CC BY
9
№ 6 (108)
июнь, 2023 г.
PHYSICAL CHEMISTRY
DOI - 10.32743/UniChem.2023.108.6.15577 CATALYST SELECTION AND TECHNOLOGY FOR OBTAINING DIMETHYL ETHER
Jasur Shukurov
Doctoral Student, Samarkand State University, Republic of Uzbekistan, Samarkand E-mail: shukjasni@gmail.com
Normurot Fayzullaev
Doctor of Technical Sciences, Professor, Department of Polymer Chemistry and Chemical Technology,
Samarkand State University, Republic of Uzbekistan, Samarkand E-mail: _ f-normurot@samdu uz
ВЫБОР КАТАЛИЗАТОРА И ТЕХНОЛОГИЯ ПОЛУЧЕНИЯ ДИМЕТИЛОВОГО ЭФИРА
Жасур Шукуров Хошимович
докторант,
Самаркандский государственный университет, Республика Узбекистан, г. Самарканд
Нормурот Файзуллаев Ибодуллаевич
д-р техн. наук, профессор, кафедра химии полимеров и химической технологии, Самаркандский государственный университет, Республика Узбекистан, г. Самарканд
АННОТАЦИЯ
В работе рассмотрен процесс моделирования производства метанола и диметилового эфира.Количество веществ на выходе из реактора анализировали хроматографическим методом.Синтез органических веществ на основе природного газа снижает долю его использования в качестве топлива и создает возможности для получения необходимых продуктов.Именно поэтому разработка способов синтеза различных веществ на основе природного газа, получение катализаторов на основе местного сырья для процесса относятся к числу актуальных задач.Исследован процесс получения диметилового эфира из СО и Щ синтеза метанола и его дегидратации в присутствии катализатора, состоящего из ZnO•AЪOз•ZrO2•CuO•CaO/бентонит: Y-AhOзв условиях их послойного послойная загрузка.
ABSTRACT
In the work, the process of modelling methanol and dimethyl ether production was considered. The number of substances at the exit from the reactor was analysed by chromatographic method. Synthesis of organic substances based on natural gas reduces the share of its use as fuel and creates opportunities for obtaining necessary products. That is why the development of ways to synthesize various substances based on natural gas, and obtaining catalysts based on local raw materials for the process are among the urgent problems. The process of obtaining dimethyl ether from CO and H2, synthesis of methanol and its dehydration in the presence of a catalyst consisting of ZnO-AhO3-ZrO2-CuO- CaO/bentonite: y-AhO3was studied in terms of their layer-by-layer loading.
Ключевые слова: метанол, диметиловый эфир, температура, катализатор, конверсия.
Keywords: methanol, dimethyl ether, temperature, catalyst, conversion.
Introduction
Currently, dimethyl ether is considered an alternative source of energy to diesel fuel. The synthesis of dimethyl ether (DME) from synthesis gas is carried out by direct
or indirect methods. For the direct synthesis of DME, two types of compositions are used such as methanol synthesis catalyst and CH3OH dehydration catalyst storage compositions. Dimethyl ether-dimethyl sulphate is an
Библиографическое описание: Shukurov J., Fayzullaev N. CATALYST SELECTION AND TECHNOLOGY FOR OBTAINING DIMETHYL ETHER // Universum: химия и биология : электрон. научн. журн. 2023. 6(108). URL:
https://7universum.com/ru/nature/archive/item/15577
important chemical raw material for the production of chemicals such as methyl acetate and ethylene, propylene, and is also environmentally safe for aerosol cans. According to the physical properties of dimethyl ether, liquefied oil is similar to gases and can be stored under the same conditions, and easily transported [1-4].
Worldwide research shows that various carbon-containing raw materials can be processed into valuable chemical products. One of the recycling ideas is to oxidize raw materials (natural gas, household waste, gas from oil refineries, etc.) into carbon dioxide and hydrogen [5-6].
Carbon dioxide and hydrogen can then be converted to oxygenates (DME or CH3OH), which can be a synthetic source of hydrocarbons [7-8] or valuable chemical products [9]. The combination of high activity in methanol synthesis and its dehydration can be achieved not only by optimal selection of process parameters but also by proper selection of methanol synthesis and dehydration components [10-11].
Physicochemical and catalytic properties of Cr2O3*ZnO*Al2O3, aluminosilicate and CuO*ZnO*A^O3 catalysts for dehydrating alcohol to dimethyl ether were previously studied and described in works [12-13]. Synthesis, textural characteristics and application of catalysts based on UKTs are detailed in works [14-16].
Experimental part
In the work, since two processes-methanol syntheses and their dehydration occurred simultaneously in one reactor, CuO• ZnO• AI2O3 ZrO2• CaO/bentonite: y- AkO3in the presence of a catalyst provided a) 1:1, b) 2:3, c)2:1:2 ratios, fold-by-loading methods. Operating conditions T=290 °C, P=0.5 MPa, H2/CO=2, volume velocity at a pressure of 1000 h-1, conversion of CO to methanol and DME in a single pass through the catalyst bed "Crystal 5000" gas chromatograph, Determinations were made
using a TriStar II (3020) automatic gas adsorption analyzer model BJH (Barett-Joyner-Halenda). The phase composition of the catalyst samples was studied by X-ray phase analysis (XRD) using a Shimadzu XRD-6000 diffractometer. The surface morphology of the samples was studied by scanning electron microscope based on IILMU VEGA electron microscope and INCA ENERGY 370 energy dispersive microanalysis. Diffrac-tometry (XRD Pan Analytical) was used to study the phase composition of the catalysts, and scanning electron microscopy (SEM) was used to study the surface characteristics.
Results and discussion
When several compounds are applied to aluminium oxide, its surface properties change significantly, and a new catalyst with certain acid-base and oxidation-reduction properties determines the selectivity of methanol decomposition or conversion. A sample with a small copper content (~1 wt.%) slightly reduces the catalytic activity of the system in the CH3OH dehydration reaction, but its general laws are preserved. Modification of the support surface with zinc oxide also reduces the catalytic activity in this reaction, and the more zinc oxide in the system, the lower the catalyst performance for dimethyl ether. This is because zinc oxide reduces the concentration of acid centres on the surface. If copper oxide is added to the initial carrier (bentonite) in sufficiently high concentrations (5-10 wt.%), a significant change in the catalytic properties of the system is observed. Other components appear in the reaction products: H2, HCOOCH3, CH4, carbon dioxide and carbon dioxide. As the amount of copper in the catalyst increases, the relative efficiency of dimethyl ether and methyl formate increases at relatively low temperatures (150-2400C)
(Fig. 1).
Figure 1. Dependence of the reaction temperature on the degree of methanol decomposition (2, 2^ and the relative efficiency of the CuO*ZnO*AhO3*ZrO2* CaO/bentonite catalyst on dimethyl ether with different amounts of copper in the catalyst: 1, 2 - 4.1 wt. % Cu, V, 2^ - 8.2 wt.% Cu
The change in the copper content of the catalyst has almost no effect on the specific indicators of carbon dioxide and carbon dioxide. Light gases such as hydrogen, carbon dioxide and carbon dioxide are formed as a result of methanol conversion and decomposition reactions:
CHpH + Hp = CO + 3H2 (1)
CHpH ^ CO + 2H2
(2)
Water is a dehydration product of methanol. With an increase in temperature, the formation of dimethyl ether in the substance component of the catalyst decreases, and methanol decomposes into carbon monoxide and two hydrogen molecules (reaction 2).
At relatively low temperatures (170-2350C), HCOOCH3 is formed on the catalyst (reaction 3), and at higher temperatures, the yield of dimethyl ether decreases sharply and methane appears in the products, which suggests the following reactions:
2СНЪОН ^ СНъОСНО + 2Н2 (3) СНЪОСНЪ ^ СН4 + СО + Н (4)
In this system, there is a high activity for methyl formate (Figure 2), and in such a system, in the low-temperature range (170-215 0C), the performance of dimethyl ether is higher than that of pure aluminium oxide. This indicates that the methoxy groups located in the copper component are also involved in the formation of dimethyl ether. The formation of methyl formate is endothermic, that is, instead of increasing the equilibrium
июнь, 2023 г.
concentration of methyl formate with increasing temperature, it decomposes into CO and hydrogen at high temperatures (above 2200C):
СЩОСНОН ^ 2СО + 2Н (5)
Experiments to determine the catalytic activity of samples with different catalyst loadings confirm that DME, CH3OH and HCOOCH3 are intermediates in the decomposition reactions of methanol to simpler substances. With a decrease in the sample size of the catalyst, its relative productivity for CH3OCH3 and HCOOCH3 increases, which means that these products do not have time to decompose due to the short reaction time of the substances with the catalyst (Fig. 2).
Since hydrogen is a product of the dehydration of CH3OH, it pushes both the equilibrium concentration of HCOOCH3 and the rate of the chemical reaction away from equilibrium. The degree of this effect depends on the mechanism of the catalytic reaction, since the dehydration reaction is a rather complex multi-step process, hydrogen atoms are not gradually separated from the CH3OH molecule, and further interaction of oxygen groups (formyl and methoxy) is observed.
Figure 2. Temperature dependence of the specific efficiency of CuO*ZnO*AhO3*ZrO2*CaO/bentonite catalyst in the decomposition reaction of methanol on dimethyl ether (1, 2, 3) and methyl formate (V, 23^) at different loading of the catalyst: 1 - 0.01 g; 2 - 0.025 g; 3 - 0.05 g
Figure 3. Dependence of methanol conversion rate on reaction temperature in CuO*ZnO*AhO3*ZrO2*CaO/bentonite catalyst: 1 - initial mixture CH3OH/Ar, 1 * - initial mixture CH3OH/(Ar+H2)
1, 2, 3 - initial mixture CH3OH/Ar; r, 2] 3 * - initial mixture CH3OH /(Ar+H).
Figure 4. Dependence of the reaction temperature on the relative performance of the CuO-ZnO/AhO3catalyst in the decomposition reaction of methanol on dimethyl ether (1; V), MF (2; 2^ and methane (3; 3^
However, the amount of CH3OCH3 formed generally increases slightly at both low and high reaction temperatures, although the reasons for this increase vary between different temperature ranges. If this increases at low temperatures, it is due to the fact that the parallel pathway of methyl formate formation is suppressed and, accordingly, most of the CH3O groups can pass to DME,
then at high temperatures, a large concentration of hydrogen suppresses the decomposition reaction of dimethyl ether, since hydrogen is one of its products. This effect is positive in terms of the direct production of dimethyl ether from synthesis gas. Calculation of the Gibbs energy values of the direct reaction for the production of DME: Figure 5 prepared in the temperature range 300-650 K. 2CO+4H2 ~ CH3OCH3+H2O
Figure 5. Calculated values of the Gibbs energy of the direct reaction to produce DME from CO and H2. Under pressure of 0.5 (1), 1 (2), 1.5 (3), 2.5 (4) and 3.0 (5) MPa
A complex of physicochemical methods was used to study the properties of catalysts for obtaining DME before and after catalysisby RFA showed that the initial CuO*ZnO*Al2O3*ZrO2*CaO/bentonite catalyst consisted mainly of copper and zinc oxides. After hydrogen reduction, the intensity of the copper oxide peak decreased and a peak corresponding to metallic copper ap-peared.As shown by the REM method, after catalytic tests, the CuO*ZnO*Al2O3*ZrO2*CaO/bentonite surface coalesces with the formation of distinct dark-coloured peaks ranging from 1 to 40 jm. The surface of Y-A12O3 is covered with craters with an average diameter of 2 jim and individual particles of about 1 jm.
Conclusion
The influence of various factors on the process of direct synthesis of CH3OCH3 from CO in one step was studied on the ZnOA^O3ZrO2CuO^ CaO/bentonite: y-AhO3catalyst and the increase in the volumetric rate decreased the conversion of carbon dioxide and the yield of dimethyl ether, carbon dioxide and hydrogen mol. It has been proven that the increase in the ratio leads to an increase in the yield of dimethyl ether and the conversion of soot gas.
As a result of studies on the effect of various factors on the production of target products, the process of obtaining DME from synthesis gas, pressure, temperature, and the mole ratio of hydrogen to H2, because the reaction of direct synthesis of CH3OCH3 from synthesis gas prevails was found to lead to an increase in gas conversion.
References:
1. Chen J. et al. SAPO18 catalysts and their Bronsted acid sites //The Journal of Physical Chemistry. - 1994. - Vol. 98. -№. 40. - P.
2. RaboJ., Chemistry of zeolites and catalysis on zeolites. - Moscow: Mir, 1980. Vol.2, chapter 8, PP. 3-39.
3. Chang C. D., Lang W. H. Manufacture of light olefins: Patent. 4062905 USA. - 1977.
4. Bukhorov A. Q., Fayzullaev N. I. Kinetic laws of dimethyl ether synthesis in synthesis gas // AIP Conference Proceedings. - AIP 2022. - Vol. 1. - P. 050012.
5. Fornell R., Berntsson T., Techno-economic analysis of a kraft pulp-mill-based biorefinery producing ethanol // Energy. - 2013. - Vol. 50. - PP. 83-92.
6. Wang Z. et al. Gasification of biomass with oxygen-enriched air in a pilot scale two // Fuel. - 2015. - Vol. 150. -PP. 386-393.
7. Wang Z. et al. Gasification of biomass with oxygen- pilot scale two-stage gasifier // Fuel. - 2015. - Vol. 150. -PP. 386-393.
8. Li Y. et al. 100 t/Scale demonstrations of direct dimethyl ether synthesis from corncob //Renewable Energy. - 2010. -Vol. 35. - №. 3. - PP. 583-587.
9. Haro P. et al. syngas to gasoline and olefins via DME-a comprehensive techno-economic assessment // Applied Energy. - 2013. - Vol. 108. - PP. 54-65.
10. Mohamadian N. et al. Approach to casing collapse prediction in oil and gas well said ed by machine learning // Journal of Petroleum Science and. - 2021. - Vol. 196. - Patent. 107811.
11. Aslanov, S.C., Fayzullayev, N.I. Catalytic synthesis of C2-C4-alkenes from dimethyl ether// International Journal of Engineering Trends and Technology, 2021, 69(4), PP. 67-75
12. Chernyshev V. I. Optimization of the environment and the package of platinoid gauzes in the ammonia conversion reactor // Catalysis in industry. - 2008. - №. 3. - PP. 17-28.
13. He Z., Wang X. Hydro deoxygenation of model compounds and oil supgrading // Catalysis for sustainable energy.-2012.-Vol. 1. - №. 2013. - PP.28-52.
14. Bukina Z.M., Grafova G.M., Lin G.I., Markova N.A., Khadzhiev S.N. // Russian Federation Patent No 2442767. 2012.
15. Buronov F., Fayzullayev N. Synthesis and application of high silicon zeolites from natural sources //AIP 2022. -Vol. 2432. - №. 1. - Patent. 050004.
16. Kipnis M. A. et al. Features of preparation of the methanol synthesis component of a bifunctional dimethyl ether synthesis catalyst //- 2020. - Vol. 61. - PP. 145-154.
