Pub Date : 2022-01-01DOI: 10.15407/kataliz2022.33.074
O. Fedoryshyn
The main advantages and disadvantages of solid-phase catalysts for transesterification reactions of oils with alcohols are analyzed. Tests of the sulfonated and phosphated solid - phase catalysts synthesized by us in the transesterification reaction of rapeseed oil with 96% ethanol in order to obtain biodiesel were carried out. The chemical resistance of sulfonated synthetic (S-SCS) and synthesized from natural raw materials (S-KAU) catalysts was compared. The reasons for low chemical resistance of sulfonated carbon-containing materials are determined. Synthetic S-SCS catalysts proved to be the least stable. Regeneration of phosphated samples was performed by washing the catalyst from oil residues and reaction products in a boiling solution of 0.1 M alkali, followed by repeated washing with distilled water to slightly alkaline pH. Then, after drying, the obtained material was used as a source for re-synthesis of the catalyst. The ethanolysis reaction was carried out in autoclaves under pressure at a temperature of 150-160oC with a process duration of 5-7 hours. The ratio of catalyst to starting oil was chosen 1:15 (g : ml). The oil-alcohol ratio was 3: 4, vol. The volume of the autoclave was 45 ml. The maximum conversion under these test conditions in the first cycle for sulfonated catalysts was 100%, and for phosphated - 94%. A carbon-containing catalyst on a ceramic support has been developed, which can be regenerated by firing the carbon-containing material and applying a new one. This catalyst showed the highest chemical resistance, withstanding 7 cycles, while the conversion fell by 14% (from 89 to 75%). For more efficient use of the catalyst, the scheme of flow-circulation installation of transesterification of oils and fats of biological origin with alcohols was proposed.
{"title":"Acid transesterification of oils with ethanol on carbon catalysts","authors":"O. Fedoryshyn","doi":"10.15407/kataliz2022.33.074","DOIUrl":"https://doi.org/10.15407/kataliz2022.33.074","url":null,"abstract":"The main advantages and disadvantages of solid-phase catalysts for transesterification reactions of oils with alcohols are analyzed. Tests of the sulfonated and phosphated solid - phase catalysts synthesized by us in the transesterification reaction of rapeseed oil with 96% ethanol in order to obtain biodiesel were carried out. The chemical resistance of sulfonated synthetic (S-SCS) and synthesized from natural raw materials (S-KAU) catalysts was compared. The reasons for low chemical resistance of sulfonated carbon-containing materials are determined. Synthetic S-SCS catalysts proved to be the least stable. Regeneration of phosphated samples was performed by washing the catalyst from oil residues and reaction products in a boiling solution of 0.1 M alkali, followed by repeated washing with distilled water to slightly alkaline pH. Then, after drying, the obtained material was used as a source for re-synthesis of the catalyst. The ethanolysis reaction was carried out in autoclaves under pressure at a temperature of 150-160oC with a process duration of 5-7 hours. The ratio of catalyst to starting oil was chosen 1:15 (g : ml). The oil-alcohol ratio was 3: 4, vol. The volume of the autoclave was 45 ml. The maximum conversion under these test conditions in the first cycle for sulfonated catalysts was 100%, and for phosphated - 94%. A carbon-containing catalyst on a ceramic support has been developed, which can be regenerated by firing the carbon-containing material and applying a new one. This catalyst showed the highest chemical resistance, withstanding 7 cycles, while the conversion fell by 14% (from 89 to 75%). For more efficient use of the catalyst, the scheme of flow-circulation installation of transesterification of oils and fats of biological origin with alcohols was proposed.","PeriodicalId":9649,"journal":{"name":"Catalysis and Petrochemistry","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2022-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"82201090","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2022-01-01DOI: 10.15407/kataliz2022.33.066
O. Ivanenko, T. Shabliy, Yuliia Nosachova, M.M. Kosmyna
In this article the problems associated with the corrosion processes of equipment in oil and gas production are analyzed. The basic anticorrosive methods and means used in modern conditions are considered. Taking into account the mechanism and conditions of corrosion processes in the extraction and transportation of oil-containing products and gas condensate, the chemical method of protection of the equipment was chosen for research. Both known inhibitors based on phosphonic acids and synthesized substances based on sulfonates, imidazolines, and diamines were used as chemicals in the research. As a result of the research, the effectiveness of protection of metals from corrosion depending on the composition of highly mineralized medium, metal type, inhibitor type, and its concentration was evaluated and the effectiveness of the developed scale stabilizer (sodium dimethylsulfonate phosphinate) was evalu- ated in comparison with known reagents. It is shown that the effectiveness of protection of metals from corrosion in aqueous-petroleum mixtures with alkylimidazoline inhibitors (derivatives of 4,5-dihydro-1,3-diazole or 4,5-dihydroimidazole) and inhibitors developed on the basis of sunflower oil and diethylenetriamine (AC-1), ethylenedi-amine (AC-2) reaches 90% in doses of 5 - 50 mg/dm3. In addition, corrosion processes are often accompanied by processes of deposition of hardness salts on the surface of the equipment, which leads to a significant complication in the operation of the equipment. Therefore, studies of the anti-scale properties of these reagents under harsh conditions were performed. Real concomitant gas production waters were used as the medium. It was found that sodium di-methylsulfonate phosphinate is a very effective stabilizer of scale formation and is not inferior in effectiveness to known antiscalants. The proposed reagents can be used to stabilize water-oil mixtures and associated formation waters formed during the production and transportation of oil and gas.
{"title":"Chemical means of equipment protection during oil and gas fields operation","authors":"O. Ivanenko, T. Shabliy, Yuliia Nosachova, M.M. Kosmyna","doi":"10.15407/kataliz2022.33.066","DOIUrl":"https://doi.org/10.15407/kataliz2022.33.066","url":null,"abstract":"In this article the problems associated with the corrosion processes of equipment in oil and gas production are analyzed. The basic anticorrosive methods and means used in modern conditions are considered. Taking into account the mechanism and conditions of corrosion processes in the extraction and transportation of oil-containing products and gas condensate, the chemical method of protection of the equipment was chosen for research. Both known inhibitors based on phosphonic acids and synthesized substances based on sulfonates, imidazolines, and diamines were used as chemicals in the research. As a result of the research, the effectiveness of protection of metals from corrosion depending on the composition of highly mineralized medium, metal type, inhibitor type, and its concentration was evaluated and the effectiveness of the developed scale stabilizer (sodium dimethylsulfonate phosphinate) was evalu- ated in comparison with known reagents. It is shown that the effectiveness of protection of metals from corrosion in aqueous-petroleum mixtures with alkylimidazoline inhibitors (derivatives of 4,5-dihydro-1,3-diazole or 4,5-dihydroimidazole) and inhibitors developed on the basis of sunflower oil and diethylenetriamine (AC-1), ethylenedi-amine (AC-2) reaches 90% in doses of 5 - 50 mg/dm3. In addition, corrosion processes are often accompanied by processes of deposition of hardness salts on the surface of the equipment, which leads to a significant complication in the operation of the equipment. Therefore, studies of the anti-scale properties of these reagents under harsh conditions were performed. Real concomitant gas production waters were used as the medium. It was found that sodium di-methylsulfonate phosphinate is a very effective stabilizer of scale formation and is not inferior in effectiveness to known antiscalants. The proposed reagents can be used to stabilize water-oil mixtures and associated formation waters formed during the production and transportation of oil and gas.","PeriodicalId":9649,"journal":{"name":"Catalysis and Petrochemistry","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2022-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"84838229","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2022-01-01DOI: 10.15407/kataliz2022.33.021
O. Kiziun, V. Zazhigalov
The investigation of n-butane and n-pentane oxidation in system with two consecutive reactors confirmed the mechanism of phthalic anhydride formation by Diels-Alder reaction between maleic anhydride and C4 unsaturated hydrocarbons. The process is limited by low stationary concentration of C4 unsaturated hydrocarbons in reaction mixture which is connected with high rate of their oxidation to maleic anhydride. It was shown that n-butane oxidation leads to formation of maleic anhydride only but the introduction of unsaturated C4-hydrocarbons on inlet of the second catalytic reactor accompanied by phthalic anhydride appearance on outlet of these two consecutive reactors system. It was established that in case of 1,3-butene introduction in the second reactor the quantity of phthalic anhydride formed is more than in case of 2-butene addition. It was predicted that a decrease of the temperature in the second reactor can leads to an increase the phthalic anhydride selectivity and its yield as result of Diels-Alder reaction effectiveness. This assumption was confirmed by experimental results. In results the method of phthalic anhydride production by the use of two consecutive reactors was proposed. The summary yield of this product on this new process can reach up to 35 mol. %. In the case of n-pentane oxidation the formation of maleic and phthalic anhydrides was observed with excess of first product but the introduction of unsaturated C4-hydrocarbons in the inlet of second reactor leads to an increase of the phthalic anhydride concentration and its selectivity and yield. In result the yield of phthalic anhydride equal to 35 mol. % can be obtained. So, the proposed by us mechanism of phthalic anhydride was confirmed by new experimental results and other pathways for the selectivity and yield of this product can be predicted.
{"title":"The pathways of the phthalic anhydride selectivity and yield increase at C4-C5-hydrocarbons oxidation","authors":"O. Kiziun, V. Zazhigalov","doi":"10.15407/kataliz2022.33.021","DOIUrl":"https://doi.org/10.15407/kataliz2022.33.021","url":null,"abstract":"The investigation of n-butane and n-pentane oxidation in system with two consecutive reactors confirmed the mechanism of phthalic anhydride formation by Diels-Alder reaction between maleic anhydride and C4 unsaturated hydrocarbons. The process is limited by low stationary concentration of C4 unsaturated hydrocarbons in reaction mixture which is connected with high rate of their oxidation to maleic anhydride. It was shown that n-butane oxidation leads to formation of maleic anhydride only but the introduction of unsaturated C4-hydrocarbons on inlet of the second catalytic reactor accompanied by phthalic anhydride appearance on outlet of these two consecutive reactors system. It was established that in case of 1,3-butene introduction in the second reactor the quantity of phthalic anhydride formed is more than in case of 2-butene addition. It was predicted that a decrease of the temperature in the second reactor can leads to an increase the phthalic anhydride selectivity and its yield as result of Diels-Alder reaction effectiveness. This assumption was confirmed by experimental results. In results the method of phthalic anhydride production by the use of two consecutive reactors was proposed. The summary yield of this product on this new process can reach up to 35 mol. %. In the case of n-pentane oxidation the formation of maleic and phthalic anhydrides was observed with excess of first product but the introduction of unsaturated C4-hydrocarbons in the inlet of second reactor leads to an increase of the phthalic anhydride concentration and its selectivity and yield. In result the yield of phthalic anhydride equal to 35 mol. % can be obtained. So, the proposed by us mechanism of phthalic anhydride was confirmed by new experimental results and other pathways for the selectivity and yield of this product can be predicted.","PeriodicalId":9649,"journal":{"name":"Catalysis and Petrochemistry","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2022-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"81255048","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2022-01-01DOI: 10.15407/kataliz2022.33.059
A. Varvarin, S. Levytska, A. Mylin, O. Zinchenko, V. Brei
The gas-phase oxidation of ethylene glycol and methanol mixture into methyl glycolate С2H6O2+CH3OH+O2 = C3H6O3+2H2О over synthesized copper-containing catalysts was studied. Methyl glycolate can be considered as raw material for obtaining biodegradable polyglycolide. The CuO-containing samples were synthesized by impregnation of granular oxide-supports (γ-Al2O3, SiO2 and MgO-ZrO2) with the calculated amount of aqueous solution of Cu(NO3)2·3H2O followed by heat treatment at 400 °C. In such way the supported CuO-MexOy /Al2O3 (Me = Mg, Ti, Cr, Co, Zn, Zr, Ag) samples have been prepared. Catalytic experiments were performed in a stainless-steel flow reactor with a fixed bed of catalyst at 200-270 °C and atmospheric pressure. Oxygen of air was used as an oxidant. The reaction products were analyzed using 13C NMR spectroscopy and gas chromatography. It was found that СuO/Al2O3 catalyst provides ~ 100% ethylene glycol conversion with 56% selectivity towards methyl glycolate at 220 °С. The main by-products are methoxymethanol, 1,1-dimethoxymethane, methyl methoxyacetate, and methyl formate. Use of silica as catalyst support leads to a significant decrease of the ethylene glycol conversion to 57 % for CuO/SiO2, but methyl glycolate selectivity does not change significantly. Promotion of СuO/Al2O3 with MgO increases methyl glycolate yield to 64%. According to the scheme of ethylene glycol sequential oxidation the increase in selectivity for methyl glycolate over CuO-MgO/Al2O3 catalyst is caused by the basic sites that promote intramolecular Cannizzaro rearrangement of the intermediate reaction product – glyoxal hemiacetal to methyl glycolate. It’s found that mixed CuO-CrO3 oxide supported by γ-Al2O3 provides 80 % methyl glycolate selectivity with 95-100% ethylene glycol conversion at 200-210 °C.
{"title":"Vapor-phase oxidation of ethylene glycol methanolic solution into methyl glycolate over CuO-containing catalysts","authors":"A. Varvarin, S. Levytska, A. Mylin, O. Zinchenko, V. Brei","doi":"10.15407/kataliz2022.33.059","DOIUrl":"https://doi.org/10.15407/kataliz2022.33.059","url":null,"abstract":"The gas-phase oxidation of ethylene glycol and methanol mixture into methyl glycolate С2H6O2+CH3OH+O2 = C3H6O3+2H2О over synthesized copper-containing catalysts was studied. Methyl glycolate can be considered as raw material for obtaining biodegradable polyglycolide. The CuO-containing samples were synthesized by impregnation of granular oxide-supports (γ-Al2O3, SiO2 and MgO-ZrO2) with the calculated amount of aqueous solution of Cu(NO3)2·3H2O followed by heat treatment at 400 °C. In such way the supported CuO-MexOy /Al2O3 (Me = Mg, Ti, Cr, Co, Zn, Zr, Ag) samples have been prepared. Catalytic experiments were performed in a stainless-steel flow reactor with a fixed bed of catalyst at 200-270 °C and atmospheric pressure. Oxygen of air was used as an oxidant. The reaction products were analyzed using 13C NMR spectroscopy and gas chromatography. It was found that СuO/Al2O3 catalyst provides ~ 100% ethylene glycol conversion with 56% selectivity towards methyl glycolate at 220 °С. The main by-products are methoxymethanol, 1,1-dimethoxymethane, methyl methoxyacetate, and methyl formate. Use of silica as catalyst support leads to a significant decrease of the ethylene glycol conversion to 57 % for CuO/SiO2, but methyl glycolate selectivity does not change significantly. Promotion of СuO/Al2O3 with MgO increases methyl glycolate yield to 64%. According to the scheme of ethylene glycol sequential oxidation the increase in selectivity for methyl glycolate over CuO-MgO/Al2O3 catalyst is caused by the basic sites that promote intramolecular Cannizzaro rearrangement of the intermediate reaction product – glyoxal hemiacetal to methyl glycolate. It’s found that mixed CuO-CrO3 oxide supported by γ-Al2O3 provides 80 % methyl glycolate selectivity with 95-100% ethylene glycol conversion at 200-210 °C.","PeriodicalId":9649,"journal":{"name":"Catalysis and Petrochemistry","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2022-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"88129502","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2022-01-01DOI: 10.15407/kataliz2022.33.001
V. Brei, S. Levytska, S. Prudius
Temperature-programmed reaction (TPR) method with mass spectrometric control of the products was used to study of cyclohexanol oxidation into cyclohexanone on individual and mixed oxides supported by γ-Al2O3 and silica gel. In the TPR profiles the temperature of a maximum rate of cyclohexanone formation varies from 125°C for MoO3/Al2O3 to 235°C for less active CuO/Al2O3. The catalytic activity of individual oxides decreases in the order MoO3/Al2O3> V2O5/SiO2 > Fe2O3/Al2O3 > Bi2O5/Al2O3 > TiO2/SiO2 ≈ СeO2/Al2O3 > TiO2/Al2O3 > SnO2/Al2O3. As "reactive" oxygen in our TPR experiment was supplied only from oxide lattice, oxide activity is determined by different energy of the surface Me – O bonds. The approach to search for mixed active oxides based on decreasing coordination number of O2- ions is proposed, that confirmed by the example of CuO-WO3/Al2O3 catalyst. The mixed supported oxides, especially CuOCrO3/Al2O3, CuO-MoO3/Al2O3, MoO3-SnO2/Al2O3 and Bi2O3–SnO2/Al2O3, are more active in С6Н12О + 1/2О2 → С6Н10О + Н2О oxidation. The synthesized CuO-CrO3/Al2O3 catalyst provides cyclohexanone formation without side cyclohexanol dehydration and can be used for the oxidation of ethylene glycol – methanol mixture into methyl glycolate. CuO-Cr2O3/Al2O3 with a spinel structure of CuCr2O4 ([CuO4] 6− tetrahedra, Cu2+ sp3-hybridization) is more active in cyclohexanol oxidation than CuO/Al2O3 with flat [CuO4] 6−squares, Cu2+ dsp2-hybridization. This is explained by the lower energy of Cu-O bonds at sp3-hybridization of Cu2+ ions.
{"title":"To the question of oxidation on the surface of oxides: temperature- programmed oxidation of cyclohexanol","authors":"V. Brei, S. Levytska, S. Prudius","doi":"10.15407/kataliz2022.33.001","DOIUrl":"https://doi.org/10.15407/kataliz2022.33.001","url":null,"abstract":"Temperature-programmed reaction (TPR) method with mass spectrometric control of the products was used to study of cyclohexanol oxidation into cyclohexanone on individual and mixed oxides supported by γ-Al2O3 and silica gel. In the TPR profiles the temperature of a maximum rate of cyclohexanone formation varies from 125°C for MoO3/Al2O3 to 235°C for less active CuO/Al2O3. The catalytic activity of individual oxides decreases in the order MoO3/Al2O3> V2O5/SiO2 > Fe2O3/Al2O3 > Bi2O5/Al2O3 > TiO2/SiO2 ≈ СeO2/Al2O3 > TiO2/Al2O3 > SnO2/Al2O3. As \"reactive\" oxygen in our TPR experiment was supplied only from oxide lattice, oxide activity is determined by different energy of the surface Me – O bonds. The approach to search for mixed active oxides based on decreasing coordination number of O2- ions is proposed, that confirmed by the example of CuO-WO3/Al2O3 catalyst. The mixed supported oxides, especially CuOCrO3/Al2O3, CuO-MoO3/Al2O3, MoO3-SnO2/Al2O3 and Bi2O3–SnO2/Al2O3, are more active in С6Н12О + 1/2О2 → С6Н10О + Н2О oxidation. The synthesized CuO-CrO3/Al2O3 catalyst provides cyclohexanone formation without side cyclohexanol dehydration and can be used for the oxidation of ethylene glycol – methanol mixture into methyl glycolate. CuO-Cr2O3/Al2O3 with a spinel structure of CuCr2O4 ([CuO4] 6− tetrahedra, Cu2+ sp3-hybridization) is more active in cyclohexanol oxidation than CuO/Al2O3 with flat [CuO4] 6−squares, Cu2+ dsp2-hybridization. This is explained by the lower energy of Cu-O bonds at sp3-hybridization of Cu2+ ions.","PeriodicalId":9649,"journal":{"name":"Catalysis and Petrochemistry","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2022-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"84329345","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2022-01-01DOI: 10.15407/kataliz2022.33.010
A. Trypolskyi
The paper is devoted to the development of a catalyst for the synthesis of the higher hydrocarbons from carbon dioxide and hydrogen. The conversion of greenhouse gas CO2 into value-added chemicals contributes not only to sol-ving environmental problems, but also to obtaining valuable fuel. Catalysts that are active in the hydrogenation reaction of CO are also active in the process of CO2 hydrogenation. The most active catalysts in the hydrogenation of carbon dioxide are based on transition metals, in the presence of which mainly methane and a small amount of carbon monoxide are formed. Investigation of the kinetics of hydrocarbons synthesis by hydrogenation of carbon dioxide in the presence of transition metals allowed establishing the mechanism of the process and no perspective of such catalytic systems for hydrocarbons synthesis via intermediate formation of carbon monoxide. It is established that the optimal method of synthesis of higher hydrocarbons is the indirect path, through the intermediate formation of methanol with its further dehydration. The synthesis of methanol from gas mixtures of H2, CO, and CO2 with different composition in the presence of industrial catalysts takes place along the same macroscopic route, by reducing CO2, and is accompanied by a reverse water-gas shift reaction. Therefore, gas mixtures of different composition can be used as raw material for methanol production. Based on our own and literature data, the general peculiarities of the carbon dioxide hydrogenation reaction were obtained, which allowed developing a complex multifunctional catalyst for the synthesis of higher hydrocarbons from carbon dioxide and hydrogen. The proposed catalyst combines the properties of ones for the synthesis of oxygenates from carbon dioxide, and catalysts for the processes of hydrocarbons synthesis from me-thanol and other alcohols. The synthesis of higher hydrocarbons with a predominant content of branched hydrocarbons on the developed bifunctional catalyst was carried out and the optimal conditions for the process were determined.
{"title":"Development of catalysts for the synthesis of higher hydrocarbons from carbon dioxide","authors":"A. Trypolskyi","doi":"10.15407/kataliz2022.33.010","DOIUrl":"https://doi.org/10.15407/kataliz2022.33.010","url":null,"abstract":"The paper is devoted to the development of a catalyst for the synthesis of the higher hydrocarbons from carbon dioxide and hydrogen. The conversion of greenhouse gas CO2 into value-added chemicals contributes not only to sol-ving environmental problems, but also to obtaining valuable fuel. Catalysts that are active in the hydrogenation reaction of CO are also active in the process of CO2 hydrogenation. The most active catalysts in the hydrogenation of carbon dioxide are based on transition metals, in the presence of which mainly methane and a small amount of carbon monoxide are formed. Investigation of the kinetics of hydrocarbons synthesis by hydrogenation of carbon dioxide in the presence of transition metals allowed establishing the mechanism of the process and no perspective of such catalytic systems for hydrocarbons synthesis via intermediate formation of carbon monoxide. It is established that the optimal method of synthesis of higher hydrocarbons is the indirect path, through the intermediate formation of methanol with its further dehydration. The synthesis of methanol from gas mixtures of H2, CO, and CO2 with different composition in the presence of industrial catalysts takes place along the same macroscopic route, by reducing CO2, and is accompanied by a reverse water-gas shift reaction. Therefore, gas mixtures of different composition can be used as raw material for methanol production. Based on our own and literature data, the general peculiarities of the carbon dioxide hydrogenation reaction were obtained, which allowed developing a complex multifunctional catalyst for the synthesis of higher hydrocarbons from carbon dioxide and hydrogen. The proposed catalyst combines the properties of ones for the synthesis of oxygenates from carbon dioxide, and catalysts for the processes of hydrocarbons synthesis from me-thanol and other alcohols. The synthesis of higher hydrocarbons with a predominant content of branched hydrocarbons on the developed bifunctional catalyst was carried out and the optimal conditions for the process were determined.","PeriodicalId":9649,"journal":{"name":"Catalysis and Petrochemistry","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2022-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"79271114","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2022-01-01DOI: 10.15407/kataliz2022.33.031
V. Ivasiv, R. Nebesnyi, S. V. Maykova
In this work we aim for developing a kinetic model for the methyl methacrylate and methacrylic acid synthesis by the combined condensation and esterification of methyl propionate and propionic acid with formaldehyde and methanol in the presence of the silica-supported boron-phosphorus-oxide catalyst promoted by oxides of tungsten and zirconium. The dependencies of the formation rates of methyl methacrylate, methacrylic acid and diethyl ketone from the concentrations of methyl propionate, propionic acid, formaldehyde and methanol were studied, and reaction orders of every product formation with respect to each reagent were determined. Methacrylic acid is formed predominantly by condensation of methyl propionate with formaldehyde, and methyl methacrylate hydrolysis is insignificantly. The methyl methacrylate formation reaction rate is limited by the methyl propionate adsorption rate on the catalyst surface, and both reactions of methyl methacrylate and methacrylic acid formation are inhibited due to adsorption of formaldehyde, propionic acid and methanol. Based on obtained data, the reaction scheme was offered, which includes formation of intermediates such as 3-hydroxy-2-methylpropanoic acid, its methyl ester and 3,3-dihydroxy-2-methylpentanoic acid. From this reaction scheme the kinetic model was derived using steady state approximation. The reaction rate constants and their activation energies for this model were calculated from experimental data. Validity of the model was experimentally confirmed by the correlation between experimental and theoretically calculated data. Therefore, the developed kinetic model satisfactorily describes the process of the combined condensation and esterification of methyl propionate and propionic acid with formaldehyde and methanol as well as partial cases of condensation of methyl propionate with formaldehyde and propionic acid with formaldehyde, and is suitable for process optimization and technological calculations.
{"title":"The kinetic model of the combined heterogeneously catalyzed condensation and esterification of propionic acid and methyl propionate with formaldehyde and methanol","authors":"V. Ivasiv, R. Nebesnyi, S. V. Maykova","doi":"10.15407/kataliz2022.33.031","DOIUrl":"https://doi.org/10.15407/kataliz2022.33.031","url":null,"abstract":"In this work we aim for developing a kinetic model for the methyl methacrylate and methacrylic acid synthesis by the combined condensation and esterification of methyl propionate and propionic acid with formaldehyde and methanol in the presence of the silica-supported boron-phosphorus-oxide catalyst promoted by oxides of tungsten and zirconium. The dependencies of the formation rates of methyl methacrylate, methacrylic acid and diethyl ketone from the concentrations of methyl propionate, propionic acid, formaldehyde and methanol were studied, and reaction orders of every product formation with respect to each reagent were determined. Methacrylic acid is formed predominantly by condensation of methyl propionate with formaldehyde, and methyl methacrylate hydrolysis is insignificantly. The methyl methacrylate formation reaction rate is limited by the methyl propionate adsorption rate on the catalyst surface, and both reactions of methyl methacrylate and methacrylic acid formation are inhibited due to adsorption of formaldehyde, propionic acid and methanol. Based on obtained data, the reaction scheme was offered, which includes formation of intermediates such as 3-hydroxy-2-methylpropanoic acid, its methyl ester and 3,3-dihydroxy-2-methylpentanoic acid. From this reaction scheme the kinetic model was derived using steady state approximation. The reaction rate constants and their activation energies for this model were calculated from experimental data. Validity of the model was experimentally confirmed by the correlation between experimental and theoretically calculated data. Therefore, the developed kinetic model satisfactorily describes the process of the combined condensation and esterification of methyl propionate and propionic acid with formaldehyde and methanol as well as partial cases of condensation of methyl propionate with formaldehyde and propionic acid with formaldehyde, and is suitable for process optimization and technological calculations.","PeriodicalId":9649,"journal":{"name":"Catalysis and Petrochemistry","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2022-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"77312245","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2022-01-01DOI: 10.15407/kataliz2022.33.038
L. Patrylak, S. Konovalov, A. Yakovenko, O. Pertko, V. Povazhnyi, O. Melnychuk
Biomass-derived 5-hydroxymethylfurfural (5-HMF) is a potential raw material for the production of a wide range of valuable chemicals and biofuels. Industrial production of 5-HMF from hexoses on solid catalysts is promising nowadays. Acid zeolites have great potential in application as catalysts for the dehydration of sugars. The purpose of this work was to obtain granular zeolite catalysts with optimal acidity and evaluate their effectiveness depending on the nature of the binder used. A zeolite catalyst without binder and samples with 10 wt % of kaolin/alumina were prepared. Their porous characteristics and acidity were studied by means of nitrogen low temperature adsorption/desorption, ammonia thermo-programmed desorption, and pyridine adsorption with IR control. The activity and selectivity of the catalysts for 5-HMF synthesis from glucose in the dimethyl sulfoxide medium at 160 ◦C were studied. The high efficiency of granular samples in glucose transformation into 5-HMF is confirmed. They are not only not inferior to, but even superior to, powdered samples. The component sources of Brønsted and Lewis acidity of the ammonium form of zeolite, which demonstrates acceptable activity (selectivity for 5-HMF is 34 %) despite the small number of Lewis centers, are considered in detail. The highest efficiency is demonstrated by the sample with aluminum oxide, which not only does not significantly deteriorate the microporous characteristics but also improves the mesoporosity of the catalyst. The selectivity towards 5-HMF on it reaches 44%. However, the developed mesoporosity of the sample with aluminum oxide is not critical to its activity. The main influence on the effectiveness of the catalyst in the synthesis of 5-HMF is played by the presence of acid centers of medium strength.
{"title":"Conversion of glucose into 5-hydroxymethylfurfural on granular zeolite catalysts","authors":"L. Patrylak, S. Konovalov, A. Yakovenko, O. Pertko, V. Povazhnyi, O. Melnychuk","doi":"10.15407/kataliz2022.33.038","DOIUrl":"https://doi.org/10.15407/kataliz2022.33.038","url":null,"abstract":"Biomass-derived 5-hydroxymethylfurfural (5-HMF) is a potential raw material for the production of a wide range of valuable chemicals and biofuels. Industrial production of 5-HMF from hexoses on solid catalysts is promising nowadays. Acid zeolites have great potential in application as catalysts for the dehydration of sugars. The purpose of this work was to obtain granular zeolite catalysts with optimal acidity and evaluate their effectiveness depending on the nature of the binder used. A zeolite catalyst without binder and samples with 10 wt % of kaolin/alumina were prepared. Their porous characteristics and acidity were studied by means of nitrogen low temperature adsorption/desorption, ammonia thermo-programmed desorption, and pyridine adsorption with IR control. The activity and selectivity of the catalysts for 5-HMF synthesis from glucose in the dimethyl sulfoxide medium at 160 ◦C were studied. The high efficiency of granular samples in glucose transformation into 5-HMF is confirmed. They are not only not inferior to, but even superior to, powdered samples. The component sources of Brønsted and Lewis acidity of the ammonium form of zeolite, which demonstrates acceptable activity (selectivity for 5-HMF is 34 %) despite the small number of Lewis centers, are considered in detail. The highest efficiency is demonstrated by the sample with aluminum oxide, which not only does not significantly deteriorate the microporous characteristics but also improves the mesoporosity of the catalyst. The selectivity towards 5-HMF on it reaches 44%. However, the developed mesoporosity of the sample with aluminum oxide is not critical to its activity. The main influence on the effectiveness of the catalyst in the synthesis of 5-HMF is played by the presence of acid centers of medium strength.","PeriodicalId":9649,"journal":{"name":"Catalysis and Petrochemistry","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2022-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"89364480","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2022-01-01DOI: 10.15407/kataliz2022.33.046
O. Diyuk
Bulk and supported vanadium-phosphorus oxide VPO catalysts were synthesized by traditional and barothermal methods. It was shown that the use of aerosil as a support for the VPO phase, depending on the time of its introduction into the reaction mixture. It can lead to the formation of catalyst precursor of vanadyl hydrogen phosphate VOHPO4 0.5H2O, or a phase of vanadyl pyrophosphate (VO)2P2O7 as already the catalytically active phase for selective oxidation of n-butane to maleic anhydride. The use of a modified aerosil gel formed from pyrogenic aerosol, as a support for the VPO phase, leads to the formation of VOHPO4∙0.5H2O phase. It has been found that the nature of support affects the features of formation of VOHPO4∙0.5H2O phase, in particular, the ratio of crystallographic planes in resulting VPO phase. The use of aerosil as a support leads to a decrease in the relative content of the basal plane, while use of aerosil gel leads to an increase in the relative content of the basal plane in applied VPO phase. The catalytic properties of bulk and supported VPO samples were studied in the selective oxidation of n-butane to maleic anhydride in standard (1.7 vol.%) and enriched (3.4 vol.%) n-butane mixtures. It has been found that in an enriched n-butane mixture for bulk samples, the n-butane conversion and selectivity for maleic anhydride are sharply reduced. It has been found that supported VPO samples have a higher specific rate of n-butane oxidation and higher productivity compared to bulk samples. It was shown that use of barothermal synthesis and aerosol gel as a support made it possible to increase the selectivity of maleic anhydride, which is associated with an increase in the relative content of the basal plane of VPO phase. The achieved improved catalytic properties of VPO catalysts supported with aerosol gel make recycling technology promising. This can make the production of maleic anhydride more economical.
{"title":"Synthesis and properties of VPO catalysts for oxidation of n-butane to maleic anhydride","authors":"O. Diyuk","doi":"10.15407/kataliz2022.33.046","DOIUrl":"https://doi.org/10.15407/kataliz2022.33.046","url":null,"abstract":"Bulk and supported vanadium-phosphorus oxide VPO catalysts were synthesized by traditional and barothermal methods. It was shown that the use of aerosil as a support for the VPO phase, depending on the time of its introduction into the reaction mixture. It can lead to the formation of catalyst precursor of vanadyl hydrogen phosphate VOHPO4 0.5H2O, or a phase of vanadyl pyrophosphate (VO)2P2O7 as already the catalytically active phase for selective oxidation of n-butane to maleic anhydride. The use of a modified aerosil gel formed from pyrogenic aerosol, as a support for the VPO phase, leads to the formation of VOHPO4∙0.5H2O phase. It has been found that the nature of support affects the features of formation of VOHPO4∙0.5H2O phase, in particular, the ratio of crystallographic planes in resulting VPO phase. The use of aerosil as a support leads to a decrease in the relative content of the basal plane, while use of aerosil gel leads to an increase in the relative content of the basal plane in applied VPO phase. The catalytic properties of bulk and supported VPO samples were studied in the selective oxidation of n-butane to maleic anhydride in standard (1.7 vol.%) and enriched (3.4 vol.%) n-butane mixtures. It has been found that in an enriched n-butane mixture for bulk samples, the n-butane conversion and selectivity for maleic anhydride are sharply reduced. It has been found that supported VPO samples have a higher specific rate of n-butane oxidation and higher productivity compared to bulk samples. It was shown that use of barothermal synthesis and aerosol gel as a support made it possible to increase the selectivity of maleic anhydride, which is associated with an increase in the relative content of the basal plane of VPO phase. The achieved improved catalytic properties of VPO catalysts supported with aerosol gel make recycling technology promising. This can make the production of maleic anhydride more economical.","PeriodicalId":9649,"journal":{"name":"Catalysis and Petrochemistry","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2022-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"90459336","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2022-01-01DOI: 10.15407/kataliz2022.33.084
G. Krymets, M. Litynska, O. Melnychuk
Acid tars are wastes from the processing of coal, petroleum, and petrochemicals (oil refining, benzene refining and petroleum fractions refining and alkylation of isobutane with butenes). Acid tar compositions include resinous substances, organic matter, and polymerization products of unsaturated hydrocarbons. The presence of free sulfuric acid in acid tars often reaches 70 % by weight. Almost all metals from oil are concentrated in tars, and the content of vanadium and nickel can reach 0.046 and 0.014 %, respectively. A lot of countries keep acid tar in the open air in spent quarries, storage ponds, barns, lagoons or near landfills. It poses a risk or even potential threat to people and to the environment nearby due to soil, water, and air pollution. Thus, disposal of the acid tars is a very important ecological and industrial task. In this study, we have researched catalytic cracking and distillation as the utilization methods for acid tar. Anhydrous AlCl3 was used as a catalyst during the cracking of petroleum residues to obtain volatile gasoline fractions due to its catalytic activity in many organic reactions. The catalyst ratios (0.15 g/g of tar or 0.1 g/g of tar) had a very significant influence on the number of volatile fractions and boiling temperature in the acid tar cracking process. According to the results of 1H NMR research, the main components of volatile fractions in the case of catalytic cracking were alkanes CH3-(CH2)n-CH3. The compositions of these fractions were similar to the compositions of gasoline and diesel fuel. A series of distillation experiments (distillation of previously deacidified and centrifuged tar, acid tar without deacidification and centrifugation, and previously deacidified tar without centrifu-gation) gave different results for each type of material. Aliphatic hydrocarbons were the main components of volatile fractions (~ 80, ~ 60 and ~ 90 %, respectively) and the contents of aliphatic S-organic compounds were also significant (~ 10, ~ 30 and ~ 8 %). Thus, both for catalytic cracking and for tar distillation, aliphatic hydrocarbons were the main component of volatile fractions. Deacidification of tar increased the yield of aliphatic hydrocarbons during tar distillation and decreased production of S-organic compounds due to its reactions with calcium carbonate. It is perspective in the context of fuel production.
{"title":"Catalytic processing of the acid tars","authors":"G. Krymets, M. Litynska, O. Melnychuk","doi":"10.15407/kataliz2022.33.084","DOIUrl":"https://doi.org/10.15407/kataliz2022.33.084","url":null,"abstract":"Acid tars are wastes from the processing of coal, petroleum, and petrochemicals (oil refining, benzene refining and petroleum fractions refining and alkylation of isobutane with butenes). Acid tar compositions include resinous substances, organic matter, and polymerization products of unsaturated hydrocarbons. The presence of free sulfuric acid in acid tars often reaches 70 % by weight. Almost all metals from oil are concentrated in tars, and the content of vanadium and nickel can reach 0.046 and 0.014 %, respectively. A lot of countries keep acid tar in the open air in spent quarries, storage ponds, barns, lagoons or near landfills. It poses a risk or even potential threat to people and to the environment nearby due to soil, water, and air pollution. Thus, disposal of the acid tars is a very important ecological and industrial task. In this study, we have researched catalytic cracking and distillation as the utilization methods for acid tar. Anhydrous AlCl3 was used as a catalyst during the cracking of petroleum residues to obtain volatile gasoline fractions due to its catalytic activity in many organic reactions. The catalyst ratios (0.15 g/g of tar or 0.1 g/g of tar) had a very significant influence on the number of volatile fractions and boiling temperature in the acid tar cracking process. According to the results of 1H NMR research, the main components of volatile fractions in the case of catalytic cracking were alkanes CH3-(CH2)n-CH3. The compositions of these fractions were similar to the compositions of gasoline and diesel fuel. A series of distillation experiments (distillation of previously deacidified and centrifuged tar, acid tar without deacidification and centrifugation, and previously deacidified tar without centrifu-gation) gave different results for each type of material. Aliphatic hydrocarbons were the main components of volatile fractions (~ 80, ~ 60 and ~ 90 %, respectively) and the contents of aliphatic S-organic compounds were also significant (~ 10, ~ 30 and ~ 8 %). Thus, both for catalytic cracking and for tar distillation, aliphatic hydrocarbons were the main component of volatile fractions. Deacidification of tar increased the yield of aliphatic hydrocarbons during tar distillation and decreased production of S-organic compounds due to its reactions with calcium carbonate. It is perspective in the context of fuel production.","PeriodicalId":9649,"journal":{"name":"Catalysis and Petrochemistry","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2022-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"89242915","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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