REMOVAL OF SODIUM FROM LIGNITE CY ION EXCHANGING WITH CALCIUM CHLORIDE SOLUTIONS

L. E. Paulson and J. R. Futch

Grand Forks E n e r g y Technology Center, DOE Box 8213 U n i v e r s i t y Station Grand Forks, ND 58202 Lignite resources in N o r t h Dakota a r e estimate? a t 350 billion tons, comprising 20 percent o f t h e nation's total coal resources on a tonnage basis. Using present technology, 16 billion tons o f t h i s l i g n i t e i s mineable (1). Analyses o f over 400 samples o f coal taken t h r o u g h o u t the region show t h a t t h e average sodium oxide content is 5.5 percent of t h e ash (2). T h e major use o f lignite i s as fuel f o r electric power generation. These large power plants (up to 450 MW) cannot operate efficiently burning high sodium lignite because of fouling o f heat t r a n s f e r surfaces. Field tests and boiler experience have shown t h a t when sodium oxide content in t h e ash becomes greater.than 5 percent, excessive boiler f o u l i n g can be expected (3). Sodium does n o t occur as in t h e discrete mineral particles in lignite but i s Sodium, along w i t h calcium, evenly dispersed t h r o u g h o u t t h e coal matrix (4,5). magnesium, iron and aluminum cation, i s attached to exchange sites on t h e lignite s t r u c t u r e and can be replaced by ion exchange w i t h other elements (6). Combustion tests u s i n g l i g n i t e in which sodium has been replaced by calcium in ion exchange h a v e shown less f o u l i n g t h a n untreated lignite. T h i s paper presents selected results based on laboratory batch tests in which calcium from calcium chloride solution i s used t o replace sodium in a high sodium lignite. Test parameters include coal moisture content, particle size, solution concentration, temperature, solid-to-liquid ratio and contact time. EXPERIMENTAL PROCEDURE Lignite selected f o r t h e tests was from t h e Beulah mine (North Dakota) and contained 8.7 percent sodium oxide in t h e ash. Ash analysis, as determined b y x - r a y fluorescence, i s shown in Table 1. Ash content o f t h e coal was 10.8 percent on a dry basis.

Table 1 . Ash Analysis of Test Coal by X-ray Fluorescents: (Beulah mine, North Dakota) Element Si0 *l2'3 Fe203 Ti02
'2'5
224

Percent
19.7

12.0

1.6
0.5 0.3

CaO

19.3 5.2

MgO

Na20
K2
s03 TOTAL

8.7
0.7 25.0
99.0

The test coal was crushed t o desired size and stored in double plastic bags t o minimize moisture loss. T h e test procedure consisted o f combining t h e desired weight ratio o f l i g n i t e w i t h calcium chloride solution in a 400 ml beaker and s t i r r i n g w i t h a propeller-type mixer f o r t h e specified length o f time. The lignite was separated from solution by f i l t e r i n g w i t h a Buchner funnel u s i n g Whatman No. 41 f i l t e r paper. The f i l t r a t e was analyzed f o r p H and specific g r a v i t y , and t h e dissolved elements were measured by an inductively coupled argon plasma spectrometer (ICAP). The lignite was rinsed with 200 rnl deionized water a n d filtered. This f i l t r a t e was also analyzed. T h e coal sample was dried a n d ashed, and t h e ash analyzed b y x - r a y fluorescence spectrometry. RESULTS AND DISCUSSION Each o f t h e test parameters i s discussed individually. Coal Moisture T h e relationship between t h e extent o f sodium removal by ion exchange and lignite moisture content i s shown in Figure 1. Moisture reduction was accomplished In t h i s set of tests, coal sized t o 80 x 0 mesh by air d r y i n g t h e lignite a t 2SC. was contacted w i t h .OS molar calcium chloride solution f o r 5 minutes. T h e coalto-liquid weight ratio was 1 t o 4. The moisture content o f t h e coal varied from 34 t o 15 percent. Results indicate t h a t reducing t h e coal moisture t o 28 percent had l i t t l e effect on t h e r a t e o f exchange. Below 28 percent moisture, t h e r a t e of exchange was reduced considerably. Lignite has a porous s t r u c t u r e and t h e inherent water i s believed t o b e trapped in capillaries (7). Organically bound ions such as sodium may adhere t o In t h e ion exchange process, calcium diffuses from t h e surface of t h e capillaries. t h e solution i n t o t h e water-filled passages and replaces sodium. Reducing t h e lignite's moisture content collapses and seals o f f a portion gf t h e capillary t h u s reducing ion exchange potential. Particle Size The effect of particle size on t h e r a t e of ion exchange i s shown in Figure 2. set o f tests, various sized coal was treated w i t h .05 molar CaCI2 f o r 5 minutes a t solid to liquid weight ratio o f 1 t o 4. Coal moisture content was 34 percent.
In this

Results show t h a t t r e a t i n g 40 x 0 mesh lignite reduced t h e sodium content in t h e lignite by 80 percent, while t r e a t i n g 8 x 0 mesh, a t t h e same test conditions, reduced t h e sodium by 63 percent. T r e a t i n g $ x 0 i n c h sized lignite removed only 15 percent of t h e sodium originally in t h e coal. T h e lignite's particle size determines the distance t h a t t h e exchanging ion must t r a v e l t h r o u g h t h e capillary network and, f o r t h a t reason, effects t h e r a t e and e x t e n t o f exchange.

225

Solution Concentration T h e sodium content of t h e treated l i g n i t e (dry basis) as a function o f starting calcium concentration in solution i s shown in Figure 3. T h e calcium content of lignite resulting from t h e treatment i s also shown. In t h i s series o f tests, calcium c h l ~ r l d c :n!utlr\n in mder concentration v a r y i n g from 0 t o .2 molarity was mixed w i t h 80 x 0 mesh lignite for 3 minutes. T h e solid-to-liquid weight ratio was 1 to 5. Results indicate a d i r e c t relationship between solution concentration and sodium removal. T h e calcium content of t h e l i g n i t e increases proportionally t o t h e decrease in sodium content. Temperature T h e relationship between t h e temperature o f the calcium solution and sodium removal is shown in Figure 4. In t h i s t e s t series, 8 x 0 mesh lignite was treated w i t h .05 molar CaCl solution f o r 5 minutes. T h e solid-to-liquid r a t i o was 1 t o 4. T h e solution t e m p e r h r e was varied f r o m 70 t o 145 degrees F. Results indicate t h a t 63 percent of t h e sodium was removed from t h e lignite a t 70 degrees F., while 72 percent was removed a t 120 degrees F. Temperatures h i g h e r t h a n 120 degrees F. d i d not increase t h e removal efficiency. Figure 5 shows t h e moles o f sodium removed from the lignite p e r mole o f Under these test conditions, one mole calcium added as a function of temperature. o f calcium will replace 1.15 t o 1.25 moles o f sodium. Under ideal conditions, this r a t i o should be two sodiums removed f o r e v e r y calcium added. In t h e present case, other metals in t h e lignite, such as magnesium o r iron, which are also ion exchangeable, may have been replaced, t h u s reducing t h e molar ratio o f calcium replacing sodium. Solid-Liquid Weight Ratio T h e solid-to-liquid ratio effects sodium removal efficiency as i s shown in Figure 6. In t h i s series of tests, l i g n i t e sized 8 x 0 mesh was contacted w i t h .05 molar calcium chloride f o r 5 minutes. T h e solid-to-liquid weight ratios were 1 t o 2, 3 t o 8, and 1 t o 4. Results in Figure 6 show t h a t increasing t h e q u a n t i t y o f liquid (thus increasing t h e q u a n t i t y o f calcium present) in proportion t o solids will increase the sodium removed. T h e reason i s t h a t w i t h h i g h e r ratios more calcium is in contact w i t h t h e coal. Figure 7 shows t h e r a t i o o f moles o f sodium removed t o moles o f calcium added t o t h e l i g n i t e f o r t h i s set o f tests. As shown, t h e molar quantity o f sodium removed t o calcium added t o t h e coal varied from 1.25 t o 1.35 and compared favorably t o t h a t previously shown in Figure 5. Contact Time The effect o f solid-liquid contact time on sodium removal efficiency i s shown in Figure 8. I n t h i s series of tests, .05 molar CaCl solution was mixed w i t h 8 x 0 mesh lignite in a weighed solid-to-liquid ratio o f t o 4. Contact time was 5, 30 and 120 minutes.

Results show t h a t t h e q u a n t i t y o f sodium removed f o r t h i s size coal increased A f t e r 30 minutes, there was no significant with contact time u p t o 30 minutes. increase. T h i s indicates t h a t equilibrium under these test conditions w i t h t h i s size limit has Seen achieved in less than 30 minutes.
226

SUMMARY T h e quantity of sodium removed from lignite b y ion exchange w i t h calcium i s a function of t h e coal's moisture content, particle size, q u a n t i t y o f calcium present in solution, solution temperature and contact time. T h e greatest exchange occured w i t h lignite containing more t h a n 28 percent moisture and smallest particle size (80 mesh x 0). T h e r a t e o f exchange increases s l i g h t l y w i t h temperature t o 10F 2'. T h e sodium removal i s a d i r e c t function o f solution calcium concentration. solution concentration and solid-liquid r a t i o are interdependent variables which determine total q u a n t i t y o f calcium which contacts a unit q u a n t i t y o f lignite. REFERENCES

1.
2.

Wiebner, J. D., "Lignite and N o r t h Dakota." No. 8 (August, 1977).

Mining Engineering,

Vol.

29,

Cooley, S. A. and R. C. Ellman, "Analysis o f Coal and Ash from Lignite m d Subbituminous Coals o f N o r t h Dakota and Eastern Montana," unpublished. Gronhovd, G. H., A. E. Harak, and P. H. Tufte, "Ash Fouling and Air Pollution Studies Using a Pilot Plant T e s t Furnace," Proceedings of the Symposium on Technology and Use o f Lignite, Bureau of Mines U n i v e r s i t y of North Dakota, Grand Forks, ND, May 1-2, 1969, Comp. by J. L. Elder and W. R. Kube, Bureau o f Mines IC 8471, 1970, pp 69-88.

3.

4.

Tufte,

Proposed Mechanism f o r Ash Fouling presented a t Winter Annual Meeting of American Society o f Mechanical Engineers, New York, NY, November 17-22,
H.

P.

and W.

Beckering,

"A

Burning Northern Great Plains Lignite,"

1974.
5.
Paulson, L. E., W. Beckering, and W. W. Fowkes, "Separation and Identification o f Minerals from N o r t h e r n Great Plains Province Lignite," Fuel, Vol. 51, No. 3, July, 1972, p p 224. Paulson, L. E. and W. W. Fowkes, "Changes in Ash Composition o f North Dakota Lignite Treated b y Ion Exchange," Bureau o f Mines Report of Investigation 7176, September, 1968. Lavine,
I.,

6.

7.

Lignite Occurrence and Properties,

Grand Forks,

N o r t h Dakota,

1939.

227

50'

1 5

30 LIGNITE MOISTURE CONTENT, percent

20

25

35

40

FiGURE 1.

- Sodium removal

as a function o f l i g n i t e

moisture content.

0)

2
0)

8
a

f E

g:

SIZE, mesh

FIGURE 2 .

Sodium removal as a function o f l i g n i t e p a r t i c l e size.

2 2%

.-

b\

229

80
c

E a

8 70

9 o> 6 0 - / 5
8

3 z
50

TEMPERATURE,
O F

FIGURE 4.

Sodium removal from l i a n i t e as a function of temperature o f treating solution.

9
l.5-

90 >& z2 w
a
5-

- .o 3 0.50

23 $ 3

FIGURE 5.

Ratio of sodium removal from i i g n i t e t o calcium added as a function of solution temperature.

c m C

L?

70

B B 5
a 60

5 B

50

I TO 4

3 TO 8 SOLID - LIQUID RATIO

I TO 2

FIGURE 6,

Sodium removal from lignite as a function

o f solid to liquid ratio.

"

lTO4

3 TO 8
SOLID LIQUID RATIO

1 TO 2

FIGURE 7.

Ratio of sodium removal from the lignite to calcium added as a function of solid to liquid ratio.
231

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8
. r

c, U
8
S

YQ

u l

al

232