu
A third set of reaction mixtures containing salt solu tion) and was diluted to a standard volume. The pyritic
tions such as, for example, sodium formate, sodium 20 iron samples were then determined using a Varian
acetate, sodium propronate, sodium butyrate, sodium atomic absorption spectrometer. After pyritic and sul
valerate, sodium iso-bitryate, and sodium iso-valerate fate sulfur was determined, their values were subtracted
were prepared by adding a stoichiometric amount of from the total sulfur percentage to give the organic
base for example, sodium hydroxide to the acid to make sulfur percentage.
a 2M solution of the salt. 25 The
A fourth set of reaction mixtures containing 10 grams gives data results are shown in the following tables. Table 1
of coal and basic salt reaction mixtures was made by resulting from the first reaction set; Table 2
adding one and one-half equivalents of base for exam shows the percentage reductions of the data of Table l;
ple, sodium hydroxide, to the carboxylic acid, produc Table 3 gives data resulting from the second reaction
ing a solution that was 2M in the salt and 1M in sodium 30 set; Table 4 shows the percentage reductions of the data
hydroxide. of Table 3; Table 5 gives the data resulting from the
A fifth set of reaction mixtures was prepared using third reaction set; Table 6 shows the percentage reduc
peracids were prepared by adding 10 grams of coal and tions of the data of Table 5; Table 7 gives the data re
hydrogen peroxide to the acid solution. One milliliter of sulting from the fourth reaction set; Table 8 shows the
sulfuric acid was added to catalyze the formation of the 35
peracids. The only peracids used were performic and percentage reductions of the data of Table 7: Tables 9,
peracetic. Reactions were carried out using the perac tion set; Tablegive
11, 13 and 15 the data resulting from the fifth reac
ids, their buffered solution, their salt solutions and their reduction of Table 9,12,11,1413and
10,
and
16 show the percentage
15, respectively; Tables
basic salt solutions. Sodium hydroxide was used to form 17, 19 and 21 give the data resulting from the sixth and
these mixtures. A base such as, for example, sodium 40
hydroxide, was added one hour after the peracid mix seventh reaction sets; and Tables 18, 20 and 22 show the
ture was made, and the mixture was cooled during the percent reduction of Tables 17, 19 and 21 respectively.
neutralization of the peracids to prevent decomposition Table 23 shows the percent reduction resulting from the
of the peracids. eighth reaction set.
A sixth set of reaction mixtures were prepared by 45 TABLE 1
mixing 10 grams of coal and 100 ml. of 2Macid such as
formic or acetic acid. The reaction mixture was reacted Acid Reaction Analysis
under an initial pressure of 600 psi. Air was used to Vol. Fixed Total Organic Pyritic
Matter Ash Carbon Sulfur Sulfur Sulfur
pressurize the reactor to 600 psi. The sixth set of reac
tion mixture was carried out through the range of their 50 F 42.9 9.34 57.09 3.95 2.58 1.3
respective acid, buffer and salt solutions. A.
P
43.48
43.37
9.72
9.64
56.52
56.52
3.91
3.87
2.17
2.28
1.69
1.71
A seventh set of reaction mixtures were prepared by B 40.36 9.67 56.04 3.84 2.3 1.54
mixing 10 grams of coal with a combination of formic V 44.93 9.73 55.07 4.02 2.5 1.53
and acetic solution. The reaction mixture was reacted IB 43.36 10.60 56.64 4.04 2.46 1.58
under 600 psi pressure using air. These reaction solu 55 IV 43.65 9.73 56.35 3.92 2.67 1.25
tions were 1M in both formic and acetic acids. This set Analysis percentages are in dry ash free basis except ash which is in dry basis.
of reaction mixtures was carried through the range of
acid, buffer and salt solutions.
An eighth set of reaction mixtures containing 2M TABLE 2
formic and 2M iso-valeric salts and 10 grams of coal 60 Acid Reaction Reductions
were prepared using -60 mesh coal. The same reaction Vol. Fixed Total Organic Pyritic
conditions were used during these experiments (150 Matter Ash Carbon Sulfur Sulfur Sulfur
degrees celsius, 2M solution in each salt, and one atmo F -.43 14.39 29 5.5 5.49 10.34
sphere initial pressure). The -60 mesh coals were fil A -1.76 10.9 1.29 6.45 20.51 - 16.59
tered in the same way as the other reactions. However, 65 P - 1.5 11.64 1.11 7.41 16.48 - 17.94
the coals were not dried in a vacuum oven. Instead the B 5.54 1.36 2.13 8.3 15.75 - 6.21
coals were dried at 110 degrees celsius with an air flow V -5.15 10.81 3.82 3.82 8.42 -5.52
to prevent loss of volatile matter by the vacuum. IB - 1.48 2.84 1.08 3.34 9.89 -8.97
 5
4,701, 183
6
TABLE 2-continued TABLE 6-continued
Acid Reaction Reductions Acid Salt Reaction Reductions
Vol. Fixed Total Organic Pyritic Vol. Fixed Total Organic Pyritic
Matter Ash Carbon Sulfur Sulfur Sulfur 5 Matter Ash Carbon Sulfur Sulfur Sulfur
IV -2.16 10.81 1.58 6.22 2.19 13.79 IV -.99 8.6 .7 8.85 5.86 14.48
All reductions in percent of original analysis All reductions in percent of original analysis
Negative sign means increase Negative sign means increase
F = formic acid F = formic acid
A = acetic acid A = acetic acid
P = propionic acid 10 P = propionic acid
B = butyric acid B = butyric acid
V = valeric acid W = valeric acid
IB = iso-butyric acid IB = iso-butyric acid
IV = iso-valeric acid IV = iso-valeric acid

TABLE 3 15 TABLE 7
Acid Buffer Reaction Analysis Basic Acid Salt Reaction Analysis
Vol. Fixed Total Organic Pyritic Vol. Fixed Total Organic Pyritic
Matter Ash Carbon Sulfur Sulfur Sulfur Matter Ash Carbon Sulfur Sulfur Sulfur
F 43.11 9.22, 56.89 3.92 2.49 20 OH 41.56 14.65 58.44 4.29 2.19 2.10
A. 43.16 9.22 56.84 3.79 2.46 1.34 F 4.53 12.03 58.47 3.91 2.24 1.68
P 43.29 9.78 56.71 3.86 2.20 1.67 A 4.54 11.67 58.46 3.86 2.48 1.37
B 42.88 9.52 57.2 3.91 2.50 1.4 P 4.71 11.9 58.29 3.77 2.35 1.42
V 44.08 9.33 55.92 3.74 2.6 1.4 B 40.97 12.75 59.02 3.86 2.48 1.38
IB 43.41 9.54 56.57 3.83 2.44 1.39 V 42.00 15.35 58.00 3.93 2.38 55
IV 43.67 9.85 56.33 3.77 2.53 1.24 25 IB 42.62 10.78 57.38 3.87 2.68 i.19
IV 41.25 14.41 58.75 3.73 2.53 1.2
Analysis percentages are in dry ash free basis except ash which is in dry basis.
Analysis percentages are in dry ash free basis except ash which is in dry basis.
TABLE 4
TABLE 8
Acid Buffer Reaction Reductions
Vol. Fixed Total Organic Pyritic 30 Basic Acid Salt Reaction Reductions
Matter Ash Carbon Sulfur Sulfur Sulfur Vol. Fixed Total Organic Pyritic
Matter Ash Carbon Sulfur Sulfur Sulfur
F --.89 15.49 .64 6.22 8.79 2.75
A. - 1.01 15.49 .73 9.33 9.89 7.58 OH 2.73 -34.29 -2.07 -2.64 19.78 - 44.83
P - .32 10.35 .96 7.65 1941 - 5.18 F 2.8 - 10.27 -2.12 6.45 17.94 - 15.87
B -.36 12.74 .24 6.45 8.42 2.75 35 A 2.78 -6.97 -2. 7.65 9.15 5.5
V -3.16 14.48 2.34 10.52 4.76 21.37 P 2.38 -9.17 -1.8 9.8 13.91 2.06
IB - 1.6 1255 i.2 8.37 10.62 4.13 B 4.11 - 6.87 -3.08 7.65 9.15 4.82
IV -2.2 9.71 1.62 9.8 7.32 4.48 V 1.7 - 40.7 - 1.3 5.98 12.82 -6.9
IB 25 1.19 -.21 7.41 1.83 17.93
All reductions in percent of original analysis IV 3.46 -32.09 -2.61 0.76 7.32 17.24
Negative sign means increase
F = formic acid 40 All reductions in percent of original analysis
A = acetic acid Negative sign means increase
P = propionic acid F is formic acid
B = butyric acid A = acetic acid
W = valeric acid P = propionic acid
IB = iso-butyric acid B = butyric acid
IV = iso-valeric acid W = valeric acid
45 IB = iso-butyric acid
IVs iso-valeric acid
TABLE 5
Acid Salt Analysis TABLE 9
Vol. Fixed Total Organic Pyritic Peracid Analysis
Matter Ash Carbon Sulfur Sulfur Sulfur 50 Vol. Fixed Total Organic Pyritic
F 42.55 11.12 57.45 3.89 2.1 1.79 Matter Ash Carbon Sulfur Sulfur Sulfur
A 41.52 12.17 58.48 3.99 2.28 1.71 H2O2 43.14 9.03 56.86 3.37 2.28 77
P 43.15 10.57 56.85 4.02 2.8 1.84 F 43.28 8.91 56.72 3.41 2.32 .76
B 42.45 9.72 57.55 3.94 2.4 54 A. 43.33 8.67 56.67 3.26 2.46 46
V 43.94 10.35 56.05 4.01 2.55 1.46
IB 41.23 13.96 58.77 3.79 2.39 14. 55 Analysis percentages are in dry ash free basis except ash which is in dry basis.
V 43.5 9.97 56.85 3.81 2.57 1.24
Analysis percentages are in dry ash free basis except ash which is in dry basis. TABLE 10
Peracid Reductions
TABLE 6 60 Vol. Total Organic Pyritic
Matter Ash Sulfur Sulfur Sulfur
Acid Salt Reaction Reductions
Vol. Fixed Total Organic Pyritic H2O2 -.96 17.23 19.37 6.48 46.89
Matter Ash Carbon Sulfur Sulfur Sulfur F - 1.29 8.33 18.42 15.01 47.58
A. - 1.41 20.53 22 9.89 68.27
F .42 -1.93 -.34 6.93 23.07 -23.45
A. 2.83 -11.55 -2.4 4.54 16.48 -- 7.94 All reductions in percent of original analysis
5 Negative sign means increase
P -99 3.11 .7 3.82 20.14 -26.9 F = formic acid
B .65 10.9 -.5 5.74 2.08 -6.21 H2O2 = 1 M in H2O2
V -2.84 5.13 2.11 4.06 6.59 -.69 A = acetic acid
IB 3.51 -27.96 -2.64 9.33 12.45 3.44
 7 4,701,
TABLE 11 TABLE 1.8
Peracid Buffer Analysis Pressurized Acid Reductions
Vol. Fixed Total Organic Pyritic Vol. Fixed Total Organic Pyritic
Matter Ash Carbon Sulfur Sulfur Sulfur 5 Matter Ash Carbon Sulfur Sulfur Sulfur
F 42.75 9.36 57.25 3.46 2.345 77 H2O O 2. -.02 7.41 3.29 17.93
A 42.87 9.59 57.13 3.52 2.80 .73 F 09 9.8 -.09 8.85 3.66 20
Analysis percentages are in dry ash free basis except ash which is in dry basis. A. -.05 13.29 O 7.89 - 4.4 32.4
F -- A .14 12.64 -.3 8.37 - 0.99 11.72
All reductions in percent of original analysis
TABLE 12 10 Negative sign means increase
Basic Acid Salt Reaction Reductions H2O = water blank reaction run
A = acetic acid
Wol. Fixed Total Organic Pyritic F = formic acid
Matter Ash Carbon Sulfur Sulfur Sulfur F - A = formic and acetic acid combination
F -.05 14.2 0. 7.22 14.1 46.89
A. -.33 12.09 .22 15.78 -2.57 49.65 15
TABLE 19
All reductions in percent of original analysis
Negative sign means increase Pressurized Acid Buffer Analysis
F = formic acid Vol. Fixed Total Organic Pyritic
A = acetic acid
Matter Ash Carbon Sulfur Sulfur Sulfur
20 F 42.75 9.88 57.25 3.94 2.65 1.28
TABLE 13 A 42,03 0.15 57.99 3.80 2.58 1.2
Peracid Salt Analysis F -- A 42.46 0.38 57.54 4.08 2.77 1.31
Vol. Fixed Total Organic Pyritic Analysis percentages are in dry ash free basis except ash which is in dry basis.
Matter Ash Carbon Sulfur Sulfur Sulfur
F 42.52 11.00 57.48 3.69 2.63 1.04 25 TABLE 20
A. 42.92 9.26 57.08 3.47 2.55 90
Analysis percentages are in dry ash free basis except ash which is in dry basis. - Pressurized Acid Buffer Reductions
Wo. Fixed Total Organic Pyritic
Matter Ash Carbon Sulfur Sulfur Sulfur
TABLE 14 F -.08 9.44 0. 5.74 2.93 11.72
Peracid Salt Reductions 30 A 1.61 6.96 - 1.28 9.09 5.49 17.24
Vol. Fixed Total Organic Pyritic F- A .6 4.85 -.49 2.39 - 1.47 9.65
Matter Ash Carbon Sulfur Sulfur Sulfur All reductions in percent of original analysis
F 49 -.83 -39 11.72 3.66 28.27 Negative sign means increase
A -.45 15.12 31 16.98 6.59 37.93 F is formic acid
A = acetic acid
All reductions in percent of original analysis 35 F - A = formic and acetic acid combination
Negative sign means increase
F = formic acid
A sin acetic acid TABLE 21
Pressurized Acid Salt Analysis
TABLE 15 40 Wol. Fixed Total Organic Pyritic
Basic Peracid Salt Matter Ash Carbon Sulfur Sulfur Sulfur
Vol. Fixed Total Organic Pyritic F 41.84 11.25 57.51 3.89 2.45 1.45
Matter Ash Carbon Sulfur Sulfur Sulfur A 42.32 0.89 57.68 3.86 2.52 1.32
F 42.55 13.88 57.45 3.63 2.59 1.02 F- A 42.72 1.82 57.28 4.1 2.71 1.38
A. 42.97 9.69 57.03 3.58 2.76 .8 45 Analysis percentages are in dry ash free basis except ash which is in dry basis.
Analysis percentages are in dry ash free basis except ash which is in dry basis.
TABLE 22
TABLE 16 Pressurized Acid Buffer Reductions -
Basic Peracid Salt Reductions 50 Vol. Fixed Tota Organic Pyritic
Vol. Fixed Total Organic Pyritic Matter Ash Carbon Sulfur Sulfur Sulfur
Matter Ash Carbon Sulfur Sulfur Sulfur F 2.08 -3.12 - .44 6.93 10.25 0
F .42 -27.23 -.34 3.15 5.12 29.65 A. .95 .18 -.74 7.65 7.69 8.96
A -57 11.18 .4 14.35 - i.1 44.13 F -- A .02 -8.35 -.04 1.91 73 4.82
All reductions in percent of original analysis 55 All reductions in percent of original analysis
Negative sign means increase Negative sign means increase
F = formic acid F is formic acid
A = acetic acid A = acetic acid
F - A = formic and acetic acid combination
TABLE 17
Pressurized Acid Analysis 60 TABLE 23
Vol. Fixed Total Organic Pyritic Sulfur Reductions of Reacted -60 Mesh Coals
Matter Ash Carbon Sulfur Sulfur Sulfur Total Organic Pyritic Sulfate
H2O 42.73 10.68 57.27 3.87 2.64 1.19 Run No Sulfur Sulfur Sulfur Sulfur
F 42.69 9.84 57.31 3.81 2.63 1.6 1 16.03 8.40 41.38 - 177.8
A 42.75 9.46 57.25 3.85 2.85 98 65 2 4.35 5.34 49.66 -300.0
F- A 42.67 9.53 57.33 3.83 3.03 1.28 3 24.03 79.44 -22.5 -80.00
Analysis percentages are in dry ash free basis except ash which is in dry basis. 4. 3.33 19.80 - 19.18 - 100.00
5 5.34 28.35 -62.22 0.00
 4,701, 183
9 10
TABLE 23-continued TABLE 27
Sulfur Reductions of Reacted -60 Mesh Coals Preoxidation reations
Total Organic Pyritic Sulfate RUN #2O1 % % Reduction
Run No. Sulfur Sulfur Sulfur Sulfur ot. S. 2.99 28.4
6 23.51 46.99 12.96 - 100.00 Org. S. 238 9.1
Pyr. S. 0.40 72.4
All reductions in percent of original analysis Sul. S. 0.21
Negative sign means increase

A ninth set of reaction mixtures were prepared using O TABLE 28

eight mesh coals having three different initial sulfur Preoxidation reactions
contents. A first process was carried out with each of RUN #202 % % Reduction
the three mixtures to remove pyritic sulfur. Tot. S. 2.96 29.2
In the first process, 20 grams of the coal was mixed Org. S 2.49 4.8
with 100 ml of water to form a coal-water slurry in a 15 Pyr. S.
Sui. S.
0.32
0.15
77.9
---
bomb reactor vessel. The vessel was then pressurized to
10 atmospheres using essentially pure oxygen. The ves
sel was heated to 150 C. and maintained at 150 C. for Analysis of initial sulfur content of third coal:
about one hour. The vessel was allowed to cool to a Total Sulfur: 2.33
temperature for safe handling. The slurry was removed Organic Sulfur: 1.07
from the vessel and filtered to separate out the soluble Pyritic Sulfur: 1.20
sulfate sulfur. The filtered resulting coal product was Sulfate Sulfur: 0.05
washed with 100 ml of 2 grams/100 ml of sodium bicar TABLE 29
bonate to remove residual soluble sulfate sulfur. The 25 Preoxidation reations
washed resulting coal product was then allowed to dry. RUN #301 % % Reduction
The resulting coal product was then analyzed to deter Tot. S. 1.26 45.9
mine the percent change in organic, pyritic and sulfate Org. S. 0.51 52.3
sulfur from the initial amounts thereof. The results are Pyr. S. 0.62 48.3
Sul. S. 0.2
shown in the following Tables 24, 25, 26, 27, 28 and 29. 30
Analysis of initial sulfur content of first coal:
Total sulfur: 2.98 A second process was carried out on each of the
Organic sulfur: 0.81 above resulting coal products particularly to remove
Pyritic sulfur: 2.16 organic sulfur therefrom.
Sulfate sulfur: 0.01 35 In the second process, 10 grams of the resulting coal
(Negative reations are increases) product was mixed with 100 ml of water to form a coal
TABLE 24
product-water slurry in a bomb reactor vessel. In the
manama-ma-e-Hen first and second runs using the coal products resulting
Preoxidation reations from the first process of the first coal 0.2 moles of so
RUN iOl % % Reduction dium formate was added to the coal product-water
Tot. S. 1.32 55.7 slurry. In the subsequent runs using coal products re
Org. S. 0.89 -9.8 sulting from the first process of the first coal, and all of
Pyr. S. 0.31 85.6 the runs using coal products resulting from the first
Sul. S. 0.16 process of the second and third coals, 0.4 moles of so
45 dium formate was added to the coal product-water
TABLE 25
slurry. Each coal-product-water/sodium formate slurry
was pressurized in the bomb vessel to three atmospheres
Preoxidation reactions using essentially pure oxygen. The vessel was heated to
RUN #102 % % Reduction 150° C. and maintained at 150 C. for about one hour.
Tot. S. 1.37 54.0 50 The vessel was allowed to cool to a temperature for safe
Org. S. 0.87 -7.4 handling. The resulting slurry was removed from the
Pyr. S.
Sui. S.
0.34
0.16
84.3 vessel and filtered to separate out the soluble sulfate
sulfur. The filtered resulting coal product was washed
with 100 ml of water to remove residual soluble sulfate
TABLE 26 55 products. The washed resulting coal was then analyzed
to determine the percent change in organic, pyritic and
Preoxidation reactions sulfate sulfur from the amounts remaining in the respec
RUN #103 % % Reduction tive coals from the first process. The results are shown
Tot. S. 1.40 53.0 in the following Tables 30, 31, 32, 33, 34 and 35.
Org. S. 0.69 14.8 60
Pyr. S. 0.59 72.7 SULFUR ANALYSIS OF FIRST COAL
Sul. S. 0.10 TABLE 30
RUN #11 % % Reduction
Analysis of initial sulfur content of second coal: Tot. S. 1.03 65.4
Total Sulfur: 4.18 65 Org. S. 0.56 30.9
Organic Sulfur: 2.62 Pyr. S. 0.39 819
Sul. S. 0.08 orm
Pyritic Sulfur: 1.45
Sulfate Sulfur: 0.09
 4,701, 183
11 12
TABLE 31 C is carbon
R is hydrogen or a hydrocarbon group
RUN #112 % % Reduction In addition, it is contemplated that pressurizing the
Tot. S.
Org. S.
06
0.64
64.4
21.0 5
coal-water slurry with an inert gas instead of air or
Pyr. S. 0.35 83.8 oxygen will also function in the process for removing
Sul. S. 0.06 organic sulfur from coal when using formic acid or its
salts because of what their reducing properties due to
the particular
TABLE 32
RUN #13 % % Reduction O
Tot. S. 1.12 62.4 H-C-
Org. S. 0.42 48.1
Pyr. S. 0.64 70.3
Sul. S. 0.07 group thereof.
15 The foregoing detailed description is given primarily
for clearness of understanding and no unnecessary limi
SULFUR ANALYSIS OF SECOND COAL tations are to be understood therefrom for modifications
will become obvious to those skilled in the art upon
TABLE 33 reading the disclosure and may be made without depart
Sodium Formate Reactions: 2O ing from the spirit of the invention and scope of the
RUN #211 % % Reduction appended claims.
Tot. S. 2.78 33.5 What is claimed is:
Org. S. 2.24 14.5 1. A process for removing sulfur from coal compris
Pyr. S. 0.47 67.5 ing the steps of:
Sul. S. 0.06 forming a slurry of sulfur containing coal; carrier
25
liquid and a compound selected from the group
TABLE 34
consisting of carboxylic acids, percarboxylic acids,
salts of carboxylic acids, salts of percarboxylic
RUN #212 % % Reduction acids, and any combination;
Tot. S. 2.72 34.9 heating the slurry in an atmosphere containing oxy
Org. S. 2.15 17.9 30 gen gas; and,
Pyr. S. 0.5 64.8 separating the coal from the other slurry components
Sul. S. 0.05
after heating.
2. The process of claim 1 wherein the step of heating
SULFUR ANALYSIS OF THIRD COAL 35 the slurry comprises heating the slurry to at least the
boiling temperature of the carrier liquid.
TABLE 35 3. The process of claim 1 comprising pressurizing the
Sodium Formate Reaction: 8 slurry while heating the slurry.
RUN #311 % % Reduction 4. The process of claim 3 wherein the step of heating
Tot, S. 1.11 52.3 40 the pressurized slurry comprises heating the pressurized
Org. S. 0.46 57.0 slurry to at least the boiling temperature of the liquid
Pyr. S. 0.55 54.2 carrier.
Sul. S. 0.09 5. The process of claim 5 wherein the carrier liquid is
Water.
From the foregoing, it can be concluded that carbox- 45 6. The process of claim 1 wherein the compound
ylic acids, percarboxylic acids, and the salts thereof are group consists of formic acid, salts of formic acid, per
instrumental in the removal of organic sulfur from coal. formic acid, salts of performic acid, and any combina
Furthermore, it appears that of the carboxylic acids, tion thereof.
percarboxylic acids, and the salts thereof, that formic 7. A process for removing sulfur from coal compris
acids, performic acids, formate salts, and performate 50 ing the steps of:
salts function more efficiently than the others. forming a slurry of sulfur containing coal, carrier
It is speculated from the above discussed tests that in liquid, and a compound having a carboxylate con
addition to carboxylic acid, percarboxylic acids, and taining group;
salts thereof that any compound containing a carboxyl heating the slurry in an atmosphere containing oxy
ate group would also be useful to remove organic sulfur 55 gen gas to a reaction temperature of at least the
from coal. By carboxylate group, it is meant the follow boiling temperature of the carrier liquid and main
ing structure: taining the slurry constant at the reaction tempera
ture for a period of time sufficient to permit the
coal and selected compound to react; and,
60 separating the coal from the other slurry components
R-C-O- at the end of the reaction time.
8. The process of claim 7 further comprising pressur
Where: izing the slurry while heating the slurry.
O is oxygen
65