Hydrogenolysis of Aqueous Glycerol over Raney ... - ACS Publications

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Hydrogenolysis of Aqueous Glycerol over Raney Nickel Catalyst: Comparison of Pure and Biodiesel By-Product Halit L. Hoşgün,*,† Mehmet Yıldız,† and H. Ferdi Gerçel‡ †

Department of Chemical Engineering, Eskişehir Osmangazi University, 26480, Meşelik, Eskişehir, Turkey Department of Chemical Engineering, Anadolu University, Ik̇ i Eylül Campus, 26470, Eskişehir, Turkey

‡

ABSTRACT: The hydrogenolysis of pure and biodiesel byproduct glycerol in the presence of Raney nickel catalyst using an autoclave was studied. The effects of stirring speed, temperature, amount of catalyst, H2 pressure, and glycerol content on the conversion of glycerol, the yield of liquid products, and the selectivity of 1,2-propanediol were investigated, and the results were compared to chemically pure glycerol and crude glycerol from biodiesel production. All the experimental results obtained from the use of crude glycerol from biodiesel production were close to those obtained from the use of chemically pure glycerol. The highest conversion of glycerol (80%) was achieved under the conditions of 35 g catalyst L−1 solution, 20% glycerol content, 40 bar H2 pressure, 400 rpm stirring speed, and 230 °C temperature for the chemically pure glycerol. In order to reach the highest liquid products yield (95%) and the 1,2-propanediol selectivity (54%), the catalyst amount was decreased from 35 g catalyst L−1 solution to 7 g catalyst L−1 solution while the other conditions were unchanged. On the other hand, the highest conversion of glycerol (74%) and the highest selectivity of 1,2-propanediol (50%) for the crude glycerol were obtained under the same reaction conditions with those obtained in the use of chemically pure glycerol while the liquid products yield was 74% under the reaction conditions of 21 g catalyst/L solution, 20% glycerol content, 40 bar H2 pressure, 400 rpm stirring speed, and 200 °C temperature. According to the obtained results, increasing the temperature and amount of catalyst led to the increase in the glycerol conversion and decrease in the liquid products yield and in the 1,2-propanediol selectivity. The glycerol conversion decreased and the liquid products yield and the 1,2-propanediol selectivity increased with the increasing hydrogen pressure.

1. INTRODUCTION Today, the energy demand and the consumption have been increasing with the growing human population. The reserves of the fossil fuels, coal, oil, and natural gas, which currently dominate in the energy market, are being consumed.1 Shafiee and Topal2 have proposed according to their model that the oil, coal, and natural gas will run out in approximately 35, 107, and 37 years, respectively. Investigations on renewable energy sources as alternatives to fossil fuels have gained a growing importance due to the environmental concerns and sustainability as well as the depletion of resources. Biodiesel is a bio-based fuel which is used in diesel engines, and its use increases continuously because it has some significant advantages such as renewability, biodegradability, and nontoxicity. Furthermore, the use of biodiesel results in lower particular matter emissions without any modification in engines. Thus the use of biodiesel all over the world is increasing steadily day by day. The transesterification reaction between triglycerides and methanol over the basic catalysts, as shown in the equation below, produces biodiesel and byproduct glycerol.3,4

produced for every 9 kg of biodiesel synthesized. The increased production of biodiesel has resulted in the large surplus of glycerol. Thus, the glycerol price has dropped in the market.6,7 As a feedstock, glycerol can be converted to value-added chemicals. A number of reactions such as acetalization,8,9 dehydration,10,11 esterification,12,13 etherification,14,15 aqueous phase reforming,16,17 and oxidation18,19 have been studied for the evaluation of byproduct glycerol by several research groups. One of the possible transformations of glycerol is hydrogenolysis. Glycerol reacts with hydrogen to produce 1,2propanediol (1,2-PD), 1,3-propanediol (1,3-PD), and ethylene glycol (EG) in the presence of metallic catalysts.20 The reactions between glycerol and hydrogen can be written as follows:

Two reaction pathways have been proposed in the literature for the hydrogenolysis of glycerol. Montassier et al.21 suggested that the reaction consists of three steps: dehydrogenation, dehydroxylation, and hydrogenation. Glyceraldehyde is formed as an intermediate product. Dasari et al.22 proposed a dehydration-hydrogenation mechanism for glycerol hydro-

1 mol triglycerides + 3 mol alcohol ⇌ 3 mol fatty acid methyl ester + 1 mol glycerol (biodiesel)

(1)

The worldwide commercial use of biodiesel has increased rapidly. In EU countries, biodiesel production has increased 9 times from 2002 to 2009.5 According to the transesterification reaction stoichiometry, approximately 1 kg of glycerol is © 2012 American Chemical Society

Received: Revised: Accepted: Published: 3863

August 10, 2011 January 12, 2012 February 10, 2012 February 10, 2012 dx.doi.org/10.1021/ie201781q | Ind. Eng. Chem. Res. 2012, 51, 3863−3869

Industrial & Engineering Chemistry Research

Article

genolysis. In this mechanism, glycerol was dehydrated and acetol was formed as an intermediate. 1,2-PD was produced by hydrogenation of acetol. Maris and Davis23 highlighted the importance of the water content in the glycerol solution for the dehydration step. They reported that acetol was not detected at low glycerol concentration. On the contrary, 80% glycerol solution was used and acetol was detected in the study of Dasari et al.22 On the other hand, Lahr and Shanks24 investigated the kinetics of the reaction of glycerol hydrogenolysis in the presence of Ru/C catalyst under the basic conditions. The reaction mixture consists of glycerol and glycols (ethylene glycol, 1,2-PD) or their combination. They developed a kinetic model based on Langmuir−Hinshelwood mechanism. According to that study, hydrogenolysis reaction was affected by pH. The hydrogenolysis of glycerol has been studied by several researchers25−32 in the presence of different metallic, bimetallic, and mixed oxide catalysts. Especially ruthenium and copper stand in the forefront of the metals.33−45 Among the noble metals, Ru based catalysts showed better activity, but Ru caused too much C−C bond cleavages. Cu based catalysts also gave better activity; in addition, they caused selective C−O bond cleavages without C−C bond cleavages.46 On the other hand, Raney nickel is also used in hydrogenation reaction as catalyst.47−49 Raney nickel catalyst has been investigated for the hydrogenolysis of glycerol under high temperature and low H2 pressure conditions by Perosa and Tundo.50 They reported that 190 °C was the optimum temperature and 1,3-PD was not observed. They reached 97% glycerol conversion and 71% 1,2PD selectivity after 44 h reaction time. The crude glycerol produced from the biodiesel process has some impurities like excess methanol, water from the washing procedure, and salts formed after neutralization. The use of glycerol as a renewable feedstock requires high purity, and the purification procedures for crude glycerol are costly.51,52 There is no study in the literature on hydrogenolysis of crude glycerol from biodiesel production over Raney nickel catalyst. The aim of this work is to compare the hydrogenolysis reactions of the chemically pure glycerol (CPG) and the crude glycerol from biodiesel production (CGBP) with respect to the glycerol conversion, the liquid products yield, and the 1,2-PD selectivity over the Raney nickel catalysts. Additionally, the effects of stirring speed, temperature, amount of catalysts, H2 pressure, and glycerol content on the conversion of glycerol, the yield of liquid products, and the selectivity of 1,2-PD were examined for both hydrogenolysis reactions.

Figure 1. Steps of byproduct glycerol purification.

a typical experiment, the catalyst and 80 mL of aqueous glycerol solution were loaded into the reactor. The autoclave was purged with nitrogen for removal of air. Then hydrogen was fed to the system. When the desired temperature was reached, a sample was taken. This moment has been noted as an initial time of reaction. In order to investigate the reaction parameters, one parameter was changed while the others were kept constant. At the end of the 9 h reaction time, the reactor was cooled to room temperature. A small portion of the reaction mixture was centrifuged for removing the catalyst. 2.3. Analysis. Liquid products were analyzed by GC (Agilent, model 6890; Santa Clara, CA, USA) and GC-MS (Agilent, model 5975; Santa Clara, CA, USA). A HPINNOWAX column (30 m × 0.32 mm ×0.25 μm; J&W Scientific, California, USA) was used for separation of components. 1-Butanol was used as the internal standard, and acetone was used as the solvent in the preparation of samples for analysis. The inlet and detector temperatures were 250 and 280 °C, respectively, and the split ratio was 10:1. The following oven temperature program was applied: 1 min at 50 °C, 10 min at 100 °C with 5 °C/min heating rate, and 1 min 250 °C with the rate of 20 °C/min. The amounts of gas phase products were calculated from a material balance. 2.4. Calculations. Conversion of glycerol (Xg), yields of liquid products (Ylp) and selectivity of 1,2-PD (S1,2PD) were calculated as follows;

2. EXPERIMENTAL SECTION 2.1. Materials. All chemicals used in this study except CGBP were analytical grade and used without further purification. CPG, 1,2-PD, ethylene glycol, and other reagents, which are used as solvent and internal standard for gas chromatography, were purchased from Merck (KGaA, Darmstadt, Germany). Hydrogen used was in high purity (99.99%). The Raney Nickel catalyst was also purchased from Merck (KGaA, Darmstadt, Germany). CGBP was supplied from Biodiesel Research Laboratory at Dumlupınar University, Kütahya, Turkey. The purification procedure of CGBP is shown in Figure 1. 2.2. Apparatus and Procedure. All hydrogenolysis reactions of glycerol were carried out in a 160 mL stainless steel autoclave (Parr, model: 4360; Parr Instrument Company, Illinois, USA) equipped with stirrer, heater, and sample port. In

Xg =

Amount of consumed glycerol Amount of initial glycerol

(5)

Ylp =

Total amount of liquid products Amount of consumed glycerol

(6)

S1,2PD =

Amount of formed 1, 2‐PD Total amount of liquid products

(7)

3. RESULTS AND DISCUSSION The achieved results showed that the glycerol conversion, liquid products yield, and 1,2-PD selectivity values obtained from the hydrogenolysis reaction of CGBP were close to those 3864

dx.doi.org/10.1021/ie201781q | Ind. Eng. Chem. Res. 2012, 51, 3863−3869


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obtained from the hydrogenolysis of CPG, although the CGBP included impurities. Meher et al. reported that the highest glycerol conversion was about 40% with 77% 1,2-PD selectivity for purified glycerol.32 In our study, 70% glycerol conversion with 30% 1,2-PD selectivity was achieved under the conditions of 35 g catalyst/L solution, 20% glycerol content, 40 bar H2 pressure, 400 rpm stirring speed, and 230 °C temperature. 3.1. Effect of Stirring Speed. The effect of stirring speed was investigated to provide the basis for the further kinetic studies. The experiments were carried out with three different stirring speeds in order to examine the effect of stirring speed on the glycerol conversion, the liquid products yield, and the 1,2-PD selectivity. According to the results shown in Figure 2,

to 65%, and the 1,2-PD selectivity increased from 23% to 33% when the stirring speed was increased from 200 to 400 rpm for CPG. 3.2. Effect of Temperature. The results for the effect of temperature are represented in Figure 3. The similar glycerol

Figure 3. Effect of temperature on the conversion of glycerol, the yields of liquid products, and the selectivity of 1,2-PD at 21 g catalyst L−1 solution, 20% glycerol content, 40 bar H2 pressure, and 400 rpm stirring speed.

conversion, the liquid products yield, and 1,2-PD selectivity values are observed for CPG and CGBP. The glycerol conversion increased from 25% to 64%, liquid products yield decreased from 78% to 50%, and 1,2-PD selectivity did not change significantly (33% to 30%) with increasing the temperature from 200 to 240 °C for CPG. The similar results were also obtained for CGBP. The results obtained in our study were in a good agreement with the literature.53,54 Magliano and He53 reported two reactions, glycerol reforming and hydrogenolysis of glycerol, which occurred simultaneously. According to the aqueous phase reforming reaction equation of glycerol, 10 mol of gaseous products were produced from 1 mol glycerol as follows:

Figure 2. Effect of stirring speed on the conversion of glycerol, the yields of liquid products, and the selectivity of 1,2-PD at 21 g catalyst L−1 solution, 20% glycerol content, 40 bar H2 pressure, and 230 °C temperature.

glycerol conversion was changed in the range of 48−52% for the hydrogenolysis of CPG with the increasing stirring speed while glycerol conversion increased from 31% to 46% for the hydrogenolysis of CGBP. The conversion values obtained for CPG at three different stirring rates were very close to each other, which mean that there is no significant external mass transfer limitation. On the other hand, the dramatic increase in the glycerol conversion for the hydrogenolysis of CGBP underlined that the external mass transfer limitations should be taken into account in the kinetic studies on the CGBP hydrogenolysis. The liquid products yield increased from 49%

C3H8O3 + 3H2O → 3CO2 + 7H2

(8)

The increase in glycerol conversion with the decrease in the liquid products yield at higher temperatures could be explained with the higher aqueous phase reforming activity than that of hydrogenolysis. It is important to note that, at higher 3865



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3.4. Effect of Amount of Catalyst. The effect of the amount of catalyst on the glycerol conversion is seen in Figure 5. The expected results were obtained. The glycerol conversion

temperatures, the methanation reaction between CO2 and H2 could reduce the activity of the hydrogenolysis reaction.55 Manfro et al.56 reported that nickel has a good activity for both water gas shift and methanation reaction. In addition, Huang et al.57 claimed that the decrease occurred in the liquid products yield by the further degradation of the liquid products via C−C cleavage at higher temperatures. 3.3. Effect of Hydrogen Pressure. Figure 4 shows the influence of the hydrogen pressure on the glycerol conversion,

Figure 5. Effect of amount of catalyst on the conversion of glycerol, the yields of liquid products, and the selectivity of 1,2-PD at 20% glycerol content, 40 bar H2 pressure, 400 rpm stirring speed, and 230 °C temperature.

increased from 23% to 80%, the liquid products yield decreased from 95% to 43%, and the 1,2-PD selectivity decreased from 54% to 23% with the increased catalyst amount from 7 g catalyst L−1 solution to 35 g catalyst L−1 solution for CPG. The experiments carried out with CGBP gave similar results. It is well-known that increasing the catalyst amount leads to an increase in the number of the active sites, and thus the conversion is enhanced. In our study, the increase in the glycerol conversion was achieved by increasing the catalyst amount. This is obviously due to the higher numbers of active sites. However, glycerol was not converted to liquid products, especially 1,2-PD. This must be due to the increased C−C cleavage by the higher nickel catalyst amount. 3.5. Effect of Glycerol Content. The effect of glycerol content on the glycerol conversion, liquid products yield, and 1,2-PD selectivity was investigated at the 10%, 20%, and 30% glycerol contents. The results are depicted in Figure 6. It is observed that, for CPG, the glycerol conversion, liquid products yield, and 1,2-PD selectivity decreased from 57% to 42%, from 72% to 54%, and from 36% to 28%, respectively, for CGBP, and the glycerol conversion, liquid products yield, and 1,2-PD

Figure 4. Effect of hydrogen pressure on the conversion of glycerol, the yields of liquid products, and the selectivity of 1,2-PD at 21 g catalyst L−1 solution, 20% glycerol content, 400 rpm stirring speed, and 230 °C temperature.

the liquid products yield, and the 1,2-PD selectivity in the range of 20−60 bar hydrogen pressure. Increasing the hydrogen pressure caused the glycerol conversion to decrease from 56% to 46%, the liquid products yield to increase from 52% to 73%, and the 1,2-PD selectivity to increase from 28% to 35% for CPG. On the contrary, the hydrogen pressure increase resulted in decreasing the glycerol conversion from 49% to 40%, increasing the liquid products yield from 39% to 52% and increasing the 1,2-PD selectivity 24% to 34% for CGBP. As discussed above, the aqueous phase reforming of glycerol and the hydrogenolysis of glycerol occurred competitively. The increase in the hydrogen pressure favored the hydrogenolysis reaction, and it leads to the increase in the liquid products yield and 1,2-PD selectivity. It was probable that a C−O cleavage occurred at higher hydrogen pressure. 3866



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highest glycerol conversion for chemically pure glycerol was 80% under the reaction conditions of 35 g catalyst L−1 solution, 20% glycerol content, 40 bar H2 pressure, 400 rpm stirring speed, and 230 °C temperature while the highest yield of liquid products and selectivity of 1,2-PD were 95% and 54%, respectively, at the conditions of 7 g catalyst L−1 solution, 20% glycerol content, 40 bar H2 pressure, 400 rpm stirring speed, and 230 °C temperature. On the contrary, for crude glycerol from biodiesel production, the highest glycerol conversion up to 74% was obtained under 35 g catalyst L−1 solution, 20% glycerol content, 40 bar H2 pressure, 400 rpm stirring speed, and 230 °C temperature conditions. The highest liquid products yield was observed as 74% under the reaction conditions of 21 g catalyst L−1 solution, 20% glycerol content, 40 bar H2 pressure, 400 rpm stirring speed, and 200 °C temperature. The 1,2-PD selectivity was 50% at the conditions of 7 g catalyst L−1 solution, 20% glycerol content, 40 bar H2 pressure, 400 rpm stirring speed, and 230 °C temperature for crude glycerol from biodiesel production. As a conclusion, the hydrogenolysis of glycerol can be achieved even by the use of crude glycerol from biodiesel production, and Raney nickel is a suitable catalyst for this reaction.

■

AUTHOR INFORMATION

Corresponding Author

*Telephone number: +902222393750. Fax number: +902222393613. E-mail address: [email protected]. Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This project was supported by The Scientific and Technological Research Council of Turkey (TUBITAK), Project Number 106M375. The authors also would like to thank Assist. Prof. Iṡ met Ç elik, Dumlupınar University, Kütahya, Turkey, for supplying of crude glycerol from biodiesel production.

Figure 6. Effect of glycerol content on the conversion of glycerol, the yields of liquid products, and the selectivity of 1,2-PD at 21 g catalyst L−1 solution, 40 bar H2 pressure, 400 rpm stirring speed, and 230 °C temperature.

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selectivity decreased from 57% to 29%, from 63% to 54%, and from 41% to 37%, respectively, as the glycerol content was increased. These results are in accordance with those obtained by Balaraju et al.39 They explained that the decrease is expected in the glycerol conversion with the increase in the initial glycerol content since the available numbers of active sites are constant.

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4. CONCLUSIONS In this study, the hydrogenolysis of chemically pure glycerol and crude glycerol from biodiesel production was studied over Raney nickel catalyst. The results obtained in this study showed that the hydrogenolysis reaction could be useful even by the use of crude glycerol from biodiesel production. The effects of reaction parameters such as stirring speed, temperature, amount of catalysts, H2 pressure, glycerol content on the glycerol conversion, the liquid products yield, and the 1,2-PD selectivity were investigated. In the presence of nickel catalyst, aqueous phase reforming of glycerol and hydrogenolysis of glycerol were conducted simultaneously. The increased catalyst amount and temperature favored the reforming reaction while H2 pressure favored the hydrogenolysis reaction. When the glycerol content was increased, the glycerol conversion and the liquid products yield were decreased since the numbers of active sites per mole of glycerol content were decreased. It was observed that the 3867



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