Effect of catalyst impregnation conditions on Greek lignite hydrogasification

P. S. Kokorotsikos, G. G. Stavropoulos
Aristotle

and G. P. Sakellaropoulos
University of Thessaloniki, PO BOX 466,

Department of Chemical Engineering, Thessaloniki, 540 06 Greece

Hydrogasification of Greek lignite impregnated with potassium salts and metal chlorides was studied isothermally, between 750and 900C in a fixed bed reactor, in correlation with the impregnation conditions (pH, molarity, temperature). Potassium carbonate favours light hydrocarbon formation. Lowering of pH of impregnation significantly decreases potassium chemisorption on the lignite matrix and is followed by a drastic decrease in methane production and carbon conversion during hydrogasification. Initial porosity and surface area decrease with catalyst impregnation and their development during hydrogasification is suppressed. (Keywords: gasifKation; lignite; catalysis)

studies have already been made on the influence of various chemicals acting as catalysts on coal and char gasification processes, when these chemicals are impregnated or mixed with the reacting material. However, little is known about the initial step of impregnation and insertion of metal ions in the coal matrix and about its influence on the final gasification process. The use of alkali carbonates and hydroxides has been reported in few hydropyrolysis, hydrocarbonization, or hydrogasification3 studies. The catalytic role of these compounds has been attributed to K+ ions, which may act as agglomerating inhibitors or depolymerization accelerators or they may form K-polyaromatic ion couples that destabilize and facilitate attack of the aromatic ring structure. In contrast, alkali oxides are suggested4 to play a significant role in the oxygen transfer mechanism in steam and CO, gasification. In this work, the parameters which influence chemisorption of potassium ions on lignite and the effect of adsorbed species on conversion and on gaseous product rate and yield, in lignite hydrogasification are studied. Parameters investigated include molarity, temperature and pH of the lignite impregnating solution. Catalysts tested here were selected from previous with emphasis given to K,CO,. For screenings5, comparison, some results are also reported on NiCI,, which, along with other metal chlorides tested, was found to act adversely on gaseous hydrocarbon formation.
Several

Proximate: moisture 60 wt %; volatile matter 43.1; fixed carbon 32.8; ash 24.1; CO, 1.3 wt % on dry basis. Ultimate: C 44.2; H 4.2; N 1.2; S 0.8; 0 25.6 wt Y0 on dry basis. Lignite was impregnated with various metal compounds at loads of 10 to 20% w/w, under a procedure described previously5. In order to distinguish between chemisorbed and physically held catalyst ions, the following methodology was developed. After drying, 1 g of each impregnated sample was extracted with water in a centrifuge, and cations (K+, Ni2 +) in the extract were analysed by atomic absorption. The difference between the total and the extracted amount of cations represents the chemisorbed metal ions on the lignite. Samples were gasified at ambient pressure under Hz flow (70ccmin-) in a tubular (0.8cmi.d.), fixed bed reactor for 100 min. Gaseous products were analysed for CH,, C2H6, C,H,, and CO, by on-line g.c. (Varian, Vista 6000). Ultimate analyses of chars were done by a LECO C-H-N-800 analyser. The development of surface area during hydrogasification was determined from CO2 isotherms at 195 K (with a Quantachrome continuous flow apparatus), using the BET equation. In addition, the micropore volume and micropore size distribution were obtained by Medeks method6. RESULTS AND DISCUSSION

EXPERIMENTAL Greek lignite from the Ptolemais reserve (= 4 x lo9 t) was used as a starting material (150 to 250~), symbolized as Km. Its proximate and ultimate analysis gave: -at the International Symposium Fundamentals ofcatalytic Coal and Carbon Gasification, Rolduc, The Netherlands, 5-7 May 1986 0016-2361/86/101462~4$3.00 0 1986 Butterworth & Co. (Publishers) Ltd. 1462

* This paper was presented

Adsorption of metal-ions on lignite Lignite impregnation with the examined catalysts, proceeded easily when samples were used as received (with 5&60% humidity). Predrying alters the wetability of lignite and hinders slurry formation. Impregnation of humid lignite with catalyst under vacuum was almost complete after 1 h and the fraction of adsorbed metal ions reached a constant value7. The amount of chemisorbed metal ions, at constant final catalyst load (10% w/w), depends on the molarity of

FUEL, 1986,

Vol 65, October

Effect of catalyst impregnation

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on Greek lignite:

P. S. Kokorotsikos

et al.

the impregnating solution, as shown in Figure I for K,CO,, KOH and NiCI,. Hence K+ adsorption increases with molarity by 2&25%, while that of Ni2+ declines quite drastically for solutions above 0.5 M. The different amounts of K+ and Ni2+, adsorbed from dilute solutions, probably arise from attachment to different sites in the lignite and/or the ash and from different strengths of adsorption. As molarity increased, Ni2+ adsorption dropped, probably due to slower diffusion of nickel ions into the pores, resulting from higher solution viscosities. With all catalysts, the chemisorbed amount of metal ions increased slowly with temperature, by lc15%, Figure 2. This relatively small change, may be attributed to either chemical phenomena or low energetic requirements (such as adsorption), or even to a physical transport effect. Indeed, viscosity decrease and higher ion mobility at elevated temperature would facilitate cation access into finer pores. The effect of temperature is more pronounced at different pHs, as shown for K,CO, at pH 13 and 14. The solution pH plays the most significant role in cation adsorption on lignite. For K,CO,, which as a 1 M solution has a pH of 13, acidification with HCl to pH3 gives quite lower fractions of chemisorbed K+, Figure 3. The amount of adsorbed K+ should not be related directly to an inhibiting action by Cl-, since small variations occur with large quantities of Cl- added, as e.g. between pH 13 and 10 or 7 and 3 (cf. neutralization curves*). Chemisorption decline at low pH may result from suppression of the Briinsted acid activity of the sites on which adsorption takes place. For NiCl,, whose solution (0.5 M) pH is 4, acidification increases somewhat the fraction of adsorbed Ni2+ (Note: for pH>7, Ni2+ precipitates as a hydroxide, thus, no adsorption results can be obtained). From these preliminary results it appears that Ni and K+ adsorb on different lignite sites. The significance of solution pH on K+ chemisorption is further supported by impregnation results with other potassium salts. Figure3 shows the fraction of K+ chemisorbed from 1M solutions of KOH (at pH 14), of KF (at pH 8), of K,SO, (at pH 6.5) and of KC1 (at pH 5.5), at 10% w/w loading. All points are in good agreement
100

with K,CO, adsorption results; deviations could be attributed to some anion effect. The phenomena of cation adsorption on the lignite matrix are quite complex, since lignite is a mixture of inorganic and organic substances with acidic and basic behaviour. Aluminosilicate structures can accommodate cations at the surface of a lattice with broken and free bonds; also at sites in the tetrahedral or octahedral lattice which contain ions other than Al or Si and of lower valence, thus having excess electrons.. Phenolic hydrogen inside carbon clusters can also be substituted by cations. On these sites adsorption takes place almost irreversibly and accounts for a fixed cation exchange substrate capacity at normal lignite pH between 5.5 and 7. Variations in impregnating solution pH can create new sites for cation (as well as for anion) adsorption. This pHdependent cation exchange is attributed to the influence of pH on the weak acid character of aluminosilicates and acidic groups of the organic matter through the following reactions:

Aluminosilicates

O-H

I
-O-Al+

I I

I+)

-O-

b $i-O-I :, I

, I I OHI I

+H+(pHI) t)

-o-

/y-o-AK

P-

, t-1
I 1 + 1H I I

+OH-(pH

P -0-Si-O-

Carboxylic

groups

I (+I I --Lo; -1:

-H ;OH4 +H+ (PH 1)

y-y=o -C-H (pH t)

, i-1 +I_K+ I / H+ I
Hz0

I R

+ OH-

(Excess H+) + (Lignite OH-) 4 (Excess OH-) + (Lignite H+)

-+ HP0 P

A
40 -

I
20 t

01 0

Increase of pH results in abstraction of lignite H+ by OH- and formation of water. The remaining sites have a free negative load where potasium cations can adsorb. The reverse happens with pH decrease and results in decline of the cation exchange capacity. The amount of organic sites participating in these reactions is much higher than that of the inorganic ones due to the high carboxylic content of lignite. From this brief discussion it is apparent that metal cation adsorbed on lignite can be distinguished into two categories: those which have been firmly adsorbed within the lignite matrix, primarily on inorganic sites, and which are almost independent on solution pH; and those which adsorb mainly on organic matter and their amount varies with pH. The latter should be considered responsible for any catalytic action.
Hydrogasification results

0.5

1.0
Molarity CM)

1.5

2.0

Figure 1 Effect of molarity of the impregnating solution on the amount of cation chemisorbed on lignite: A. Ni+ from NiC12; 0, K+ from
K,CO,; 0, K+ from KOH

Previous TGA, non-isothermal experiments have shown that the best temperature region for catalytic and

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Effect of catalyst impregnation

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on Greek lignite:

P. S. Kokorotsikos

et al.

A-

o60

o,,

Al -e

A-A-A -.-

o-o-

:*
0 20 40

60
Temperature (9)

80

100

Figure 2 Effect of impregnation temperature on the amount of cation chemisorbed on lignite: A, Nif + from NiCI,; l , K+ from KOH (pH 14); 0, K+ from K&O, (pH 13); 0, K+ from K&O, (pH 4)

O-------A -------*

.A
0 4

/-/ .A.
8 Solution pH 12

lOOmin experiment, 10% of CH,, 95-99x of C,H,, C2Hs, and S&90% of CO, and CO is produced in the first stage. Total, as well as C and H conversions of lignite and yields of light gaseous hydrocarbons under various conditions are summarized in Tuble 1. Potassium based salts, i.e. K,CO, and K-Zn bimetallics, at 25C and pH 12-13 give the highest conversion to CH,, while NiCl, gives the lowest C conversion and gaseous hydrocarbons yields. Surface area studies have shown that catalyst addition, especially above lo%, affects initial pore structure and its development by reaction (Table I). A blockage of pores is observed at the expense of smaller pores, as shown from the slight increase in the estimated mean pore radius. This probably results from inaccessibility of small pore branches interconnected with blocked larger pores. The BET surface area increases with hydrogasification by one order of magnitude. However, in the presence of catalysts (e.g. 20 % K,CO,) areas after reaction are 2 10 times less. This area decrease in conjunction with the observed higher yields of light HCs indicate a strong catalytic effect in lignite hydrogasification. From experiments with samples impregnated differently it is evident that lignite conversions and yields depend on impregnation conditions and/or metal ion chemisorption. Decrease in alkalinity of impregnating solution lowers KC chemisorption (Figure 3) as well as C conversion and

Figure 3 Effect of impregnating solution pH on the amount chemisorbed on lignite (at 25C): a, Ni+ from NiCl,; 0, K,CO,

of cation K from

non-catalytic hydrogasilication is 750 to 900C. Isothermal experiments reported here were performed in this region with emphasis on gaseous product yields and lignite conversion. Methane is one of the main gaseous hydrocarbon products. The total yield of methane throughout an experiment, expressed as the fraction of lignite C atoms converted to methane C atoms, is shown in Figure 4 for various temperatures and catalysts. The total conversion of uncatalysed lignite increases with temperature, but methane yields decline due to formation of higher hydrocarbons in the first stage of devolatilization. Potassium carbonate improves methane yields by lO20x, depending on T and catalyst load. Nickel chloride lowers methane formation significantly, yielding mainly liquid products. In all cases, isothermal hydrogasification can be divided into two stages: a, the rapid hydropyrolysis step, which lasts l-3 min and where devolatilization and hydrogenation of volatile products occurs; b, the char hydrogasilication region, where the main product is methane at an almost stable rate of formation. For a

01

700

750

800
Temperature

850
('Cl

900

950

Figure 4 Fraction of lignite C-atoms converted to C-atoms of CH,, at various hydrogasification temperatures for: 0, unimpregnated; 0, 20 (w/w) NiCI,: a, 10% (w/w) K&O,; W, 20~ (w/w) K&O,, impregnated lignite

Table 1 structure -~

Effect ofcatalyst

impregnation

and hydrogasification

on pore

Unreacted Sample Km K,,, + IO K,CO K,,, +20; K,CO: S 7 5 0.88 re 7.9 8.1 8.9 V,x103 11.65 S

Reacted re 6.6 5.8 7.8

at 800C V,xlO 50 43 5

1.90
0.36

138 131 16

S: Surface area by multipoint r,: Mean pore radius (A) V,: Pore volume (cm3/g)

BET (m/g)

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Effect of catalyst impregnation conditions on Greek lignite: P. S. Kokorotsikos et al.

Table 2 Results of isothermal hydrogasification at 85oC _ CH, Sample ~~.__~ K,,, uncatalysed K,,, +20,, (w;w) NiCI, K,,, +20,, (WW) K,CO, K,,, pH pH pH pH pH pH pH + IO,, (w/w) K,CO, I3 at 25C I1 at 25-C 9 at 25 C 7 at 25 C 4 at 25C 13 ar 100 C 4 at 60 C ,w,w Total conversion -__ 56.9 53.5 53.7 54.0 54.4 51.7 51.1 48.6 60.3 51.7 OwJw Carbon conversion 52.5 39.6 49.1 51.7 49.0 44.2 40.8 36.6 54.1 39.9 w/w Hydrogen conversion 90.7 83.6 94.1 90.5 88.7 89.4 88.6 93.3 93.5 92.0 84.0 89.9 u 10.7 6.1 16.5 12.0 10.5 10.1 7.9 5.5 11.3 9.7 14.8 6.4 yields h 20.5 15.5 33.1 23.1 21.4 22.9 19.4 IS.1 20.6 25.6 30.2 16.4 a 1.28 1.19 1.95 2.19 1.88 2.03 1.42 C,H, yields h 2.4 3.0 3.9 4.2 3.8 4.5 3.5 3.4 2.4 6.0 4.2 4.8 u 0.36 0.23 0.34 0.50 0.30 0.37 0.23 0.20 0.25 0.08 0.44 0.34 C,H, ytelds h 0.68 0.58 0.69 0.97 0.55 0.72 0.45 0.4 I 0.46 0.22 0.9 I 0.58

1.20
1.30 2.27 2.06 1.86

K,,, + 20,, (w;w) K-Zn pH 12at25C pH I at 25C (I C atoms hC atoms of CH,, of CH,, C2H, C,H,

52.0 49.1 or C,H, or C,H, formed formed

49.0 39.0

___

per 100 C atoms of unreacted lignite per 100 converted C atoms of lignite

1
\ :0
I \

i-

22; ---01
o-0,
r,
O-OI

o_o_Q

-o-o-_o-o
0-0-0~ v-v-v-v

DA--A-

O-0
A

~.:~v-v-v-D_
.-._

0 0

l I I

O-0
I I

C and total conversion, while K+ chemisorption and light hydrocarbon yields do not show significant variations. This probably results from hydrolysis (during impregnation) of lignite compounds and easier devolatilization, since it is known that low rank coal substances can be converted to alkali-soluble materials at elevated temperatures (> 1OOC). At 6oC and pH 4, however, CH, yields improve as well, compared with those at 25C at pH 4, while adsorbed K also increase 33 to 447: (Figures 2 and 3). These results provide further support to the significant catalytic role which adsorbed metal ions play in hydrogasilication. This work suggests that lignite hydrogasification is catalysed by potassium salts impregnated from highly activity depends on alkaline solution. Catalytic impregnation conditions, especially pH and temperature, which also affect the amount of metal ions chemisorbed in the lignite matrix. ACKNOWLEDGEMENT The authors wish to thank the European Coal and Steel Community and the Chemical Process Engineering Research Institute of Thessaloniki for financial support of this work. P. Kokorotsikos also thanks the Alexander S. Onassis Foundation for a research fellowship. REFERENCES
I 2 3 4 5 6 7 8 Ouchi, K., Hosokawa, S., Maeda, K. and Itoh. H. Furl 1982,61, 627 Youngblood,L.,Cochran.H., Westmoreland,P..Brown.C.and Oswald, G. Ind. Eng. Chum. Prod. Rrs. Dev. 1980, 19. 29 McCoy, L. rf al., Department of Energy, DE 83013130, 1983, Final Report McKee, D. Fuel 1983,62, 170 Kokorotsikos, P., Stavropoulos, G. and Sakellaropoulos, G. P. Proc. Int. Conf. Coal Sci., Sydney 1985, 253 Medek. J. Furl 1977, 56, 131 Sakellaropoulos, G. P., ECSC 7220 EC 701, 1984, Report 1 Pietrzyk, D. and Frank. C., Analytical Chemistry, Academic Press, New York, 1974, 287 Sternberg, H., Raymond, R. and Schweigherd, F. Science 1975, 188,49 Alexiades, K., Clays-inorganic and organic colloids in soil, Thessaloniki, 1972 Alexiades, K., Physicochemical Analysis of Soils. Thessaloniki, 1972 Elliot, M., Chemistry of Coal Utilization, Second Supplementary Volume, John Wiley, New York, 1981, 30

20

40

60 Time imin)

80

100

Figure 5 Methane formation in isothermal hydrogasilication of lignite (850(Y), impregnated with lo,, (w/w) KZCO, at: 0, pH 13; Cl, pH 11; A,pH9;V,pH7;e,pH4

methane yields (Table 2 and Figure 5). This decrease should not be attributed to the amount of chlorides added, since pH lowering from I3 to 11 requires addition of 10 times more HCI than from pH 9 to 7; in the same pH ranges K + chemisorption and CH, yields decline only by about loo/ and 207; respectively. Similar behaviour with pH is also exhibited by bimetallic catalysts, such as K-Zn (Table I), for which methane yields at pH 1 drop to less than half their value at pH 12. Thus, low pH values appear to suppress the amount of metal ion chemisorption and hence, the hydrogasification rates and yields. If the latter assumption is correct, we should anticipate that potassium salts, whose solutions have a low pH should be worse hydrogasification catalysts value, compared with weak-acid salts and hydroxides. Indeed, this is the case of KC1 and K,SO, (with pH 667) which show low catalytic activity3, in contrast to K,CO, and KOH (pH 12-14). The temperature of impregnation at pH 13 affects more

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