Startseite CO2 hydrogenation to dimethyl ether over In2O3 catalysts supported on aluminosilicate halloysite nanotubes
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CO2 hydrogenation to dimethyl ether over In2O3 catalysts supported on aluminosilicate halloysite nanotubes

  • Alexey Pechenkin EMAIL logo , Dmitry Potemkin , Sukhe Badmaev , Ekaterina Smirnova , Kirill Cherednichenko , Vladimir Vinokurov und Aleksandr Glotov
Veröffentlicht/Copyright: 6. Oktober 2021
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Green Processing and Synthesis
Aus der Zeitschrift Green Processing and Synthesis Band 10 Heft 1

Abstract

This work presents results on CO2 hydrogenation to dimethyl ether (DME) over bifunctional catalysts consisting of In2O3, supported on natural clay halloysite nanotubes (HNT), and HNT modified with Al-MCM-41 silica arrays. The catalysts were characterized by TEM, STEM, EDX-mapping, NH3-TPD, XRD, low-temperature nitrogen adsorption, TPO, and H2-TPR techniques. Catalytic properties of In2O3/HNT and In2O3/Al-MCM-41/HNT in the CO2 hydrogenation to DME were investigated in a fixed-bed continuous flow stainless steel reactor at 10–40 atm, in the temperature range of 200–300°C, at GHSV = 12,000 h−1 and molar ratio of H2:CO2 = 3:1. The best catalyst for CO2 hydrogenation was In2O3/Al-MCM-41/HNT that provided DME production rate 0.15 gDME·(gcat·h)−1 with DME selectivity 53% and at 40 bar, GHSV = 12,000 h−1, and T = 250°C. It was shown that In2O3/Al-MCM-41/HNT exhibited stable operation for at least 40 h on stream.

Keywords: CO2 hydrogenation; dimethyl ether; indium oxide catalysts; halloysite nanotubes; mesoporous aluminosilicates

1 Introduction

Currently, many efforts of various researchers around the world are being made to solve environmental problems. Air pollution is considered one of the main such problems. Various options are offered – the use of alternative energy sources, such as solar [1], wind [2], and biofuel [3]. However, it is also necessary to pay great attention to the utilization of CO2. The ever-growing production capabilities of different countries lead to an increase in carbon dioxide emissions into the atmosphere. This is the reason for the increase in the so-called “greenhouse effect,” which leads to an increase in the global temperature of the planet and, accordingly, climate change. This, as well as the fact that CO2 is an inexpensive, readily available compound, requires the search for new technologies, methods, and ways of processing carbon dioxide. Recently, more and more attention of researchers from all over the world has been attracting the study of the reaction of CO2 hydrogenation into various compounds such as methane [4], methanol [5,6,7,8], dimethyl ether (DME) [9,10,11], or hydrocarbons [12]. Among these compounds, DME attracts attention as a multipurpose product – it is used in the synthesis of methyl acetate, dimethyl sulfate, various petrochemical compounds, as a feedstock for powering fuel cells [13,14,15]. Due to its properties – high cetane number (55–60), low autoignition temperature, and high oxygen content (∼35%), DME is considered as an alternative to diesel fuel or LPG. In terms of its physicochemical properties, DME is close to LPG, which allows its simple storage and transportation.

Commonly, DME is synthesized according to a two-stage scheme through the synthesis of methanol (MeOH) from synthesis gas on Cu/ZnO/Al2O3 (CZA) catalyst and its subsequent conversion into DME on a solid acid catalyst. However, the direct synthesis of DME is thermodynamically more favorable than the synthesis of methanol [16], which attracts more attention to the study of this process. Catalysts for the direct synthesis of DME by hydrogenation of CO2 are divided into two types: first, a mechanical mixture of catalysts for the synthesis of methanol and a catalyst for its dehydration; second, a catalyst called “bifunctional” which contains both types of necessary catalytic sites on its surface. Typically, first type systems are prepared by mixing or grinding of methanol synthesis and acidic components. Such method has some disadvantages like disintegration of its components during the reaction, mass, and heat transfer limitations [17]. So, recently, bifunctional catalysts have attracted much attention of scientists [10]. Another challenge is to perform direct DME synthesis with high selectivity without formation of CO. Industrial Cu/ZnO/Al2O3 methanol synthesis catalyst is also known to be active in reverse water gas shift (RWGS) reaction causing hydrogen losses due to formation of CO.

According to the recent density functional theory calculations [18], it is possible to obtain methanol with high selectivity via the hydrogenation of CO2 on indium oxide. The reaction proceeds by the cyclic mechanism of the formation of oxygen vacancies and subsequent activation of CO2 on them. Later, these calculations were experimentally confirmed. It was shown that methanol with ∼100% selectivity is achieved on bulk In2O3 at low CO2 conversions [19]. These works gave an impetus to further extensive studying of catalysts on indium oxide in the hydrogenation of CO2 – the effect of various supports, preparation methods, the structure of indium oxide, and various additives on the catalytic activity [20–24]. Thus, indium oxide as a catalyst for methanol synthesis looks promising. An acid component is required for the design of a bifunctional DME direct synthesis catalyst. Usually, γ-Al2O3 or various zeolites – H-ZSM-5, Y, MOR, FER – are used as an acid catalyst in a two-stage process [17,25–33].

In this work for the first time, halloysite aluminosilicate nanotubes (HNT) were used as an acid support for the direct synthesis of DME catalysts. Halloysite nanotubes (HNT) have a rolled tubular structure (length ∼1–2 μm, inner diameter 10–30 nm) [34–37]. In particular, halloysite was successfully applied as a support for catalysts of various applications, including aromatics hydrogenation [38–42], DME conversion to olefins [43], hydrogen production [44], Fischer–Tropsch synthesis [45], xylene isomerization [46,47], catalytic cracking [48], photocatalysis [49,50], etc. Its feature is that HNT contains two different types of active centers – functional groups of SiO2 are present on the surface of nanotubes, while Al2O3 groups are located inside. This surface chemistry allows the metal component to be applied to both the external and internal surfaces, depending on the desired properties.

Nowadays, core-shell structure catalysts, such as Cu–ZnO–Al2O3@HZSM-5 [51] or CuO–ZnO–Al2O3@SiO2–Al2O3 [52], are intensively studying in direct DME synthesis from CO2. These systems prevent metal particles from sintering [53] and deactivation due coke formation by side reactions [54]. So, in the literature there are works on the modification surface of halloysite with MCM-41 [36] to make core-shell structure. This core-shell halloysite – based aluminosilicate composite is promising for catalytic applications due to high specific surface area and enhanced thermal and mechanical properties [39]. However, pure MCM-41 doesn’t have the required acid sites on its surface. Therefore, before using it as a support, the surface was modified with aluminum in order to increase acid sites. The resulting Al-MCM-41 has a large amount of acid sites, which are necessary to produce DME by CO2 hydrogenation.

In this work, we present novel bifunctional In2O3 catalysts supported on natural clay nanotubes (10 wt% In2O3/HNT) and composite with structured mesoporous silica (10 wt% In2O3/MCM-41/HNT) for CO2 hydrogenation to DME.

2 Experimental section

2.1 Synthesis and characterization of catalysts

As a support for catalysts, HNT (≥98%, Sigma-Aldrich, St. Louis, MO, USA) and ordered mesoporous composite Al-MCM-41/HNT were used. This modified support was prepared by the template synthesis method as described in literature [43]. Cetyltrimethylammonium bromide (≥98%, Sigma-Aldrich, St. Louis, MO, USA) was used for the formation of MCM-41. Aluminum isopropoxide (≥98%, Sigma-Aldrich, St. Louis, MO, USA) was used as an aluminum source. The weight ratio between Al-MCM-41 and HNT in the synthesized support was 60:40%.

In2O3/HNT and In2O3/Al-MCM-41/HNT catalysts were synthesized by the incipient wetness impregnation method of HNT and Al-MCM-41/HNT with aqueous solutions of indium nitrate(iii) (Reakhim, Moscow, Russia, purity 99.99%) taken at desired ratio, respectively. The samples were dried at 80°C in air for 4 h and after that calcined at 400°C (heating rate 1°C·min−1) for 3 h in air.

Actual In2O3 loadings in the catalysts were determined by inductively coupled plasma atomic emission spectrometry (Optima instrument; Perkin-Elmer).

Transmission electron microscope (TEM) JEOL JEM-2100 (UHR) operated at 200 kV (the lattice resolution of 0.19 nm) and equipped with LaB6 gun was employed to investigate structure, morphology, and chemical composition of the obtained samples. The samples for the TEM analysis were prepared by the dispersing in ethanol. The as-prepared dispersed solution was dropped onto carbon-coated formvar TEM Cu grid (300 mesh, Ted Pella, Inc.). The acquisition of TEM/HRTEM images was performed in TEM mode using Olympus Quemesa 11 megapixel CCD camera. The collection of each EDX map was performed in STEM mode with help of EX-24065JGT energy dispersive X-ray (EDX) analyser.

The specific BET surface areas (S BET) and pore volume (V p) of the support and the catalysts were determined using the low-temperature N2-adsorption method using a TriStar3000 apparatus. Before experiment, all samples were outgassed in vacuum at 300°C, then nitrogen adsorption/desorption isotherms were recorded at −196°C. The specific surface area of the samples was calculated by the Brunauer–Emmett–Teller (BET) equation. The pore volume was evaluated in accordance with Barrett–Joyner–Halenda model.

NH3 temperature-programmed desorption (NH3-TPD) was used to evaluate the acid properties of the samples. The catalyst was saturated by mixture of NH3 and N2 at 100°C for 30 min. After that, the sample was purged with a stream of nitrogen to remove physisorbed ammonia at same conditions. Then NH3-TPD curve was recorded up to 700°C with a rate of 10° per minute.

Temperature-programmed reduction (H2-TPR) and temperature-programmed oxidation (TPO) experiments were carried out using a STA 409 PC Luxx derivatograph fitted with a QMS-200 mass spectrometer. For H2-TPR, the samples (∼50 mg) were heated from room temperature to 500°C (5°C·min−1) in a 10 vol% H2–Ar mixture flowing at 100 mL·min−1. For TPO, samples were heated from 25°C to 800°C in a 10 vol% O2–Ar mixture flowing at 100 mL·min−1.

X-ray structural analysis (XRD) of the samples was recorded on a Bruker D8 Advance (Bruker, Germany) diffractometer (CuKα) in the 2θ range of 8°–63° with a step 0.05° per 4 s. Analysis of the obtained diffraction data was carried out using the PowderCell 2.4 programme using the JCPDS international diffraction database as a reference.

2.2 Catalyst testing

Catalytic experiments on CO2 hydrogenation were studied in a fixed-bed continuous-flow stainless steel reactor (inner diameter 8 mm) at a 10–40 atm pressure in the temperature interval 200–300°C, at GHSV = 12,000 h−1 and molar ratio H2:CO2 = 3:1. Prior to the reaction, all the catalysts (V cat = 2 cm3, m cat = ∼1.4 g for In2O3/HNT and ∼0.5 g for In2O3/Al-MCM-41/HNT, particle size of 0.5–1 mm) were pretreated at 300°C for 1 h in helium flow. The temperature was measured using a chromel-alumel thermocouple, which was placed in the middle of the catalytic bed. The results were obtained after multiple catalytic experiments. The catalysts were tested in several temperature increasing/decreasing cycles. At each temperature, the catalyst was kept for 1–2 h. Thus, total time onstream under CO2 hydrogenation conditions was not less than 10 h. The catalytic performance during this period remained stable. The compositions of the inlet and outlet gas mixtures were analyzed by a gas chromatograph (Chromos-1000) equipped with TCD and FID detectors and molecular sieve (5A) and Carbowax columns. Argon was used as a carrier gas. The detection limits for CO, CO2, CH4, DME, and methanol were 5 × 10−3 vol%. The carbon imbalance in all catalytic experiments was ±5%.

CO2 conversion ( X CO 2 ), MeOH, and DME selectivity (S MeOH, S DME) were calculated as follows:

(1) X CO 2 ( % ) = C CO + C CH 4 + C MeOH + 2 × C DME C CO + C CH 4 + C MeOH + 2 × C DME + C CO 2 × 100

(2) S MeOH ( % ) = C MeOH C CO + C CH 4 + C MeOH + 2 × C DME × 100

(3) S DME ( % ) = 2 × C DME C CO + C CH 4 + C MeOH + 2 × C DME × 100

(4) W DME ( g DME ⋅ (g cat ⋅ h ) − 1 ) = F DME × M DME m cat

where C i  – outlet concentrations (vol%), F i  – flow rate (mol·h−1), n i  – mole amount (mol), m – catalyst weight (g), M i  – molecular weight (g·mol−1).

3 Results and discussion

3.1 Characterization of catalysts

The catalysts were characterized by TEM, STEM, EDX-mapping, NH3-TPD, XRD, low-temperature nitrogen adsorption, TPO, and H2-TPR techniques. The In2O3 loading, textural parameters, and structural data obtained from XRD patterns of fresh and used In2O3, In2O3/HNT, and In2O3/Al-MCM-41/HNT are presented in Table 1. We can see that for the In2O3/HNT and In2O3/Al-MCM-41/HNT, real loadings of In2O3 are less than calculated. This is due to the fact that during impregnation supports absorbed lower volume of the indium nitrate water solution. The BET surface (Figure A1 in Appendix) areas of In2O3 and HNT are quite similar and equal 68 and 71 m2·g−1, respectively. After the impregnation of In2O3 on the HNTs’ surface, morphological characteristics are practically unchanged: S BET and pore volume slightly decreased to 62 m2·g−1 and 0.13 cm3·g−1, respectively. The most likely reason is blocking of some pores by the indium oxide particles.

Table 1

In2O3 loading, S BET, pore volume, and coherent scattering region

Textural characteristics In2O3
Catalyst S BET (m2·g−1) V p (cm3·g−1) wt% CSRa (nm)
HNT 71 0.16 — —
MCM-41/HNT 514 0.42 — —
In2O3 Fresh 68 0.41 100 13
10% In2O3/HNT Fresh 62 0.13 9.12 16.5
Used 61 0.13 9.12 16.4
10% In2O3/Al-MCM-41/HNT Fresh 412 0.31 8.71 10.1
Used 410 0.3 8.71 10.1
  1. a

    CSR – coherent scattering region.

Formation of MCM-41 phase on HNT leads to significant increase of surface area due to ordered structure of silica arrays. After deposition of indium oxide, specific surface area decreased by 100 m2·g−1, for the same reason as on the In2O3/HNT catalyst. Acidity parameters of the catalysts and supports calculated from NH3-TPD method are listed in Table 2 (Figure A2). Based on the desorption spectra, the acidity was classified as weak and medium (amount of ammonia (μmol·g−1) desorbed below 300°C) and strong sites (amount of ammonia (μmol·g−1) desorbed above 300°C).

Table 2

Acidity properties of catalysts and supports

Sample Acidity parameters
Weak and medium acid sites (μmol·g−1) Strong acid sites (μmol·g−1) Total acidity (μmol·g−1)
HNT 22 122 144
Al-MCM-41/HNT 35 495 530
10% In2O3/HNT 17 98 115
10% In2O3/Al-MCM-41/HNT 31 451 482

As shown in Table 2, the acidity of unmodified halloysite is seriously lower than that of HNT/Al-MCM-41 due to the fact that modified with aluminum MCM-41 has strong acid sites on the surface [43]. The total amount of acid sites on the surface of In2O3 supported catalysts is reduced in comparison with supports. This fact can be explained by partial blocking of the pores by the indium oxide particles. For the catalysts after the experiment, we can say that total amount of acid sites remained the same.

Figure 1 shows the XRD patterns for fresh and used catalysts. According to XRD data, we can say that indium oxide on the surface 10% In2O3/HNT has cubic crystal phase structure [21] with crystallite size of 13 nm. In case of 10% In2O3/Al-MCM-41/HNT, the crystallite size of the indium oxide is slightly smaller – 10 nm. We assumed that this is due to the higher dispersion of indium oxide particles. As we can see from the diffraction patterns of the used catalysts (curve 3 and 5 on Figure 1), there are no significant changes in the number and composition of the peaks. We only note that for the used catalysts, the peaks related to indium oxide are slightly smaller compared to fresh catalysts. Both used catalysts don’t have any considerable changes in the crystal structure – pore volume and CSR remained almost the same. This tells us that indium oxide particles are stable on the catalysts surface.

Figure 1 XRD patterns of catalysts. (1) halloysite, (2) In2O3/HNT fresh, (3) In2O3/HNT used, (4) In2O3/Al-MCM-41/HNT fresh, and (5) In2O3/MCM-41/HNT used.
Figure 1

XRD patterns of catalysts. (1) halloysite, (2) In2O3/HNT fresh, (3) In2O3/HNT used, (4) In2O3/Al-MCM-41/HNT fresh, and (5) In2O3/MCM-41/HNT used.

The In2O3/HNT and In2O3/Al-MCM-41/HNT catalysts were studied by TEM, STEM, and EDX techniques. Figure 2 shows the TEM images of the fresh and used catalyst In2O3/Al-MCM-41/HNT, which are obviously similar.

Figure 2 TEM images of fresh (a and b) and used (c and d) In2O3/Al-MCM-41/HNT catalyst.
Figure 2

TEM images of fresh (a and b) and used (c and d) In2O3/Al-MCM-41/HNT catalyst.

HNT were observed in both samples, and the images show that the nanotubes remained stable under reaction conditions. The same results were obtained for the In2O3/HNT catalyst. Also, in Figure 2b and d, we can see the structure of the mesoporous MCM-41 type silica deposited on the outer surface of HNTs. Some agglomerates of fresh and used In2O3/Al-MCM-41/HNT catalysts were studied by STEM and EDX-mapping. Results are shown in Figure 3. It is seen that the STEM images (Figure 3c and d) of both catalysts are similar. It can be noted that the indium particles are located mainly in the same place as the silicon particles in the case of both catalysts. Thus, it can be concluded that In2O3/Al-MCM-41/HNT catalyst contains two types of active sites on the surface – indium oxide particles, supported on silica, and alumina oxide particles.

Figure 3 TEM images (a,c), STEM images (b,d) and the corresponding Al, Si and In mapping of fresh (a,c) and used (b,d) In2O3/Al-MCM-41/HNT catalyst.
Figure 3

TEM images (a,c), STEM images (b,d) and the corresponding Al, Si and In mapping of fresh (a,c) and used (b,d) In2O3/Al-MCM-41/HNT catalyst.

Catalysts were examined by H2-TPR (Figure 4) to study reducibility of catalysts. We can see that pure indium oxide isn’t reduced in the investigated temperature range. For the In2O3/Al-MCM-41-HNT, hydrogen consumption occurs only at ∼170°C, indicating that the indium oxide nanoparticles are mainly localized on mesoporous silica of Al-MCM-41 type. This peak can be correlated to reduction of In2O3 surface and can also be attributed as indirect evidence of the formation of oxygen vacancies on the surface of indium oxide [57,58]. For the In2O3/HNT, there is also a peak at ∼170, which could be assigned to reduction of In2O3 surface particles on the outer (SiO2) tubes surface as for the In2O3/Al-MCM-41/HNT. Calculation of H2-consumption over In2O3/Al-MCM-41/HNT shows us that 20% of In2O3 loading was reduced. In the case of In2O3/HNT, there are 16% In2O3 on 170°C peak. So, in In2O3/Al-MCM-41/HNT, a higher amount of surface active indium oxide is observed.

Figure 4 H2-TPR profiles of fresh In2O3/HNT and In2O3/Al-MCM-41/HNT catalysts.
Figure 4

H2-TPR profiles of fresh In2O3/HNT and In2O3/Al-MCM-41/HNT catalysts.

Based on the data obtained, it can be concluded that the 10% In2O3/HNT and 10% In2O3/Al-MCM-41/HNT catalysts contain two types of sites on their surface – In2O3 particles as a metal component for the synthesis of methanol and acidic sites of HNT or Al-MCM-41/HNT for its further dehydration to DME.

3.2 Catalytic results

The catalytic properties of the In2O3, 10% In2O3/HNT, and 10% In2O3/Al-MCM-41/HNT in CO2 hydrogenation samples were measured at T = 200–300°C, P = 10–40 atm, and GHSV = 12,000 h−1, respectively. Figure 5 shows temperature dependencies of CO2 conversion and selectivity to MeOH (Figure 5a) and DME (Figure 5b) for In2O3, In2O3/HNT, and In2O3/Al-MCM-41/HNT catalysts. Only CO, H2O, CH3OH, and DME were detected as products; no hydrocarbons were identified.

Figure 5 (a) Effect of temperature on CO2 conversion and methanol selectivity over In2O3, In2O3/HNT, and In2O3/Al-MCM-41/HNT catalysts in CO2 hydrogenation. (b) Effect of temperature on CO2 conversion and dimethyl ether selectivity over In2O3/HNT and In2O3/Al-MCM-41/HNT catalysts in CO2 hydrogenation. Reaction conditions: P = 40 atm, GHSV = 12,000 h−1; inlet composition (vol%): H2:CO2 = 3:1.
Figure 5

(a) Effect of temperature on CO2 conversion and methanol selectivity over In2O3, In2O3/HNT, and In2O3/Al-MCM-41/HNT catalysts in CO2 hydrogenation. (b) Effect of temperature on CO2 conversion and dimethyl ether selectivity over In2O3/HNT and In2O3/Al-MCM-41/HNT catalysts in CO2 hydrogenation. Reaction conditions: P = 40 atm, GHSV = 12,000 h−1; inlet composition (vol%): H2:CO2 = 3:1.

Among the tested catalysts, In2O3 catalyst exhibited the lowest CO2 conversion, but the highest methanol selectivity over the entire temperature range. This can be explained by the fact that no DME was observed in reaction products. It seems to be quite obvious, since this catalyst does not have required acid sites on its surface. We can see that CO2 conversion increases with increasing temperature from 1% at 200°C up to 4% at 300°C. The selectivity for methanol, on the contrary, decreases with increasing temperature from 99% at 200°C to 65% at 300°C due to the CO formation by RWGS reaction.

In contrast to bulk In2O3 for the supported In2O3/HNT and In2O3/Al-MCM-41/HNT catalysts, DME appears in reaction products, due to the presence of acid sites. Temperature dependence for DME selectivity is similar to methanol in case of bulk In2O3 – the curve decreases with increasing temperature. There are some reasons for that. First, methanol dehydration is exothermic reaction, so increasing temperature leads to decrease of DME/MeOH equilibrium ratio. Second, at high temperatures, RWGS reaction (which is endothermic) contributes more to product distribution. So, it should be an optimal temperature, where the combination of formation rate of DME and CO2 conversion will be maximum. Over the temperature range, we can see that on In2O3/Al-MCM-41/HNT there are higher values of CO2 conversion and DME selectivity than on In2O3/HNT. Most likely, it is connected with higher surface area and more acid sites on In2O3/Al-MCM-41/HNT catalyst. Figure 6 shows temperature dependencies of DME production rate on In2O3, In2O3/HNT, and In2O3/Al-MCM-41/HNT catalysts.

Figure 6 Effect of temperature on DME production rate over In2O3, In2O3/HNT, and In2O3/Al-MCM-41/HNT catalysts. Reaction conditions: P = 40 atm, GHSV = 12,000 h−1; inlet composition (vol%):H2:CO2 = 3:1.
Figure 6

Effect of temperature on DME production rate over In2O3, In2O3/HNT, and In2O3/Al-MCM-41/HNT catalysts. Reaction conditions: P = 40 atm, GHSV = 12,000 h−1; inlet composition (vol%):H2:CO2 = 3:1.

The highest DME formation rate of 0.15 gDME·(gcat·h)−1 was observed at 250°C on In2O3/Al-MCM-41/HNT. Further, the performance of the most active and selective catalyst In2O3/Al-MCM-41/HNT was studied in more detail.

It is well-known that with increasing pressure, the equilibrium of the CO2 hydrogenation reaction shifts towards the products according to the Le Chatelier principle. So, we studied the pressure influence on catalytic activity in DME direct synthesis from CO2 and H2. The results are shown in the Figure 7. The experiments were carried out at T = 250°C, GHSV = 12,000 h−1.

Figure 7 Effect of pressure on CO2 conversion, methanol, and DME selectivity and DME production rate over In2O3/Al-MCM-41/HNT catalyst. Reaction conditions: T = 250°C, GHSV = 12,000 h−1; inlet composition (vol%): H2:CO2 = 3:1.
Figure 7

Effect of pressure on CO2 conversion, methanol, and DME selectivity and DME production rate over In2O3/Al-MCM-41/HNT catalyst. Reaction conditions: T = 250°C, GHSV = 12,000 h−1; inlet composition (vol%): H2:CO2 = 3:1.

As expected, with increasing pressure, CO2 conversion and DME selectivity also increase, while MeOH passes through the maximum at 20 atm and then decreases. This is in accordance with thermodynamic equations for this system [9]. The highest value of the DME formation rate is observed at 4 MPa. Note that at temperatures higher than 250°C, W DME decreased, despite an increase in the CO2 conversion due to a significant drop of DME selectivity.

One of the key properties of the catalyst, in addition to activity, is the stability under reaction conditions. A series of experiments were carried out to investigate this aspect. Figure 8 shows the effect of time-on-stream on the outlet product concentrations and CO2 conversion. The In2O3/Al-MCM-41/HNT catalyst was tested at 250°C, the inlet mixture H2:CO2 = 3:1, and GHSV = 12,000 h−1. Under these conditions, only CO, MeOH, and DME were detected as reaction products; methane appeared only in trace amounts. During 10 h on stream, no significant changes were observed either in the conversion of CO2 or in the MeOH and DME selectivity. No significant changes in the selectivity of DME were observed after 8 h of the experiment. After that, catalyst remained in operation conditions for 24 h, and after that catalyst activity was recorded. All the parameters, such as methanol, DME selectivity, and CO2 conversion, remained the same. In our view, these results mean that indium oxide particles remained stable as well as acid sites of modified HNT. In addition, the spent catalyst was tested by TPO. No carbon deposition was observed. This means that acidic properties of HNT (strength and number of acidic sites) are optimal for DME synthesis reaction and do not induce condensation reactions.

Figure 8 Effect of time on stream on CO2 conversion, methanol, and DME selectivity, DME production rate over In2O3/Al-MCM-41/HNT catalyst. Reaction conditions: T = 250°C, P = 40 atm, GHSV = 12,000 h−1; inlet composition (vol%): H2:CO2 = 3:1.
Figure 8

Effect of time on stream on CO2 conversion, methanol, and DME selectivity, DME production rate over In2O3/Al-MCM-41/HNT catalyst. Reaction conditions: T = 250°C, P = 40 atm, GHSV = 12,000 h−1; inlet composition (vol%): H2:CO2 = 3:1.

Up to now, almost no works of using indium oxide for direct synthesis of DME can be found in literature; only one work devoted to the study Cu–In–Zr–O catalyst mixed with SAPO-34 zeolite for direct DME synthesis is available [59]. Basically, all works on the direct synthesis of DME from CO2 and H2 are devoted to the study of copper catalysts mixed with zeolites. So, we compared the best In2O3/Al-MCM-41/HNT catalyst with literature data. Table 3 shows comparative data, in particular, experimental conditions (temperature, pressure, flow), CO2 conversion, and DME selectivity. Since a fairly large number of works devoted to the hydrogenation of CO2 to DME are currently presented in the literature, the table shows those with similar experimental conditions with this work, in particular – pressure of 10–50 atm, temperature of 200–300°C, and inlet composition H2:CO2 = 3:1.

Table 3

Comparison of catalyst activities in CO2 hydrogenation to dimethyl ether

Catalyst T (°C) Pressure (atm) GHSV (mL·(gcat·h)−1) W (DME) (gDME·(gcat·h)−1) Reference
In2O3/Al-MCM-41/HNT 250 40 12,000 0.15 This work
CIZO1/SAPO-34 250 30 6,000 0.08 [59]
CZA2/HZSM-5 260 30 1,500 0.12 [28]
CZZ3/ferrierite 260 50 8,800 0.435 [29]
CZA/HZSM-5 260 50 3,000 0.29 [30]
CZZ/MFI 240 50 10,000 0.251 [17]
CZZ/BEA 260 30 8,800 0.3 [31]
CZZ/WO x −ZrO2 260 30 4,333 0.27 [32]
PdZn/TiO2-H-ZSM-5 270 20 3,500 0.025 [33]
  1. 1

    CuO-In2O3-ZrO2;

  2. 2

    CuO-ZnO-Al2O3;

  3. 3

    CuO-ZnO-ZrO2.

Catalytic activity of In2O3/Al-MCM-41/HNT is lower than literature data, but study of these systems is at the very beginning. Such systems look very promising due to the following factors: the possibility of a significant increase in CO2 conversion and selectivity for DME after optimization of the catalyst composition, its dispersion, the method of preparation, and adding of promoters. According to the literature data [60], catalysts based on indium oxide make it possible to obtain methanol with a selectivity of about 100%, and with the appropriate selection of the acid component, high DME yields can be achieved. It is also important that In2O3/MCM-41/HNT catalyst shows good stability, due to the fact that indium oxide particles do not sinter during the reaction, and acid sites remain stable in presence of water. There is a wide field for further catalyst improvement, including optimization of In2O3 morphology and interaction with the support, tuning acidic properties, doping by metals active in CO hydrogenation, such as Cu, Pd, Ga, and even Ni and Co. These points will be the subject of our further studies.

4 Conclusion

Indium oxide catalysts, bulk and supported on aluminosilicate HNTs and modified HNTs with ordered Al-MCM-41 silica arrays, were studied in CO2 hydrogenation to DME. Based on data from physicochemical methods, such as XRD, S BET, FTIR, and H2-TPR, we can suggest that these catalysts have two types of active sites – indium oxide particles, which are responsible for methanol formation, and acid sites of HNT, which are responsible for methanol dehydration to DME. The influence of temperature and pressure was studied. The best catalyst for CO2 hydrogenation was In2O3/Al-MCM-41/HNT that provides 4% CO2 conversion with DME selectivity 53% and DME production rate 0.15 gDME·(gcat·h)−1 at 40 bar, GHSV = 12,000 h−1, and T = 250°C. It was shown that this catalyst didn’t lose activity after 40 h of experiment. So, it is very promising systems, based on new material for direct hydrogenation of CO2 to DME.

  1. Funding information: This research was funded by RFBR project 19-33-60056 and as a part of the state task of Gubkin University (synthesis of MCM-41/HNT, textural properties evaluation, TEM), project number FSZE-2020-0007 (0768-2020-0007, A.G., V.V., K.Ch.).

  2. Author contributions: Alexey Pechenkin: conceptualization, writing – original draft, writing – review and editing, methodology, formal analysis, investigation; Dmitry Potemkin: writing – review and editing, investigation, conceptualization, formal analysis; Sukhe Badmaev: resources, investigation; Ekaterina Smirnova: methodology, visualization; Kirill Cherednichenko: methodology, visualization, resources; Vladimir Vinokurov: writing – review and editing, project administration; Aleksandr Glotov: writing – review and editing, supervision.

  3. Conflict of interest: Authors state no conflict of interest.

Appendix

Figure A1 Low-temperature nitrogen adsorption isotherms for the HNT, Al-MCM-41/HNT, In2O3/HNT, and In2O3/Al–MCM-41/HNT samples.
Figure A1

Low-temperature nitrogen adsorption isotherms for the HNT, Al-MCM-41/HNT, In2O3/HNT, and In2O3/Al–MCM-41/HNT samples.

Figure A2 NH3-TPD curves for HNT, In2O3/HNT, Al-MCM-41/HNT, and In2O3/Al-MCM-41/HNT catalysts.
Figure A2

NH3-TPD curves for HNT, In2O3/HNT, Al-MCM-41/HNT, and In2O3/Al-MCM-41/HNT catalysts.

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Received: 2021-06-14
Revised: 2021-08-10
Accepted: 2021-09-01
Published Online: 2021-10-06

© 2021 Alexey Pechenkin et al., published by De Gruyter

This work is licensed under the Creative Commons Attribution 4.0 International License.

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  71. Synthesis of tert-amylbenzene for side-chain alkylation of cumene catalyzed by a solid superbase
  72. Punica granatum peel extracts mediated the green synthesis of gold nanoparticles and their detailed in vivo biological activities
  73. Simulation and improvement of the separation process of synthesizing vinyl acetate by acetylene gas-phase method
  74. Review Articles
  75. Carbon dots: Discovery, structure, fluorescent properties, and applications
  76. Potential applications of biogenic selenium nanoparticles in alleviating biotic and abiotic stresses in plants: A comprehensive insight on the mechanistic approach and future perspectives
  77. Review on functionalized magnetic nanoparticles for the pretreatment of organophosphorus pesticides
  78. Extraction and modification of hemicellulose from lignocellulosic biomass: A review
  79. Topical Issue: Recent advances in deep eutectic solvents: Fundamentals and applications (Guest Editors: Santiago Aparicio and Mert Atilhan)
  80. Delignification of unbleached pulp by ternary deep eutectic solvents
  81. Removal of thiophene from model oil by polyethylene glycol via forming deep eutectic solvents
  82. Valorization of birch bark using a low transition temperature mixture composed of choline chloride and lactic acid
  83. Topical Issue: Flow chemistry and microreaction technologies for circular processes (Guest Editor: Gianvito Vilé)
  84. Stille, Heck, and Sonogashira coupling and hydrogenation catalyzed by porous-silica-gel-supported palladium in batch and flow
  85. In-flow enantioselective homogeneous organic synthesis
https://doi.org/10.1515/gps-2021-0058
Schlagwörter für diesen Artikel
CO2 hydrogenation; dimethyl ether; indium oxide catalysts; halloysite nanotubes; mesoporous aluminosilicates
Creative Commons
BY 4.0

Artikel in diesem Heft

  1. Research Articles
  2. MW irradiation and ionic liquids as green tools in hydrolyses and alcoholyses
  3. Effect of CaO on catalytic combustion of semi-coke
  4. Studies of Penicillium species associated with blue mold disease of grapes and management through plant essential oils as non-hazardous botanical fungicides
  5. Development of leftover rice/gelatin interpenetrating polymer network films for food packaging
  6. Potent antibacterial action of phycosynthesized selenium nanoparticles using Spirulina platensis extract
  7. Green synthesized silver and copper nanoparticles induced changes in biomass parameters, secondary metabolites production, and antioxidant activity in callus cultures of Artemisia absinthium L.
  8. Gold nanoparticles from Celastrus hindsii and HAuCl4: Green synthesis, characteristics, and their cytotoxic effects on HeLa cells
  9. Green synthesis of silver nanoparticles using Tropaeolum majus: Phytochemical screening and antibacterial studies
  10. One-step preparation of metal-free phthalocyanine with controllable crystal form
  11. In vitro and in vivo applications of Euphorbia wallichii shoot extract-mediated gold nanospheres
  12. Fabrication of green ZnO nanoparticles using walnut leaf extract to develop an antibacterial film based on polyethylene–starch–ZnO NPs
  13. Preparation of Zn-MOFs by microwave-assisted ball milling for removal of tetracycline hydrochloride and Congo red from wastewater
  14. Feasibility of fly ash as fluxing agent in mid- and low-grade phosphate rock carbothermal reduction and its reaction kinetics
  15. Three combined pretreatments for reactive gasification feedstock from wet coffee grounds waste
  16. Biosynthesis and antioxidation of nano-selenium using lemon juice as a reducing agent
  17. Combustion and gasification characteristics of low-temperature pyrolytic semi-coke prepared through atmosphere rich in CH4 and H2
  18. Microwave-assisted reactions: Efficient and versatile one-step synthesis of 8-substituted xanthines and substituted pyrimidopteridine-2,4,6,8-tetraones under controlled microwave heating
  19. New approach in process intensification based on subcritical water, as green solvent, in propolis oil in water nanoemulsion preparation
  20. Continuous sulfonation of hexadecylbenzene in a microreactor
  21. Synthesis, characterization, biological activities, and catalytic applications of alcoholic extract of saffron (Crocus sativus) flower stigma-based gold nanoparticles
  22. Foliar applications of plant-based titanium dioxide nanoparticles to improve agronomic and physiological attributes of wheat (Triticum aestivum L.) plants under salinity stress
  23. Simultaneous leaching of rare earth elements and phosphorus from a Chinese phosphate ore using H3PO4
  24. Silica extraction from bauxite reaction residue and synthesis water glass
  25. Metal–organic framework-derived nanoporous titanium dioxide–heteropoly acid composites and its application in esterification
  26. Highly Cr(vi)-tolerant Staphylococcus simulans assisting chromate evacuation from tannery effluent
  27. A green method for the preparation of phoxim based on high-boiling nitrite
  28. Silver nanoparticles elicited physiological, biochemical, and antioxidant modifications in rice plants to control Aspergillus flavus
  29. Mixed gel electrolytes: Synthesis, characterization, and gas release on PbSb electrode
  30. Supported on mesoporous silica nanospheres, molecularly imprinted polymer for selective adsorption of dichlorophen
  31. Synthesis of zeolite from fly ash and its adsorption of phosphorus in wastewater
  32. Development of a continuous PET depolymerization process as a basis for a back-to-monomer recycling method
  33. Green synthesis of ZnS nanoparticles and fabrication of ZnS–chitosan nanocomposites for the removal of Cr(vi) ion from wastewater
  34. Synthesis, surface modification, and characterization of Fe3O4@SiO2 core@shell nanostructure
  35. Antioxidant potential of bulk and nanoparticles of naringenin against cadmium-induced oxidative stress in Nile tilapia, Oreochromis niloticus
  36. Variability and improvement of optical and antimicrobial performances for CQDs/mesoporous SiO2/Ag NPs composites via in situ synthesis
  37. Green synthesis of silver nanoparticles: Characterization and its potential biomedical applications
  38. Green synthesis, characterization, and antimicrobial activity of silver nanoparticles prepared using Trigonella foenum-graecum L. leaves grown in Saudi Arabia
  39. Intensification process in thyme essential oil nanoemulsion preparation based on subcritical water as green solvent and six different emulsifiers
  40. Synthesis and biological activities of alcohol extract of black cumin seeds (Bunium persicum)-based gold nanoparticles and their catalytic applications
  41. Digera muricata (L.) Mart. mediated synthesis of antimicrobial and enzymatic inhibitory zinc oxide bionanoparticles
  42. Aqueous synthesis of Nb-modified SnO2 quantum dots for efficient photocatalytic degradation of polyethylene for in situ agricultural waste treatment
  43. Study on the effect of microwave roasting pretreatment on nickel extraction from nickel-containing residue using sulfuric acid
  44. Green nanotechnology synthesized silver nanoparticles: Characterization and testing its antibacterial activity
  45. Phyto-fabrication of selenium nanorods using extract of pomegranate rind wastes and their potentialities for inhibiting fish-borne pathogens
  46. Hydrophilic modification of PVDF membranes by in situ synthesis of nano-Ag with nano-ZrO2
  47. Paracrine study of adipose tissue-derived mesenchymal stem cells (ADMSCs) in a self-assembling nano-polypeptide hydrogel environment
  48. Study of the corrosion-inhibiting activity of the green materials of the Posidonia oceanica leaves’ ethanolic extract based on PVP in corrosive media (1 M of HCl)
  49. Callus-mediated biosynthesis of Ag and ZnO nanoparticles using aqueous callus extract of Cannabis sativa: Their cytotoxic potential and clinical potential against human pathogenic bacteria and fungi
  50. Ionic liquids as capping agents of silver nanoparticles. Part II: Antimicrobial and cytotoxic study
  51. CO2 hydrogenation to dimethyl ether over In2O3 catalysts supported on aluminosilicate halloysite nanotubes
  52. Corylus avellana leaf extract-mediated green synthesis of antifungal silver nanoparticles using microwave irradiation and assessment of their properties
  53. Novel design and combination strategy of minocycline and OECs-loaded CeO2 nanoparticles with SF for the treatment of spinal cord injury: In vitro and in vivo evaluations
  54. Fe3+ and Ce3+ modified nano-TiO2 for degradation of exhaust gas in tunnels
  55. Analysis of enzyme activity and microbial community structure changes in the anaerobic digestion process of cattle manure at sub-mesophilic temperatures
  56. Synthesis of greener silver nanoparticle-based chitosan nanocomposites and their potential antimicrobial activity against oral pathogens
  57. Baeyer–Villiger co-oxidation of cyclohexanone with Fe–Sn–O catalysts in an O2/benzaldehyde system
  58. Increased flexibility to improve the catalytic performance of carbon-based solid acid catalysts
  59. Study on titanium dioxide nanoparticles as MALDI MS matrix for the determination of lipids in the brain
  60. Green-synthesized silver nanoparticles with aqueous extract of green algae Chaetomorpha ligustica and its anticancer potential
  61. Curcumin-removed turmeric oleoresin nano-emulsion as a novel botanical fungicide to control anthracnose (Colletotrichum gloeosporioides) in litchi
  62. Antibacterial greener silver nanoparticles synthesized using Marsilea quadrifolia extract and their eco-friendly evaluation against Zika virus vector, Aedes aegypti
  63. Optimization for simultaneous removal of NH3-N and COD from coking wastewater via a three-dimensional electrode system with coal-based electrode materials by RSM method
  64. Effect of Cu doping on the optical property of green synthesised l-cystein-capped CdSe quantum dots
  65. Anticandidal potentiality of biosynthesized and decorated nanometals with fucoidan
  66. Biosynthesis of silver nanoparticles using leaves of Mentha pulegium, their characterization, and antifungal properties
  67. A study on the coordination of cyclohexanocucurbit[6]uril with copper, zinc, and magnesium ions
  68. Ultrasound-assisted l-cysteine whole-cell bioconversion by recombinant Escherichia coli with tryptophan synthase
  69. Green synthesis of silver nanoparticles using aqueous extract of Citrus sinensis peels and evaluation of their antibacterial efficacy
  70. Preparation and characterization of sodium alginate/acrylic acid composite hydrogels conjugated to silver nanoparticles as an antibiotic delivery system
  71. Synthesis of tert-amylbenzene for side-chain alkylation of cumene catalyzed by a solid superbase
  72. Punica granatum peel extracts mediated the green synthesis of gold nanoparticles and their detailed in vivo biological activities
  73. Simulation and improvement of the separation process of synthesizing vinyl acetate by acetylene gas-phase method
  74. Review Articles
  75. Carbon dots: Discovery, structure, fluorescent properties, and applications
  76. Potential applications of biogenic selenium nanoparticles in alleviating biotic and abiotic stresses in plants: A comprehensive insight on the mechanistic approach and future perspectives
  77. Review on functionalized magnetic nanoparticles for the pretreatment of organophosphorus pesticides
  78. Extraction and modification of hemicellulose from lignocellulosic biomass: A review
  79. Topical Issue: Recent advances in deep eutectic solvents: Fundamentals and applications (Guest Editors: Santiago Aparicio and Mert Atilhan)
  80. Delignification of unbleached pulp by ternary deep eutectic solvents
  81. Removal of thiophene from model oil by polyethylene glycol via forming deep eutectic solvents
  82. Valorization of birch bark using a low transition temperature mixture composed of choline chloride and lactic acid
  83. Topical Issue: Flow chemistry and microreaction technologies for circular processes (Guest Editor: Gianvito Vilé)
  84. Stille, Heck, and Sonogashira coupling and hydrogenation catalyzed by porous-silica-gel-supported palladium in batch and flow
  85. In-flow enantioselective homogeneous organic synthesis
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