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  • Open Access

Upgrading oxygenated Fischer-Tropsch derivatives and one-step direct synthesis of ethyl acetate from ethanol - examples of the desirability of research on simple chemical compounds transformations

Chemistry Central Journal20148:77

https://doi.org/10.1186/s13065-014-0077-9

  • Received: 14 July 2014
  • Accepted: 11 December 2014
  • Published:

Abstract

Oxygenates formed as by-products of Fischer-Tropsch syntheses can be transformed into other Fischer-Tropsch derived oxygenates instead of treating them as unwanted chemicals. One-step direct synthesis of ethyl acetate from ethanol is feasible with the use of some heterogeneous catalysts. Despite their apparent simplicity, both transformations are discussed as targeted fields of research. Furthermore, the two concepts are justified due to the environmental protection. Arguments regarding the Fischer-Tropsch process are focused on the opportunities of the utilization of undesirable by-products. The effective striving for their utilization can make the oxygenates the targeted products of this process. Arguments regarding the one-step direct synthesis of ethyl acetate underline the environmental protection and sustainability as a less waste-generating method but, above all, highlight the possibility of reducing the glycerol overproduction problem. The production of ethyl acetate from bioethanol and then transesterification of fats and oils with the use of ethyl acetate allows managing all the renewable raw materials. Thus, the process enables the biosynthesis of biodiesel without glycerine by-product and potentially would result in the increase in the demand for ethyl acetate.
Graphical Abstract image
Graphical Abstract

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Keywords

  • Fischer-Tropsch
  • Oxygenates
  • Ethyl acetate
  • Bioethanol
  • Primary alcohols
  • Biodiesel

Introduction

Oxygenates are organic oxygen compounds – common oxygenated hydrocarbon derivatives. Their definition is vague although intuitively obvious – e.g. simple ethers rather than sugars. Therefore, it can be thought that simple research on transformation of oxygenates is inexpedient as it has already been performed and is generally known while the research work has moved towards more advanced structures. It is true only to certain extent. The purposefulness of the studies on transformations of certain oxygenates into other ones is justified by dynamic changes in their interdependence. In order to visualize the purposefulness of studies on the catalytic conversion of oxygenates some examples are presented hereinafter.

Here is a simple model showing why even advanced studies concerning a simple issue require some modifications over time.

In the following sequence:
hydrocarbon alcohol aldehyde ester or any other derivative
(1)

aldehydes are more highly-processed and more highly-oxidized products than alcohols. Numerous methods of oxidation or dehydrogenation of alcohols to aldehydes have been developed, especially the key ones, including catalysts, some of which are almost perfect. However, the answer to the question whether it is worth to obtain all aldehydes from alcohols or, in other words, whether it is worth to convert all alcohols into aldehydes, is “no”.

Accordingly, the research on the development of the catalytic transformations of simple oxygenates may have new motivation. The efforts to minimize the side formation of oxygenates as “unfavourable” for Fischer-Tropsch products may be abandoned in favor of the intentional exploitation of these compounds. Additionally, even uncomplicated methods of ethyl ethanoate synthesis can be replaced with even simpler, direct ones.

Review

Non-schematic catalytic transformations

Obtaining formaldehyde from methanol is an exemplary and important process in which the following sequence (1) trend is maintained. This process can be carried on silver or oxide catalysts. It can take place by dehydrogenation, oxidative dehydrogenation [1]-[3] or, optionally, by steam reforming [4]. However, seven decades ago, “oxo synthesis” or “oxo process“ occurred. It is a homogeneously catalysed hydroformylation process [5], i.e. the synthesis of aldehydes from alkenes and carbon monoxide. In particular, the hydroformylation of propylene can result in two isomeric products, butyraldehyde or isobutyraldehyde. This is the basic industrial synthesis of aldehydes. Thus, these aldehydes are cheaper than the alcohols related to them. As a consequence, these aldehydes are hydrogenated to alcohols, n-butanol and isobutanol [6]. Regular butyraldehyde, unlike isobutyraldehyde, is also transformed into 2-ethylhexanol in a sequence involving aldol condensation reaction followed by hydrogenation of the aldol product [6]. Isobutyraldehyde is sometimes regarded as a less valuable isomer [7]. A more versatile option is the tandem of hydroformylation and hydrogenation of alkene to alcohol [8].

The direction of conversion is opposite to that in sequence (1) - alcohols are obtained from aldehydes. Of course, there are many examples of new developments of reactions differing from the scheme of gradual oxidation: hydrocarbon into alcohol, alcohol into aldehyde, and so on:

- the above hydroformylation [9];

- Reppe reaction related to carbonylation is also used on the industrial scale [10];

- the Kucherov reaction, replaced by the Wacker process (also known as the Hoechst-Wacker process), i.e. method for the production of acetaldehyde via the direct oxidation of ethylene in an aqueous medium [11];

- acetic acid is obtained on the industrial scale through the carbonylation of methanol obtained from the synthesis gas (Monsanto process) [12];

- this family includes also a group of hydrocarbonylation reactions, i.e. homologation [13]. The homologation reaction is any chemical reaction that converts the reactant into the next member of the homologous series that differs by a constant unit, generally the methylene group. An example of this is the synthesis of higher alcohols [14],[15];

- in turn, the family of bimolecular condensations includes, inter alia, the Guerbet reaction, which consists in converting a primary aliphatic alcohol into its β-alkylated dimer alcohol accompanied by dehydration, e.g. ethanol to n-butanol, n-butanol to 2-ethylhexanol [16]-[24].

The purpose of the above examples is to illustrate the diversity of the seemingly similar situations and their specificity as well as to prove that "the only correct" direction of transformation of oxygenates does not exist.

Hence, the purposefulness of the work on any particular transformation of oxygenates depends on a whole range of market factors. First of all, this work comes down to the development of an active and selective catalyst. The complexity of such an undertaking includes important concepts concerning the catalysis. Many factors are significant at the same time. There is no point in discussing them individually here or even in trying to rank them. Such complexity indicates that designing the optimal solution for a specific, desired transformation, i.e. both preparation of a catalyst and the course of this transformation, will not facilitate the execution of other tasks, even closely related ones, because of the multitude of significant factors and the multitude of interdependencies. The variation of such interdependencies does not have to be linear so extrapolations and interpolations are not always effective. Another conclusion is that the number of factors to define a specific process excludes a random selection of catalyst components.

It may happen that the understanding of phenomena brings useful generalizations. In the 1920s Taylor deduced that since a catalyst can be completely poisoned by such a little amount of poison that it is able to cover only a small fraction of the catalyst surface it means that the active participants in the reaction are only certain groups of atoms on the surface [25]. In such a concept the active centres must differ from each other to meet different requirements. The same groups of atoms do not have to be active centres of various transformations. In another reaction, considering different requirements of reagents, other groups of atoms can perform the functions of centres on the same surface. There are many types of centres but their definitions are not entirely consistent. Apart from proving their presence and identifying their type it is advisable to estimate their number and power. The catalytic act itself may take different courses [26]. The basic generalizations include the Langmuir-Hinshelwood model from the 1920s where both reagents activated with adsorption on the surface reacted with each other, the Eley-Rideal model from the 1930s where one of the reagents adsorbed on the surface became an easy target for another reagent attacking from the atmosphere, and the Mars-van Krevelen model from the 1950s in which the catalyst’s oxygen participated actively and the gap after it had to be filled in to enable the next act.

The above differentiated mechanisms relate to the catalyst per se. Catalytically active materials are often affixed to the catalyst support due to their high surface area and saving of the valuable materials. Additionally, quite a while ago, the boundary between the actual catalyst and the catalytic support began to blur. Tauster found the strong metal-support interaction (SMSI effect) [27] predicted much earlier by Schwab [28].

Fischer-Tropsch derived oxygenates

Coming back to the main problem of the dependence of the justification of transformation of oxygenates on variable conditions, a new attitude regarding the products of the Fischer-Tropsch synthesis should be noted. The F-T synthesis is a technology developed in the 1920s, which consists in producing liquid fuels from any carbon materials other than petroleum. This is a technology related to that used much earlier than F-T, in tar and charcoal manufactories by tar makers and charcoal burners. Disregarding the details of gas names definitions (wood distillation gas, generator gas, coke-oven gas, town gas, water gas, or synthesis gas) from any carbon material: wood, coal, biomass, natural gas [29]-[32] (including shale gas [33]), and even better with the participation of water vapour, sometimes also oxygen, it is possible to obtain gases containing carbon monoxide and hydrogen in various proportions and also other components as a result of gasification, reforming or pyrolysis. It is possible to separate hydrogen from such gases and they are suitable for syntheses of hydrocarbons, i.e. liquid fuels but also for chemical syntheses, e.g. syntheses of methanol and higher alcohols [34]-[41]. Alcohols can be the source of hydrogen after dehydrogenation. The alcohols may also be subject to transformations to other oxygenates or hydrocarbons.

During such syntheses, oxygenates are formed as by-products quantitatively and qualitatively depending on numerous factors [42]-[54]. These relationships have usually been the subject of research. Especially important is the impact of the presence of oxygenates on the course of the process and possibility to manipulate the product spectrum by selective addition of oxygenates [55]-[61]. Therefore, there are two possibilities: treat them as unwanted products [62]-[64] and try to reduce their amount or to strive for their utilization [65]-[73], also by the use of new technologies, such as membrane separations [74]-[76]. Oxygenates can be transformed into other oxygenates or into hydrocarbons through hydrogenation. Two important coupling reactions for the upgrading of monofunctional oxygenated compounds are ketonization and aldol condensation/hydrogenation [77],[78]. The conversion of oxygenates into hydrocarbons, which are lower-processed products, may seem pointless. However, it may be an attractive direction if we have redundant oxygenates [42],[79] and if we avoid other expensive treatments such as separation or costly attempts to improve selectivity in this way. There is also the option of steam reforming [80]. Thus, oxygenates need not be a nuisance. They can be seen as a source of intermediates for value-added chemicals [81]-[85].

It is a popular opinion that the Fischer-Tropsch technology has survived only in the RSA because of the isolation of this country. This is truth but not ultimate. This technology has been developed, inter alia, in the United States, Uzbekistan, Russia and China as an alternative technology [33]. Thus, the current uproar about the underground coal gasification is much late. Since 1944 a few large plants for the F-T process have been built in the United States under the Synthetic Liquid Fuels program and they still exist as a form of strategic reserve [86].

There are several reasons for the renaissance of the Fischer-Tropsch technology. One of them is the return to the abandoned idea of using hydrogen for transport but in a different aspect. Steam reforming of natural gas, i.e. the equivalent of the coal gasification process as well as the coal gasification itself can be the sources of hydrogen. Also other chemical processes such as catalytic processes of dehydrogenation of alcohols and WGSR (Water Gas Shift Reaction) can be the sources of hydrogen.

The WGSR is the most important side reaction of the Fischer-Tropsch synthesis [87],[88] of hydrocarbons or methanol from – it should be reminded here – carbon monoxide and, after all, hydrogen. The whole point is that water is also the product of these transformations and WGSR allows hydrogen recovery. Of course, WGSR is also used as an independent reaction, unrelated to F-T.

– The increase in demand for methanol is also an important trigger. In the chemical industry worldwide there is no other product with such a mass and multi-directional use as methanol. It is an irreplaceable intermediate product for the syntheses of many chemicals, in particular formaldehyde and various related products. Methanol is also the main base for the production of top quality petrol and diesel fuels. It can be added, blended, in significant volumes, directly to petrol fuels [89] or transformed into dimethyl ether [90], a diesel fuel substitute crucial for the Methanol-to-Gasoline (MTG) and Methanol-to-Olefin (MTO) processes. The use of methanol as a component in the transesterification of triglycerides to yield a form of biodiesel [91] may become widespread to the extent similar to obtaining ethanol from biomass. Methanol is already used today on a large scale (the global demand for methanol is around 60 million ton per year [92]) and the forecasts for the average annual growth in the methanol production are estimated to be high. Along with the development of fuel cells, methanol will become a strategic resource. The Blasiak’s concept is therefore constantly evolving [93]-[97].

– The reason is also the return to the concept of using heavier fuels of natural origin. It is also a comeback, because the first diesel engine built by Rudolf Diesel was fuelled by peanut oil and such was the original intention.

Despite these facts, the preparations for the return of the Fischer-Tropsch technology proceeded slowly. This was explained by the adverse financial situation resulting from the significant decline in oil prices, which reduced the competitiveness of coal fuels in relation to petroleum fuels. The current price fluctuations emphasize the purposefulness of long-term studies in this field. May the dim prospects for shale gas not overshadow this opportunity and not be the cause of another failure to develop chemical technologies based on coal resources.

Ethyl acetate from ethanol

Another example of a new approach to transformation of a simple oxygenate is the concept of a single-stage production of ethyl acetate. Of course, the idea of primary alcohols transformation into esters had to appear during the development of organic chemistry [98] as a result of the next step of dehydrogenation of alcohols and of the earlier step of Tishchenko reaction. However, publications on the one-step direct synthesis of esters from primary alcohols with the use of heterogeneous catalysts are not numerous and are of technical reports character. Nevertheless, among the patented methods of ethyl acetate production only the achievement of the Davy Process (Kvaerner Process Technology, Sasol Chemical Industries) [99] is close to the idea. For instance, the process of Chinese National Petroleum, described in the Chemical Weekly [100], is related to a one-step process of transformation of ethanol into ethyl acetate; however, by the partial oxidation of ethanol to acetic acid and successive esterification by the excess of ethanol. In relation to other more complicated transformations, this relatively simple one is described rather poorly [76],[101]-[118]. Of course, there is a different option that illustrates the variability of the research directions – as mentioned at the beginning – the elaboration of ethyl acetate hydrogenation to ethanol [119],[120].

While observing that literature announcements on primary alcohols conversion over metal oxide containing heterogeneous catalysts are focused on the dehydration to ethers and alkenes or dehydrogenation to aldehydes, the both reactions are so popular that may be even treated as tests for acidity and basicity of the surface. However, some catalysts are able to perform a secondary condensation of created aldehydes to ketones containing 2n-1 carbon atoms in aliphatic chain [55],[56],[121]-[125], where n stands for the number of C atoms in n-alcohol undergoing the conversion. These catalysts are capable of triggering the following reaction chain:
2 R C H 2 O H 2 RCHO RCOOC H 2 R RCOR
(2)

In the reports in literature about this group of transformations there is a large divergence of views as to the route of the reaction. Among others, there are suggested pathways via aldol, via aldol and secondary alcohol, simultaneously via ester and aldol, via hemiacetal and ester, or aldol with a parallel hydrogen transfer reaction [126]-[128]. This secondary reaction is not always intentional [129]. During the alkylation of phenol [130] with alcohols higher than methanol the competitive reaction can occur: bimolecular condensation of primary alcohols to ketones containing 2n-1 carbon atoms [124],[131],[132]. Ketonization of primary alcohols, and consequently aldehydes and esters, allows the synthesis of symmetrical and unsymmetrical ketones [133],[134] and expands possibilities of utilization of such materials [134],[135]. This transformation is akin to the bimolecular ketonization of monocarboxylic acids [136]-[141], which is much more frequently described in the literature. The suitable oxide catalysts are applied in the bulk form or are often deposited on various supports, including materials of natural origin [142]-[144].

Most of the catalysts of dehydrogenative character transform primary alcohols only to aldehydes and less often to symmetric ketones. Excessive overrun of conversion optimal conditions leads to possible degradation products. Nevertheless, the proper selection of control parameters allows obtaining esters as major conversion products. Obviously, such a termination of the transformation at the ester stage is effective only with respect to specific catalysts.

The important incentive, impetus to intensify the research on the termination of the course of bimolecular condensation of primary alcohols in the ester phase is the potential increase in the ethyl acetate demand. The major driving force for that demand originates from the search for new energy sources which would be renewable and “clean” – not causing additional carbon dioxide emission. Biomass derived fuels meet these expectations and can partly replace fossil fuels. Diesel oil substitute – biodiesel – is one of them. Ethyl acetate can be used in some methods of biodiesel production. Biodiesel synthesis with the use of ethyl acetate is an attractive option because of the possibility of reducing the glycerol overproduction problem [145]. The majority of methods of the conversion of fatty materials (including rapeseed oil) to fuel components is fraught with side formation of glycerol, according to the scheme:
triglyceride + alcohol fatty acid ester + glycerol
(3)

Glycerol overproduction as well as the problems with its utilization initiate the search for new methods of its management. The use of ethyl acetate instead of alcohol in the process of cross transesterification of triglycerides in the Gliperol process is an example of such projects [146].

In this case the transformation of fats follows the scheme:
triglyceride + ethyl acetate fatty acid ethyl ester + glycerol triacetate
(4)

Glycerol triacetate (triacetin) does not require the separation from the final product as it improves biofuel combustion conditions [147]. Besides, ethyl esters have better fuel properties than methyl esters (including higher heating value, incomplete combustion products free from formaldehyde, a lower freezing point) [148]. The transesterification of fats and oils with the use of ethyl acetate allows managing all the renewable raw materials (including glycerine) for fuel production. It is therefore a very attractive method for the manufacture of the fuel components. However, one of the factors restricting its wider application is ethyl acetate deficiency in the market (ethyl acetate is widely used in industry [149] and the production methods have some disadvantages [150]-[152]: multistage processes and necessity of the catalyst separation require a complicated system of tanks and equipment, raw materials cause corrosion, whereas acetaldehyde is strongly toxic (Fischer esterification – catalyst: sulfuric acid, p-toluenesulfonic acid, Tishchenko condensation of acetaldehyde – catalyst: aluminum triethoxide, condensation of acetic acid with ethylene – catalyst: bentonites, heteropolyacids)).

Changes in the fuel market, including the strong drive towards the idea of using ethanol and, consequently, a large increase in the production of bioethanol, are consistent with this concept. Thus, ethyl alcohol can be a cheap, renewable resource for the production of ethyl acetate [153]. The concept of using ethyl acetate in the process of transesterification of oils and fats is also consistent with the increased production of rapeseed oil and with the increase in demand for transesterified oils. In addition, besides the potential demand for ethyl acetate and the availability of bioethanol, the technical simplicity of implementation of such a transformation due to few media and accompanying materials and the reduction of the amount of noxious by-products as compared to traditional methods of ethyl acetate production should be emphasized. Such a solution is convergent with ecological trends towards new technologies in order to increase the share of renewable materials in the overall fuel balance. Moreover, the method meets the requirements of green chemistry and is consistent with the principles of sustainable development.

Conclusions

Research on the development of catalytic transformations of simple oxygenates is still justified. New market conditions make the production and processing of oxygenates as part of the Fischer-Tropsch synthesis purposeful. On the other hand, the increase in the potential demand for ethyl acetate against the background of high availability of ethanol justifies further research on a direct one-step catalytic synthesis of this ester.

Declarations

Acknowledgement

The present elaboration is a secondary consequence of Project N R05 0088 10.

Authors’ Affiliations

(1)
Institute of Low Temperature and Structure Research, Polish Academy of Sciences, Okólna 2, Wrocław, 50-422, Poland

References

  1. Usachev NY, Krukovskii IM, Kanaev SA: The nonoxidative methanol dehydrogenation to formaldehyde: (A review). Pet Chem. 2004, 44: 379-394.Google Scholar
  2. Isaguliants GV, Belomestnykh IP: Selective oxidation of methanol to formaldehyde over V-Mg-O catalysts. Catal Today. 2005, 100: 441-445.Google Scholar
  3. Klimkiewicz R: Przemysłowe odwodornianie metanolu na formaldehyd wobec katalizatorów srebrowych. Wiad Chem. 1977, 31: 713-728.Google Scholar
  4. Boucher MB, Marcinkowski MD, Liriano ML, Murphy CJ, Lewis EA, Jewell AD, Mattera MF, Kyriakou G, Flytzani-Stephanopoulos M, Sykes EC: Molecular-scale perspective of water-catalyzed methanol dehydrogenation to formaldehyde. ACS Nano. 2013, 7: 6181-6187.Google Scholar
  5. Franke R, Selent D, Börner A: Applied hydroformylation. Chem Rev. 2012, 112: 5675-5732.Google Scholar
  6. Tudor R, Ashley M: Enhancement of industrial hydroformylation processes by the adoption of rhodium-based catalyst: Part I. Platinum Met Rev. 2007, 51: 116-126.Google Scholar
  7. Klimkiewicz R, Morawski I, Syper L, Biskupski A, Teterycz H: Aldehyd izomasłowy potencjalnym surowcem do ketonizacji. Przem Chem. 2003, 82: 608-610.Google Scholar
  8. Hanna DG, Shylesh S, Parada PA, Bell AT: Hydrogenation of butanal over silica-supported Shvo’s catalyst and its use for the gas-phase conversion of propene to butanol via tandem hydroformylation and hydrogenation. J Catal. 2014, 311: 52-58.Google Scholar
  9. Fonseca Y, Fontal B, Reyes M, Suárez T, Bellandi F, Díaz JC, Cancines P: Synthesis, characterization and hydroformylation catalytic activity of 1-hexene of water-soluble RuCl 2(DMSO) 2(PySO 3Na) 2complex. Av Quim 2012, 7:27–33.,Google Scholar
  10. Uzcátegui GC, Hung F, Ortega MC, Pardey AJ, Longo C, Aguirre P, Moya SA: Reppe reaction catalyzed by soluble carbonylrhodium complexes. J Chil Chem Soc. 2005, 50: 647-650.Google Scholar
  11. Ponomarev DA, Shevchenko SM: Hydration of acetylene: A 125th anniversary. J Chem Educ. 2007, 84: 1725-1726.Google Scholar
  12. Sano K, Uchida H, Wakabayashi S: A new process for acetic acid production by direct oxidation of ethylene. Catal Surv Jpn. 1999, 3: 55-60.Google Scholar
  13. Tatsumi T, Muramatsu A, Yokota K, Tominga H: Mechanistic study on the alcohol synthesis over molybdenum catalysts: Addition of probe molecules to CO-H 2. J Catal 1989, 115:388–398.,Google Scholar
  14. Chen MJ, Feder HM, Rathke JW: A general homogeneous catalytic method for the homologation of methanol to ethanol. J Am Chem Soc. 1982, 104: 7346-7347.Google Scholar
  15. Chen MJ, Rathke JW: Homologation of Methanol Catalyzed by Manganese Carbonyl in Alkali-Metal Formate-Methanol Solutions. Organometallics. 1987, 6: 1833-1838.Google Scholar
  16. Sun J, Wang Y: Recent advances in catalytic conversion of ethanol to chemicals. ACS Catal. 2014, 4: 1078-1090.Google Scholar
  17. Ndou AS, Plint N, Coville NJ: Dimerisation of ethanol to butanol over solid-base catalysts. Appl Catal A Gen. 2003, 251: 337-345.Google Scholar
  18. Zhang F-y, Liu Y-j, Fan M-g, Ma L, Li J-l, Li B: Performance of ethanol to n-butanal and n-butanol over Cu-substituted LaMnO3 catalyst. Fine Chemicals. 2011, 2: 135-140.Google Scholar
  19. Riittonen T, Toukoniitty E, Madnani DK, Leino A-R, Kordas K, Szabo M, Sapi A, Arve K, Wärnå J, Mikkola J-P: One-pot liquid-phase catalytic conversion of ethanol to 1-butanol over aluminium oxide—the effect of the active metal on the selectivity. Catalysts. 2012, 2: 68-84.Google Scholar
  20. Carvalho DL, de Avillez RR, Rodrigues MT, Borges LEP, Appel LG: Mg and Al mixed oxides and the synthesis of n-butanol from ethanol. Appl Catal A Gen. 2012, 415–416: 96-100.Google Scholar
  21. Patel AD, Telalović S, Bitter JH, Worrell E, Patel MK: Analysis of sustainability metrics and application to the catalytic production of higher alcohols from ethanol. Catal Today. 2015, 239: 56-79.Google Scholar
  22. Carlini C, Macinai A, Raspolli Galletti AM, Sbrana G: Selective synthesis of 2-ethyl-1-hexanol from n-butanol through the Guerbet reaction by using bifunctional catalysts based on copper or palladium precursors and sodium butoxide. J Mol Catal A Chem. 2004, 212: 65-70.Google Scholar
  23. Hemo E, Virduk R, Landau MV, Herskowitz M: Biogasoline and high alcohols production by one step ethanol conversion on densified MgO catalyst with enhanced concentration of surface active sites. Chem Eng Trans. 2010, 21: 1243-1248.Google Scholar
  24. Kozlowski JT, Davis RJ: Sodium modification of zirconia catalysts for ethanol coupling to 1-butanol. J Energy Chem. 2013, 22: 58-64.Google Scholar
  25. Taylor HS: A Theory of the catalytic surface. Proc R Soc Lond A. 1925, 108: 105-111.Google Scholar
  26. Ilyas M, Sadiq M: Liquid phase aerobic oxidation of benzyl alcohol catalyzed by Pt/ZrO 2. Chem Eng Technol 2007, 30:1391–1397.,Google Scholar
  27. Tauster SJ, Fung SC, Garten RL: Strong metal-support interactions. Group 8 noble metals supported on titanium dioxide. J Am Chem Soc. 1978, 100: 170-175.Google Scholar
  28. Schwab GM: Catalytic effects on the surface of semiconductors supported by metals. Surf Sci. 1969, 13: 198-200.Google Scholar
  29. Kiennemann A, Hindermann J-P: Chapter 4: Heterogeneous Carbon Monoxide Hydrogenation. Stud Surf Sci Catal. 1988, 35: 181-256.Google Scholar
  30. de Klerk A: Fischer–Tropsch fuels refinery design. Energy Environ Sci. 2011, 4: 1177-1205.Google Scholar
  31. Demirbas A: Progress and recent trends in biofuels. Prog Energ Combust Sci. 2007, 33: 1-18.Google Scholar
  32. Yang J, Ma W, Chen D, Holmen A, Davis BH: Fischer–Tropsch synthesis: A review of the effect of CO conversion on methane selectivity. Appl Catal A Gen. 2014, 470: 250-260.Google Scholar
  33. Wood DA, Nwaoha C, Towler BF: Gas-to-liquids (GTL): A review of an industry offering several routes for monetizing natural gas. J Nat Gas Sci Eng. 2012, 9: 196-208.Google Scholar
  34. Gall D, Gibson EJ, Hall CC: The distribution of alcohols in the products of the fischer-tropsch synthesis. J Appl Chem. 1952, 2: 371-380.Google Scholar
  35. Xiaoding X, Doesburg EBM, Scholten JJF: Synthesis of higher alcohols from syngas - recently patented catalysts and tentative ideas on the mechanism. Catal Today. 1987, 2: 125-170.Google Scholar
  36. Ishida T, Yanagihara T, Liu X, Ohashi H, Hamasaki A, Honma T, Oji H, Yokoyama T, Tokunaga M: Synthesis of higher alcohols by Fischer–Tropsch synthesis over alkali metal-modified cobalt catalysts. Appl Catal A Gen. 2013, 458: 145-154.Google Scholar
  37. Bao Z, Xiao K, Qi X, Wang X, Zhong L, Fang K, Lin M, Sun Y: Higher alcohol synthesis over Cu-Fe composite oxides with high selectivity to C2 + OH. J Energy Chem. 2013, 22: 107-113.Google Scholar
  38. Majocchi L, Lietti L, Beretta A, Forzatti P, Micheli E, Tagliabue L: Synthesis of short chain alcohols over a Cs-promoted Cu/ZnO/Cr2O3 catalyst. Appl Catal A Gen. 1998, 166: 393-405.Google Scholar
  39. Lu Y, Yu F, Hu J, Liu J: Catalytic conversion of syngas to mixed alcohols over Zn-Mn promoted Cu-Fe based catalyst. Appl Catal A Gen. 2012, 429–430: 48-58.Google Scholar
  40. Xiao K, Bao Z, Qi X, Wang X, Zhong L, Lin M, Fang K, Sun Y: Unsupported CuFe bimetallic nanoparticles for higher alcohol synthesis via syngas. Catal Comm. 2013, 40: 154-157.Google Scholar
  41. Yin K, Shou H, Ferrari D, Jones CW, Davis RJ: Influence of cobalt on rubidium-promoted alumina-supported molybdenum carbide catalysts for higher alcohol synthesis from syngas. Top Catal. 2013, 56: 1740-1751.Google Scholar
  42. Leckel D: Diesel production from Fischer-Tropsch: The past, the present, and new concepts. Energy Fuel. 2009, 23: 2342-2358.Google Scholar
  43. Dry ME: The Fischer–Tropsch process: 1950–2000. Catal Today. 2002, 71: 227-241.Google Scholar
  44. Kellner CS, Bell AT: Synthesis of oxygenated products from carbon monoxide and hydrogen over silica- and alumina-supported ruthenium catalysts. J Catal. 1981, 71: 288-295.Google Scholar
  45. Juan A, Damiani DE: Supported Ru-Mo catalysts for syngas reaction to oxygenates. J Catal. 1992, 137: 77-91.Google Scholar
  46. Gaube J, Klein H-F: Studies on the reaction mechanism of the Fischer–Tropsch synthesis on iron and cobalt. J Mol Catal A Chem. 2008, 283: 60-68.Google Scholar
  47. Mao W-y, Sun Q-w, Ying W-y, Fang D-y: Mechanism of oxygenates formation in high temperature Fischer-Tropsch synthesis over the precipitated iron-based catalysts. J Fuel Chem Technol. 2013, 41: 314-321.Google Scholar
  48. Zhang X, Liu Y, Liu G, Tao K, Jin Q, Meng F, Wang D, Tsubaki N: Product distributions including hydrocarbon and oxygenates of Fischer–Tropsch synthesis over mesoporous MnO2-supported Fe catalyst. Fuel. 2012, 92: 122-129.Google Scholar
  49. Zhang Q, Kang J, Wang Y: Development of novel catalysts for Fischer–Tropsch synthesis: Tuning the product selectivity. ChemCatChem. 2010, 2: 1030-1058.Google Scholar
  50. Schulz H: Short history and present trends of Fischer–Tropsch synthesis. Appl Catal A Gen. 1999, 186: 3-12.Google Scholar
  51. Mahdavi V, Peyrovi MH: Synthesis of C1–C6 alcohols over copper/cobalt catalysts Investigation of the influence of preparative procedures on the activity and selectivity of Cu–Co2O3/ZnO, Al2O3 catalyst. Catal Commun. 2006, 7: 542-549.Google Scholar
  52. Chaumette P, Courty P, Kiennemann A, Kieffer R, Boujana S, Martin GA, Dalmon J-A, Meriaudeau P, Mirodatos C, Hölhein B, Mausbeck D, Hubert AJ, Germain A, Noels A: Evolution of alcohol synthesis catalysts under syngas. Ind Eng Chem Res. 1994, 33: 1460-1467.Google Scholar
  53. Gnanamani MK, Jacobs G, Shafer WD, Ribeiro MC, Pendyala VRR, Ma W, Davis BH: Fischer Tropsch synthesis: Deuterium isotopic study for the formation of oxygenates over CeO2 supported Pt–Co catalysts. Catal Commun. 2012, 25: 12-17.Google Scholar
  54. Spivey JJ, Egbebi A: Heterogeneous catalytic synthesis of ethanol from biomass-derived syngas. Chem Soc Rev. 2007, 36: 1514-1528.Google Scholar
  55. Wang Y, Davis BH: Fischer-Tropsch synthesis. Conversion of alcohols over iron oxide and iron carbide catalysts. Appl Catal A Gen. 1999, 180: 277-285.Google Scholar
  56. Davis BH: Fischer–Tropsch synthesis: current mechanism and futuristic needs. Fuel Process Technol. 2001, 71: 157-166.Google Scholar
  57. Chuang SSC, Stevens RW, Khatri R: Mechanism of C2+ oxygenate synthesis on Rh catalysts. Top Catal. 2005, 32: 225-232.Google Scholar
  58. de Klerk A: Effect of oxygenates on the Oligomerization of Fischer-Tropsch olefins over amorphous silica-alumina. Energy Fuels 2007, 21:625-632.Google Scholar
  59. Yao F-F, Wu B-S, Zhou L-P, Gao J-H, Li Y, Li Y-W: Effect of alcohol addition on Fischer-Tropsch synthesis over cobalt-based catalysts. Acta Phys -Chim Sin. 2013, 29: 1063-1072.Google Scholar
  60. Leckel D: Selectivity effect of oxygenates in hydrocracking of Fischer-Tropsch waxes. Energy Fuels. 2007, 21: 662-667.Google Scholar
  61. Leckel D: Upgrading of Fischer-Tropsch products to produce diesel. Haldor Topsøe Catalysis Forum, Sasol Technology Research and Development, FTR and C1 Chemistry Research, Munkerupgaard, August 2010.Google Scholar
  62. Mortensen PM, Grunwaldt J-D J-D, Jensen PA, Knudsen KG, Jensen AD: A review of catalytic upgrading of bio-oil to engine fuels. Appl Catal A Gen. 2011, 407: 1-19.Google Scholar
  63. Vosloo AC: Fischer–Tropsch: a futuristic view. Fuel Process Technol. 2001, 71: 149-155.Google Scholar
  64. de Klerk A: Environmentally friendly refining: Fischer–Tropsch versus crude oil. Green Chem. 2007, 9: 560-565.Google Scholar
  65. Gnanamani MK, Ribeiro MC, Ma W, Shafer WD, Jacobs G, Graham UM, Davis BH: Fischer–Tropsch synthesis: Metal–support interfacial contact governs oxygenates selectivity over CeO 2supported Pt–Co catalysts. Appl Catal A Gen 2011, 393:17–23.,Google Scholar
  66. Lunsford JH: Catalytic conversion of methane to more useful chemicals and fuels: a challenge for the 21st century. Catal Today. 2000, 63: 165-174.Google Scholar
  67. Gharibi M, Zangeneh FT, Yaripour F, Sahebdelfar S: Nanocatalysts for conversion of natural gas to liquid fuels and petrochemical feedstocks. Appl Catal A Gen. 2012, 443–444: 8-26.Google Scholar
  68. Subramani V, Gangwal SK: A review of recent literature to search for an efficient catalytic process for the conversion of syngas to ethanol. Energy Fuels. 2008, 22: 814-839.Google Scholar
  69. Klimkiewicz R: Możliwości pozyskiwania organicznych związków tlenowych w wyniku zgazowania węgla. Górnictwo Odkrywkowe. 2014, 55: 90-94.Google Scholar
  70. Wender I: Reactions of synthesis gas. Fuel Process Technol. 1996, 48: 189-297.Google Scholar
  71. Graham UM, Jacobs G, Gnanamani M, Lipka S, Shafer WD, Swartz C, Jermwongratanachai T, Chen R, Rogers F, Davis BH: Fischer Tropsch synthesis: High oxygenate-selectivity of cobalt catalysts supported on hydrothermal carbons. ACS Catal. 2014, 4: 1662-1672.Google Scholar
  72. Tsai Y-T, Mo X, Goodwin JG: The synthesis of hydrocarbons and oxygenates during CO hydrogenation on CoCuZnO catalysts: Analysis at the site level using multiproduct SSITKA. J Catal. 2012, 285: 242-250.Google Scholar
  73. Herman RG: Advances in catalytic synthesis and utilization of higher alcohols. Catal Today. 2000, 55: 233-245.Google Scholar
  74. Iglesia E: Challenges and progress in the conversion of natural gas to fuels and chemicals. Fuel Chem Div Prepr. 2002, 47: 128-131.Google Scholar
  75. Iglesia E: Challenges and progress in the conversion of natural gas to fuels and chemicals. Prepr Pap-Am Chem Soc, Div Fuel Chem. 2004, 49: 49-50.Google Scholar
  76. Sánchez AB, Homs N, Miachon S, Dalmon J-A, Fierro JLG, de la Piscina PR: Direct transformation of ethanol into ethyl acetate through catalytic membranes containing Pd or Pd-Zn: comparison with conventional supported catalysts. Green Chem. 2011, 13: 2569-2575.Google Scholar
  77. Gürbüz EI, Kunkes EL, Dumesic JA: Integration of C–C coupling reactions of biomass-derived oxygenates to fuel-grade compounds. Appl Catal B Environ. 2010, 94: 134-141.Google Scholar
  78. Alonso DM, Bond JQ, Dumesic JA: Catalytic conversion of biomass to biofuels. Green Chem. 2010, 12: 1493-1513.Google Scholar
  79. Prasomsri T, Nimmanwudipong T, Román-Leshkov Y: Effective hydrodeoxygenation of biomass-derived oxygenates into unsaturated hydrocarbons by MoO 3using low H 2pressures. Energy Environ Sci 2013, 6:1732–1738.,Google Scholar
  80. Trane-Restrup R, Resasco DE, Degn Jensen A: Steam reforming of light oxygenates. Catal Sci Technol. 2013, 3: 3292-3302.Google Scholar
  81. Quek X-Y, Guan Y, van Santen RA, Hensen EJM: Unprecedented oxygenate selectivity in aqueous-phase Fischer–Tropsch synthesis by ruthenium nanoparticles. ChemCatChem. 2011, 3: 1735-1738.Google Scholar
  82. Dry ME: Fischer–Tropsch reactions and the environment. Appl Catal A Gen. 1999, 189: 185-190.Google Scholar
  83. Dry ME: Practical and theoretical aspects of the catalytic Fischer-Tropsch process. Appl Catal A Gen. 1996, 138: 319-344.Google Scholar
  84. Xiao K, Bao Z, Qi X, Wang X, Zhong L, Fang K, Lin M, Sun Y: Advances in bifunctional catalysis for higher alcohol synthesis from syngas. Chin J Catal. 2013, 34: 116-129.Google Scholar
  85. Fang KG, Li DB, Lin MG, Xiang ML, Wei W, Sun YH: A short review of heterogeneous catalytic process for mixed alcohols synthesis via syngas. Catals Today. 2009, 147: 133-138.Google Scholar
  86. Andrews A: Oil Shale: History, Incentives, and Policy. CRS Report for Congress, Congressional Research Service, Library of Congress, Washington, 2006, Document No. RL33359; http://www.fas.org/sgp/crs/misc/RL33359.pdf,
  87. Jacobs G, Ma W, Davis BH: Influence of reduction promoters on stability of cobalt/γ-alumina Fischer-Tropsch synthesis catalysts. Catalysts. 2014, 4: 49-76.Google Scholar
  88. Jermwongratanachai T, Jacobs G, Ma W, Shafer WD, Gnanamani MK, Gao P, Kitiyanan B, Davis BH, Klettlinger JLS, Yen CH, Cronauer DC, Kropf AJ, Marshall CL: Fischer–Tropsch synthesis: Comparisons between Pt and Ag promoted Co/Al2O3 catalysts for reducibility, local atomic structure, catalytic activity, and oxidation–reduction (OR) cycles. Appl Catal A Gen. 2013, 464–465: 165-180.Google Scholar
  89. Tarun T, Thamotharan C, Naveenchandran P: Performance of methanol blended diesel fuels in twin cylinder diesel engine. Middle-East J Sci Res. 2013, 17: 1775-1778.Google Scholar
  90. Varisli D, Tokay KC, Ciftci A, Dogu T, Dogu G: Methanol dehydration reaction to produce clean diesel alternative dimethylether over mesoporous aluminosilicate-based catalysts. Turk J Chem. 2009, 33: 355-366.Google Scholar
  91. Meher LC, Vidya Sagar D, Naik SN: Technical aspects of biodiesel production by transesterification – a review. Renew Sustain Energy Rev. 2006, 10: 248-268.Google Scholar
  92. Olah G, Prakash GKS, Goeppert A: Anthropogenic chemical carbon cycle for a sustainable future. J Am Chem Soc. 2011, 133: 12881-12898.Google Scholar
  93. Blasiak E: Sposób wytwarzania wysokoaktywnego katalizatora do syntezy metanolu. Polish Patent 34000 1947 (Błasiak E: PL 34000 B1, Urząd Patentowy Rzeczypospolitej Polskiej 1947; Wiadomości Urzędu Patentowego 1950).Google Scholar
  94. Cybulski A: Liquid-phase methanol synthesis: catalysts, mechanism, kinetics, chemical equilibria, vapor-liquid equilibria, and modeling—A Review. Catal Rev Sci Eng. 1994, 36: 557-615.Google Scholar
  95. Skrzypek J, Lachowska M, Grzesik M, Słoczyński J, Nowak P: Thermodynamics and kinetics of low pressure methanol synthesis. Chem Eng J. 1995, 58: 101-108.Google Scholar
  96. Ledakowicz S, Nowicki L, Petera J, Nizioł J, Kowalik P, Gołębiowski A: Kinetic characterisation of catalysts for methanol synthesis. Chem Proc Eng. 2013, 34: 497-506.Google Scholar
  97. Riaz A, Zahedi G, Klemeš JJ: A review of cleaner production methods for the manufacture of methanol. J Clean Prod. 2013, 57: 19-37.Google Scholar
  98. Keyes DB: Esterification processes and equipment. Ind Eng Chem. 1932, 24: 1096-1103.Google Scholar
  99. Colley SW, Tabatabaei J, Waugh KC, Wood MA: The detailed kinetics and mechanism of ethyl ethanoate synthesis over a Cu/Cr 2O 3catalyst. J Catal 2005, 236:21–33.,Google Scholar
  100. Dutia P: Ethyl acetate: A techno-commercial profile. Chemical Weekly. 2004, 49: 179-186.Google Scholar
  101. Colley SW; Tuck MWM: Ethyl ethanoate synthesis by ethanol dehydrogenation. In Catalysis in application. Edited by Jackson SD, Hargreaves JSJ, Lennon D. Royal Society of Chemistry: Cambridge; 2003:101-107.Google Scholar
  102. Inui K, Kurabayashi T, Sato S, Ichikawa N: Effective formation of ethyl acetate from ethanol over Cu-Zn-Zr-Al-O catalyst. J Mol Catal A: Chem. 2004, 216: 147-156.Google Scholar
  103. Sánchez AB, Homs N, Fierro JLG, de la Piscina PR: New supported Pd catalysts for the direct transformation of ethanol to ethyl acetate under medium pressure conditions. Catal Today. 2005, 107–108: 431-435.Google Scholar
  104. Gaspar AB, Esteves AML, Mendes FMT, Barbosa FG, Appel LG: Chemicals from ethanol – The ethyl acetate one-pot synthesis. Appl Catal A Gen. 2009, 363: 109-114.Google Scholar
  105. Santacesaria E, Carotenuto G, Tesser R, Di Serio M: Ethanol dehydrogenation to ethyl acetate by using copper and copper chromite catalysts. Chem Eng J. 2012, 179: 209-220.Google Scholar
  106. Santacesaria E, Di Serio M, Tesser R, Carotenuto G: Process for the production of ethyl-acetate from ethanol. WO 2011104738 A2 Eurochem Engineering S.R.L. 2011.Google Scholar
  107. R. Klimkiewicz, J. Trawczyński, Katalizator do katalitycznego przetwarzania alkoholu etylowego oraz sposób jego wytwarzania, Polish patent application P393737, 2011; Klimkiewicz R., Trawczyński J: Sposób wytwarzania octanu etylu. Polish patent 215884 2011.Google Scholar
  108. Pattanaik BN, Mandalia HC: Ethyl acetate: properties, production processes and applications - A review. IJCRR. 2011, 03: 23-40.Google Scholar
  109. Tang Q-H, Wei Z-W, Wang J, Zhao H-R, Zhao P-Z: Direct Synthesis of Ethyl Acetate from Ethanol over Cu-Zr-Co-O Catalysts. Petrochem Technol. 2013, 7: 780-786.Google Scholar
  110. Zonetti PC, Celnik J, Letichevsky S, Gaspar AB, Appel LG: Chemicals from ethanol – The dehydrogenative route of the ethyl acetate one-pot synthesis. J Mol Catal A Chem. 2011, 334: 29-34.Google Scholar
  111. Gaspar AB, Barbosa FB, Letichevsky S, Appel LG: The one-pot ethyl acetate syntheses: The role of the support in the oxidative and the dehydrogenative routes. Appl Catal A Gen. 2010, 380: 113-117.Google Scholar
  112. Yu X, Zhu W-C, Gao S, Chen L-L, Yuan H-J, Luo J-H, Wang Z-L, Zhang W-X: Transformation of ethanol to ethyl acetate over Cu/SiO2 catalysts modified by ZrO2. Chem Res Chin Univ. 2013, 29: 986-990.Google Scholar
  113. Xiaofei L, Haoxi J, Guiming L, Minhua Z: Investigation of Cu-Based catalyst for direct synthesis of ethyl acetate from ethanol: improvement of thermal stability of Cu–Cr–Zr composite oxide catalyst by addition of Mn promoter. Ind Eng Chem Res. 2012, 51: 8974-8978.Google Scholar
  114. Minhua Z, Guiming L, Haoxi J, Jiyan Z: Investigation on process mechanism on Cu–Cr catalysts for ethanol dehydrogenation to ethyl acetate. Catal Lett. 2011, 141: 1104-1110.Google Scholar
  115. Wang LX, Zheng DF, Ma CX, Zhu WC, Liu SY, Cui J, Wang ZL, Zhang WX: Direct transformation of ethanol to ethyl acetate over MoSx/C catalyst. Polish J Chem. 2009, 83: 1993-2000.Google Scholar
  116. Men’shchikov VA, Gol’dshtein LK, Semenov IP: Kinetics of ethanol dehydrogenation into ethyl acetate. Kinet Catal. 2014, 55: 12-17.Google Scholar
  117. Inui K, Kurabayashi T, Sato S: Direct synthesis of ethyl acetate from ethanol carried out under pressure. J Catal. 2002, 212: 207-215.Google Scholar
  118. Sato AG, Volanti DP, de Freitas IC, Longo E, Bueno JMC: Site-selective ethanol conversion over supported copper catalysts. Catal Commun. 2012, 26: 122-126.Google Scholar
  119. Zhu Y-m; Shi XWL: Hydrogenation of ethyl acetate to ethanol over bimetallic Cu-Zn/SiO2 catalysts prepared by means of coprecipitation. Bull Korean Chem Soc 2014, 35:141- 146.Google Scholar
  120. Zhang B, Lin L, Zhuang J, Liu Y, Peng L, Jiang L: Hydrogenation of ethyl acetate to ethanol over Ni-based catalysts obtained from Ni/Al hydrotalcite-like compounds. Molecules. 2010, 15: 5139-5152.Google Scholar
  121. Bloomfield G, Swallen LG, Crawford FM: Method of producing ketones. US1978404 A Commercial Solvents Corp US patent 1934.Google Scholar
  122. Plint N, Ghavalas D, Vally T, Sokolovski VD, Coville NJ: Catalysed synthesis of 4-heptanone from 1-butanol. Catal Today. 1999, 49: 71-77.Google Scholar
  123. Plint ND, Coville NJ, Lack D, Nattrass GL, Vallay T: The catalysed synthesis of symmetrical ketones from alcohols. J Mol Catal A Chem. 2001, 165: 275-281.Google Scholar
  124. Vivier L, Duprez D: Ceria-based solid catalysts for organic chemistry. ChemSusChem. 2010, 3: 654-678.Google Scholar
  125. Kamimura Y, Sato S, Takahashi R, Sodesawa T, Fukui M: Vapor-phase synthesis of symmetric ketone from alcohol over CeO2-Fe2O3 catalysts. Chem Lett. 2000, 29: 232-233.Google Scholar
  126. Grabowska H, Klimkiewicz R: Reactions of n-butanol in the presence of dehydrogenating iron catalyst. Pol J Chem. 1998, 72: 141-145.Google Scholar
  127. Klimkiewicz R: Primary alcohols, aldehydes and ester transformations into ketones over oxide catalysts. Pol J Environ Stud. 2008, 17: 727-731.Google Scholar
  128. Rodrigues CP, Zonetti PC, Silva CG, Gaspar AB, Appel LG: Chemicals from ethanol—The acetone one-pot synthesis. Appl Catal A: Gen. 2013, 458: 111-118.Google Scholar
  129. Jyothi Y, Vakati V, Satyanarayana T, Veerasomaiah P: Gas phase dehydrogenation of n-butanol to butyraldehyde on magnesia supported copper catalysts. Indian J Chem. 2014, 53A: 553-556.Google Scholar
  130. Żukowski W, Berkowicz G, Baron J, Kandefer S, Jamanek D, Szarlik S, Wielgosz Z, Zielecka M: Selective phenol methylation to 2,6-dimethylphenol in a fluidized bed of iron-chromium mixed oxide catalyst with o–cresol circulation. Chem Cent J. 2014, 8: 51-Google Scholar
  131. Wrzyszcz J, Grabowska H, Klimkiewicz R, Syper L: Reactions of normal alcohols in the presence of a dehydrogenating iron catalyst. Catal Lett. 1998, 54: 55-58.Google Scholar
  132. Klimkiewicz R, Grabowska H, Teterycz H: Sn–Ce–Rh–O monophase system as a new type of ortho-selective catalyst for phenol alkylation. Appl Catal A Gen. 2003, 246: 125-136.Google Scholar
  133. Klimkiewicz R, Grabowska H, Syper L: Ketonization of long-chain esters. Pol J Environ Stud. 2000, 9: 179-181.Google Scholar
  134. Klimkiewicz R, Grabowska H, Syper L: Oil industry waste as a basis for synthesis of new type surfactants. Pol J Environ Stud. 2001, 10: 337-339.Google Scholar
  135. Klimkiewicz R, Grabowska H, Teterycz H: Application of Zr-Mg-Y-O catalyst for ketonization of ester and alcohol type industrial wastes. Pol J Environ Stud. 2003, 12: 67-71.Google Scholar
  136. Gliński M, Zalewski G, Burno E, Jerzak A: Catalytic ketonization over metal oxide catalysts. XIII. Comparative measurements of activity of oxides of 32 chemical elements in ketonization of propanoic acid. Appl Catal A Gen. 2014, 470: 278-284.Google Scholar
  137. Pham TN, Sooknoi T, Crossley SP, Resasco DE: Ketonization of carboxylic acids: mechanisms, catalysts, and implications for biomass conversion. ACS Catal. 2013, 3: 2456-2473.Google Scholar
  138. Zaytseva YA, Panchenko VN, Simonov MN, Shutilov AA, Zenkovets GA, Renz M, Simakova IL, Parmon VN: Effect of gas atmosphere on catalytic behaviour of zirconia, ceria and ceria–zirconia catalysts in valeric acid ketonization. Top Catal. 2013, 56: 846-855.Google Scholar
  139. Nagashima O, Sato S, Takahashi R, Sodesawa T: Ketonization of carboxylic acids over CeO2-based composite oxides. J Mol Catal A Chem. 2005, 227: 231-239.Google Scholar
  140. Gliński M, Kijeński J: Catalytic ketonization of carboxylic acids synthesis of saturated and unsaturated ketones. React Kinet Catal Lett. 2000, 69: 123-128.Google Scholar
  141. Renz M: Ketonization of carboxylic acids by decarboxylation: Mechanism and scope. Eur J Org Chem. 2005, 6: 979-988.Google Scholar
  142. Cyganiuk A, Klimkiewicz R, Olejniczak A, Lukaszewicz JP: Biotechnological fabrication of LaMnO3 -carbon catalyst for n -butanol conversion to ketones. catalyst for n -butanol conversion to ketones. Carbon. 2010, 48: 99-106.Google Scholar
  143. Łukaszewicz JP, Wesołowski RP, Cyganiuk A: Enrichment of Salix viminalis wood in metal ions by means phytoextraction. Pol J Environ Stud. 2009, 18: 507-511.Google Scholar
  144. Cyganiuk AW, Klimkiewicz R, Olejniczak A, Kucińska A, Łukaszewicz JP: Nanoscale phenomena occurring during pyrolysis of Salix viminalis wood. J Materials. 2013, 2013: 1-9.Google Scholar
  145. ten Dam J, Hanefeld U: Renewable chemicals: Dehydroxylation of glycerol and polyols. ChemSusChem. 2011, 4: 1017-1034.Google Scholar
  146. Kijeński J, Różycki K, Lipkowski AW, Walisiewicz-Niedbalska W: Nowe biopaliwo estrowe Gliperol®. Przem Chem. 2007, 86: 269-272.Google Scholar
  147. Rao PV, Rao BA: Performance and emission characteristics of diesel engine with COME-Triacetin additive blends as fuel. Int J Energy Enviorn. 2012, 3: 629-638.Google Scholar
  148. Kołodziej H, Piętak A, Struś M, Vogt A: Properties of biofuels with ethyl components to diesel engines. J Kones. 2006, 13: 139-145.Google Scholar
  149. Nielsen M, Junge H, Kammer A, Beller M: Towards a green process for bulk-scale synthesis of ethyl acetate: Efficient acceptorless dehydrogenation of ethanol. Angew Chem Int Ed. 2012, 51: 5711-5713.Google Scholar
  150. Sato T, Hagiwara T: Production of ester. Tokuyama Sekiyu Kagaku K.K., Japan. Kokai Tokkyo Koho, JP 11140017, 1999.Google Scholar
  151. Giwa A, Giwa SO, Bayram I, Karacan S: Simulations and economic analyses of ethyl acetate productions by conventional and reactive distillation processes using aspen plus. Int J Eng Res & Technol. 2013, 2: 594-605.Google Scholar
  152. Gregory R, Smith DJH, Westlake DJ: The production of ethyl acetate from ethylene and acetic acid using clay catalysts. Clay Miner. 1983, 18: 431-435.Google Scholar
  153. Carotenuto G, Tesser R, Di Serio M, Santacesaria E: Bioethanol as feedstock for chemicals such as acetaldehyde, ethyl acetate and pure hydrogen. Biomass Conv Bioref. 2013, 3: 55-67.Google Scholar

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