ISSN 2070 0504, Catalysis in Industry, 2010, Vol. 2, No. 2, pp. 108112. Pleiades Publishing, Ltd., 2010.

. Original Russian Text A.L. Tarasov, Yu.A. Korolev, L.M. Kustov, S.A. Nikolaev V.V. Smirnov, 2010, published in Kataliz v Promyshlennosti.

CATALYSIS IN CHEMICAL AND PETROCHEMICAL INDUSTRY

Steam Conversion of Glycerol on Ni and AuNi Catalysts

A. L. Tarasova, Yu. A. Korolevb, L. M. Kustova, S. A. Nikolaevb, and V. V. Smirnovb
a

Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, Moscow, Russia b Moscow State University, Moscow, Russia
Received December 4, 2009

AbstractDuring primary screening, catalysts which enable production of syngas or hydrogen from glycerol with high yields under soft conditions were revealed. Nickel and nickelgold catalysts on various supports support were studied in the reaction of steam conversion of glycerol. Nickel catalysts on acidic supports (F Al2O3 and B2O3Al2O3) were ascertained to provide 73% selectivity toward H2 at temperatures as low as 520C, glycerol conversion amounting to 48%, which allows one to consider these catalysts to be applicable for H2 production from glycerol. 30% Ni/Al2O3 catalyst produced according to the original solgel proce dure allows one to obtain syngas with a composition suitable for methanol production at relatively low tem peratures (520570C) and almost complete glycerol conversion. A strongly pronounced synergetic effect was ascertained for 0.27% Au0.09% Ni/Al2O3. Glycerol conversion on this catalyst at 570C attains 67%; the composition of the resultant gas mixture is applicable for methanol production. Key words: glycerol, steam conversion, syngas, nickel catalysts, synergetic effect. DOI: 10.1134/S2070050410020030

INTRODUCTION In recent years, the problem of the search for renewable fuels has become very topical due to deple tion of oil reserves; vegetable oils and animal fats, i.e., fatty acid triglycerides, are potential sources of such fuel. Triglycerides are converted to methyl ethers, so called biodiesel, by the process of re etherification with methanol catalyzed by alkali. Glycerol is formed as a side product: 1 kg per 9 kg of biodiesel. In the United States alone, biodiesel production was as high as 2.3 million tons in 2008; therefore, 200 000 tons of glycerol were produced. However, via this process, glycerol is obtained in the form of 80% aqueous solu tion, requiring high power inputs to bring it up to com mercial quality [1]. Steam conversion of glycerol with further conversion of syngas to methanol and other valuable products is a more economically sound method for glycerol processing. The main reactions comprising the process of steam conversion of glycerol are C3H8O3 + 3H2O = 7H2 + 3CO2 + 128 kJ/mol, (1) C3H8O3 = 4H2 + 3CO + 250 kJ/mol, (2) (3) CO + H2O = CO2 + H2 41 kJ/mol, (4) CO + 3H2 = CH4 + H2O 206 kJ/mol, CO2 + 4H2 = CH4 + 2H2O 165 kJ/mol. (5) Therefore, the composition of products depends considerably upon the catalyst type and process condi tions [2]. The advantages of steam conversion are obvious. The gas mixture, H2 and CO predominating, is obtained as products which can be guided either to methanol production or to the FischerTropsch pro

cess or directly to hydrogen consumers after carrying out the additional conversion of the mixture according to the water shift reaction (3), which allows one to obtain an additional amount of hydrogen. For reac tions (1) and (2), of two cases the H2 : CO ratio is pref erable to be 23 [3]. Steam conversion of glycerol was studied in [4, 5]. It was ascertained that, on Ir, Co, and Ni catalysts applied on CeO2, glycerol is completely converted at 400450C, the selectivity toward H2 attaining 85%, and H2 : CO ratio being 2.5. Hydrogen production from glycerol on RhCe/Al2O3 catalyst in autother mal mode has been studied [6]. The selectivity toward H2 at 862C amounted to 79% and H2 : CO = 2.5 was attained upon complete glycerol conversion. The selectivity toward H2 on Ru/Y2O3 catalyst at 600C and complete glycerol conversion was shown [7] to amount to ~90%. For steam conversion of glycerol [8], commercial Ni catalyst was used for oil conversion C11 NK, which provided 77% yield of H2 at 850C. The process of steam conversion of glycerol was studied on mono lith catalysts 2.5%Ni/Al2O3 at 700900C and con stant glycerolwater molar ratio of 1 : 6 [9]. Glycerol conversion and the selectivity toward hydrogen were shown to increase from 20 to 80% in this temperature range, while the selectivity toward hydrogen rose from 48 to 60%. We studied a series of Ni catalysts on oxide sup ports, namely, aluminosilicate, titanium, aluminum, and zirconium oxides promoted by different acidic agents in the reaction of steam conversion of glycerol

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at glycerolwater molar ratio = 1 : 1, i.e., in the mix ture with water content of 20%, that is close to the actual content, which is typical for the process of biodiesel production. Ni catalysts are relatively inex pensive and quite reasonable for steam conversion of methane [10, 11]. It was shown earlier that modification of Ni/ Al2O3 catalysts with gold results in an increase in acetylene conversion in the reaction of selective hydration of acetylene by more than an order of mag nitude and appreciably depends on Au/Ni ratio [12]. Catalytic systems based on Au and Ni nanoclusters in the allyl isomerization reaction are known to exhibit an increase in catalytic activity of AuNi systems by three orders of magnitude, i.e., a clearly pronounced synergism of catalytic action is observed in systems containing nickel and gold [13]. In this connection, investigation of low content Au:Ni/ Al2O3 catalysts was of great interest for the reaction of steam conver sion of glycerol, which is of no less importance for industrial implementation. EXPERIMENTAL As the starting material, we used 99.5% glycerol (Acros). A series of catalysts was studied in this work: (1) Commercial Aldrich 65%Ni/alumosilicate. (2) Sol gel samples of 10%NiAl2O3 and 30%Ni Al2O3 prepared using the sol gel technique. Alumi num isopropylate Al(C3H7O)3 was used as a precursor for preparation of aluminum oxide, 10 g of which and the adequate amount of Ni(NO3)2 6H2O was diluted in 100 ml of distilled water at 9095C. The mixture was continuously stirred for 1 h. Then 4 ml of 1M HNO3 solution was added to the mixture, followed by stirring for 3 h at 9095C. Then water was removed on a rotary evaporator at 65C, the resultant product was left to dry overnight at 120C. The dried product was calcined at 600C in air flow (300 ml/min) for 2 h. The temperature was increased from room tempera ture to 600C with 1C/min increment. (3) Catalyst 5%Ni/TiO2: the sample was prepared by impregnating TiO2 support (P 25 Degussa, 2 g) with aqueous solution of Ni(NO3)2 6H2O (1 ml), which contained 0.1 g of Ni per 1 ml. The product was left to air dry overnight at room temperature, and then calcined for 2 h at 500C in air flow (300 ml/min). The temperature was increased from room temperature to 500C with 1C/min increment. (4) Catalysts with low Ni and AuNi content. Their compositions are as follows: 0.27%Au 0.09%Ni/Al2O3, 0.4%Ni/Al2O3, 1.68%Au/Al2O3. Microspheric catalyst Al2O3 of the IKT 02 6M brand from AO Katalizator with specific surface Sspec = 138 m2/g and total pore volume of 0.32 cm2/g was used as a support for nanoparticles. Before using it, Al2O3 was activated for 3 h by calcinations at 350C. For cat alyst preparation, we used HAuCl4 nH2O (OAO
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Aurat, USSR Specifications TU 6 09 05 1075 89) with Au content of 49.04 wt %, Ni(NO3)2 nH2O (Reakhim, analytical purity grade), distilled water, and 0.1 M aqueous solution of NaOH. Gold nanoparticles, immobilized on Al2O3, were formed using the anion adsorption procedure [14]. In general, to prepare Au/ Al2O3 catalyst, pH of aque ous solution of HAuCl is brought to 7.0 by adding NaOH, then a calculated amount of calcined support is introduced into the neutralized precursor solution, and the resultant suspension is stirred at 70C for 1 h. The catalyst precursor is isolated from the mother solution, washed with distilled water, air dried for 24 h, and calcined at 300C in inert atmosphere for 3 h. Nickel particles, immobilized on Al2O3, were formed using the moisture capacity impregnation technique [15]. The essence of the technique is as fol lows. To prepare Ni/ Al2O3 catalyst, the amount of aqueous solution of nickel nitrate calculated accord ing to the moisture capacity is added to the support calcined at 350C, air dried for 24 h, calcined at 300C in inert atmosphere for 3 h, and reduced in hydrogen flow at the same temperature for 3 h. Bimetallic catalysts AuNi/ Al2O3 were prepared by sequential application of metals: Au/ Al2O3 cata lyst was prepared by the anion adsorption technique, the second metal was applied by impregnation of cal cined Au/ Al2O3 from aqueous solution of Ni(NO3)2. Catalysts were prepared on acidic and superacidic supports 23%Ni/FAl2O3, 23%Ni/B2O3Al2O3, and 23%Ni/SZrO2. The samples were prepared by mois ture capacity impregnation of adequate supports with Ni(NO3)2 6H2O solution followed by drying at 110C for 2 h and calcinations at 350C for 5 h. Preparation of FAl2O3 (2.4 wt % of F) In 100 ml of distilled water at 9095C (H2O : Al molar ratio = 100), 11.56 g of Al(C3H7O)3 was dis solved. The mixture was continuously stirred for 1 h. Then 3.9 ml of 1 M HNO3 (HNO3 : Al molar ratio = 0.07) was added, and the resultant mixture was stirred at 9095C for 30 min. NH4F (0.194 g) was dissolved in 20 ml of distilled water, and added dropwise for 30 min under stirring of the sol. The resultant sol was stirred at 9095C for 2 h. Then water was removed on a rotary evaporator at 65C, the resultant product was left to dry overnight at 120C, and then calcined at 600C in air flow (~300 ml/min) for 2 h. The temper ature was increased from room temperature to 600C with a ramp of 1C/min. Preparation of B2O3Al2O3 (10 wt % of B2O3) The procedure of preparation of B2O3Al2O3 is analogous to that adopted for FAl2O3. Al(C3H7O)3 (11.56 g) and H3BO3 (0.264 g) were used as precursors.

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Preparation of SO4 /ZrO2 (5 wt % of SO 4 ) In 2 l of distilled water, 60 g of ZrO(NO3)2 x(H2O) was dissolved. The mixture was continuously stirred with a mechanical stirrer for 2 h. The precipitate was removed from the resultant solution using a paper fil ter. Then 60 ml of 12.5% aqueous solution of NH3 was added dropwise until pH reached 9, and it was stirred for 3 h and left overnight. The precipitate was washed with distilled water until pH reached 7, the resultant product was dried at 100C for 24 h. Afterwards, 9.7 g of 13% aqueous solution of H2SO4 was added by mois ture capacity impregnation, and the mixture was kept at room temperature for 3 h under periodic stirring. The product was dried at 110C for 36 h and then cal cined in air flow (~300 ml/min). The temperature was increased from room temperature to 200C with 1C/min increment. Then the sample was kept at 200C for 1 h, heated to 550C with the rate of 1C/min, and kept at this temperature for 3 h. Before the reaction was conducted, the catalyst samples had been reduced for 2 h in a reactor in hydro gen flow at 500C. (1) The reaction was conducted in the reactor, a quartz tube 7 mm in diameter with a thermocouple pocket. The catalyst load was 1 cm3. We used 85% aqueous solution of glycerol as a substrate, which was fed into the reactor by a plunger pump with the rate of 2.2 g/h (1.8 ml/min). A separator to isolate gas from liquid products and unreacted glycerol was installed at the reactor outlet. The amount of gas forming was measured using a gas meter, while liquid products were collected into a receiving trap. The activity was determined under temperature increase from 520C with the rate of 50C/min, the operation time at each temperature was 2 h with fur ther temperature elevation for 0.5 h. (2) Gaseous products were analyzed on a model 3700 chromatograph equipped with two packed col umns, Hayesep Q (for separation of CO + H2, CH4, CO2, C2H4, C2H6, and C3H8) and 5 nm molecular sieves (for separation of H2, CH4, and CO). The anal ysis was carried out in isothermal mode at 55C using a conductivity detector. Glycerol conversion was determined by two inde pendent methods: calculation (by measuring the amount of gas with specific composition formed) and also by the chromatographic method of absolute cali bration by analyzing liquid products using a plasma polarization detector and an SE 54 column in isother mal mode at 200C. RESULTS AND DISCUSSION The table lists the data on glycerol conversion and content and ratio of H2 and CO in gas mixtures at the reactor outlet for all catalysts studied at 520720C. In the reaction of steam conversion of glycerol, the glycerol : H2O ratio was not altered, the standard in

biodiesel production ratio of 1was used. It should be noted that even under the standard ratio of compo nents of the raw mixture, screening of nickel catalysts on supports of different types has shown an apprecia ble difference thereof both in terms of activity and selectivity toward different gases (C3H8O3 + H2O = 2CO + CO2 + 5H2) formed in the reaction, which allows one to make a series of conclusions on the rea sonability of using a particular catalyst specimen for selective hydrogen production or syngas production for further methanol synthesis. Sample nos. 8 and 9 (see table) containing 23% Ni based on FAl2O3 and B2O3Al2O3 showed an appre ciably high activity, which was continuously increasing with rising temperature. Glycerol conversion attains 9899% at 670C. The selectivity toward H2 on these catalysts at low temperature (520C) is the highest of all samples under study (~73%), corresponding to the glycerol conversion of 4648%. Therefore, these cat alysts can be regarded as promising catalysts for selec tive production of H2. For further use in methanol syn thesis, the samples have less potential, since, at low temperatures, they promote methanation (up to 10 12 vol % of CH4), and a considerable amount of CO2 is observed in the gas. For sample no. 2 (5%Ni/TiO2) over the entire tem perature range studied, the low glycerol conversion was observed with a low H2 to CO ratio (1.85), which makes the reaction gas inefficient for use in methanol synthesis. Moreover, the selectivity toward hydrogen is less than 55%. In discussion of the results, one should take notice of the stability of the catalysts in the reaction. For instance, for sample no. 10 (see table) the glycerol conversion considerably decreases with temperature risen from 570 to 620C. A large amount (up to 5 6 vol %) of C2C3 olefinic hydrocarbons is formed in gaseous reaction products, while high molecular ole finic hydrocarbons are present in the form of resins within liquid catalysate. The use of a superacidic sup port (SO4ZrO2) seems to have an adverse effect on the catalyst stability in the reaction. The same pattern of decrease in activity with tem perature rising from 620 to 670C is observed for sam ple no. 3 (see table) probably also due to the increased formation of low molecular olefins and coke forma tion at high temperature as a result of olefin oligomer ization. However, at a lower temperature (520 570C), the amount of olefins in the gas was no higher than 1%, which facilitated the enhancement of cata lyst stability; the gas forming complied with the requirements for methanol synthesis. An increase in nickel content to 30% (sample no. 1, see table) results in the fact that, as early as at 570C, the almost com plete conversion of glycerol is observed; however, the selectivity toward hydrogen appreciably decreases as compared with sample no. 3 (see table), CO2 and CH4 being formed in large amounts.
CATALYSIS IN INDUSTRY Vol. 2 No. 2 2010

STEAM CONVERSION OF GLYCEROL ON Ni AND AuNi CATALYSTS Data on the conversion of 85% aqueous glycerol solution on heterogeneous catalysts Content, vol % of the gas mixture Sample No. 1 No. 2 Catalyst 30% Ni/Al2O3 (solgel) 5% Ni/TiO2 t, C CO 520 570 520 570 620 520 570 620 670 520 570 620 670 720 520 570 620 670 520 570 620 670 520 520 570 620 670 520 570 620 670 520 570 620 26.4 23.2 33.1 33.5 30.6 18.5 24.5 27.0 26.3 3.7 6.0 10.0 18.8 19.6 33.6 29.8 34.1 28.0 39.6 34.8 32.9 30.9 26.0 3.3 10.0 15.6 20.1 3.6 10.5 15.2 20.3 25.1 30.2 24.5 H2 35.8 46.5 45.0 55.7 55.3 61.1 59.4 63.3 55.7 42.2 52.7 59.3 58.2 62.9 54.2 56.5 55.9 58.3 45.0 49.7 50.6 49.1 51.6 73.2 62.9 64.5 67.0 72.9 62.4 64.6 69.2 45.9 47.8 48.1 CO2 18.2 15.9 7.7 5.0 6.0 12.2 11.9 4.4 5.4 24.4 20.4 15.7 10.7 7.8 1.6 3.2 2.9 4.0 8.0 6.6 4.9 4.0 14.2 13.6 15.1 11.9 7.6 13.6 14.8 12.2 6.5 12.1 6.0 8.4 CH4 19.0 13.8 6.2 2.7 4.6 6.0 1.5 1.3 5.2 29.7 20.7 13.2 7.4 4.7 1.8 2.8 3.1 4.0 4.0 4.3 5.3 6.0 2.8 10.0 11.4 6.3 3.2 9.9 11.7 6.6 1.9 7.7 8.6 9.6 C2 0.1 0.2 3.7 1.4 1.9 0.4 0.4 0.7 4.4 0.0 0.0 0.0 0.0 0.0 2.4 1.1 0.9 1.7 2.5 2.7 2.6 3.7 4.2 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 4.9 3.8 4.2 C3+ 0.5 0.4 4.4 1.8 1.6 1.8 2.4 3.3 3.1 0.0 0.2 1.8 5.0 5.0 6.5 6.5 3.1 4.1 0.9 1.9 3.6 6.4 1.3 0.0 0.6 1.6 2.0 0.0 0.0 1.3 2.0 4.3 3.6 5.2 Conver sion, % 67.3 95.1 31.6 39.8 50.7 47.9 56.1 66 45.3 69.5 84 87.4 99.7 99.6 57.6 67.1 70.3 74.6 16.5 29.2 46.5 59.2 5.4 46.4 64.7 84.5 98 46.1 66.7 86.5 98.8 25.3 41.1 32.7

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H2/CO 1.4 2.0 1.4 1.7 1.85 3.3 2.4 2.3 2.1 11.4 8.8 6.0 3.1 3.2 1.6 1.9 1.6 2.1 1.2 1.4 1.5 1.6 2.0 22.5 6.3 4.1 3.3 20.3 6.0 4.3 3.4 1.8 1.6 2.0

No. 3

10% Ni/Al2O3 (solgel)

No. 4

65% Ni/SiO2Al2O3 (Aldrich)

No. 5

0.27% Au0.09% Ni/Al2O3

No. 6

0.4% Ni/Al2O3

No. 7 No. 8

1.68% Au/Al2O3 23% Ni/FAl2O3

No. 9

23% Ni/B2O3Al2O3

No. 10 23% Ni/SO4ZrO2

Commercial hydrogenation catalyst with high Ni content 65%Ni/alumosilicate appeared to be compa rable in terms of activity with the sample on a support prepared by the sol gel technique; however, CO2 and CH4 content in the gas mixture at 520C is also very high, 25 and 30%, respectively. CO2 and CH4 content decreases with temperature increasing, and at 720C amounts to 8 and 5%, respectively. Only in a high tem perature range (above 720C) glycerol conversion
CATALYSIS IN INDUSTRY Vol. 2 No. 2 2010

(approximately 100%) and syngas composition com ply with the requirements for methanol synthesis. Special attention should be paid to the behavior of the bimetallic catalyst (sample 5, see table) in the reac tion. Regardless of such low content of metals (Ni + Au), the catalyst exhibits very high activity. The glyc erol conversion on it at 570C attains 6768%, low methane and CO2 contents being observed in gas com position under H2 to CO ratio close to 2, which makes the syngas formed well suited for further methanol

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production. Monometallic Au containing sample no. 7 (see table) is virtually inactive in the reaction, while monometallic sample no. 6 (see table) exhibits moderate activity, i.e., a strongly expressed synergetic effect is observed in the same way as in [10]. CONCLUSIONS A systematic screening of Ni catalysts in the reac tion of steam conversion of aqueous glycerol, a side product formed in biodiesel production, was con ducted. The purpose was to obtain syngas and/or hydrogen for further use as raw material for Fischer Tropsch synthesis of methanol or hydrocarbons. The screening of Ni catalysts on supports of differ ent types has revealed appreciably different activity and selectivity toward gases formed in the reaction, which allows one to make a series of conclusions on the reasonability of using a particular catalyst sample for selective production of hydrogen or production of syngas for further methanol synthesis. The selectivity toward H2 on Ni catalysts applied on FAl2O3 and B2O3Al2O3 was ascertained to be ~73% even at temperatures as low as 520C, glycerol conversion amounting to 4648%; therefore, it is rea sonably safe to regard the catalysts as promising for selective production of H2. At moderate temperature (520570C), syngas formed on catalysts 30%NiAl2O3, which were pre pared using the sol gen technique, complies with the requirements of methanol synthesis upon almost com plete conversion of glycerol. For the bimetallic catalyst 0.27%Au0.09%Ni/Al2O3, a strongly pronounced synergetic effect is observed. At 570C, glycerol conversion is as high as 6768%, and low methane and CO2 content is noted in the gas com position at H2 to CO ratio close to two, which makes the syngas formed quite suitable for methanol produc tion.

The catalysts studied in this work can be used for the process of steam conversion at lower temperatures as compared with the known catalysts. REFERENCES
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