Study on Ammonia-Induced Catalyst Poisoning in the Synthesis of Dimethyl Oxalate

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Study on Ammonia-Induced Catalyst Poisoning in the Synthesis of Dimethyl Oxalate Available online at BCREC website: https://bcrec.id Bulletin of Chemical Reaction Engineering & Catalysis, 16 (1) 2021, 1-8 Research Article Study on Ammonia-induced Catalyst Poisoning in the Synthesis of Dimethyl Oxalate Hua-wei Liu*), Sheng-tao Qian, Er-fei Xiao, Ying-jie Liu, Jun Lei, Xian-hou Wang, Yu-hua Kong Gas Purification Division of Haiso Technology Co. Ltd., Hubei Industrial Gas Purification and Utilization Key Laboratory, Wuhan 430074, China. Received: 30th November 2020; Revised: 2nd January 2021; Accepted: 6th January 2021 Available online: 21st January 2021; Published regularly: March 2021 Abstract On an industrial plant, we observed and examined the ammonia-poisoning catalyst for the synthesis of dimethyl oxalate (DMO). We investigated the catalytic activity in response to the amount of ammonia and revealed the mechanism of such poisoning by X-ray photoelectron spectroscopy (XPS) characterization. Our results show that only 0.002% ammonia in the feed gas can significantly deactivate the Pd-based catalyst. Two main reasons were proposed: one is that the competitive adsorption of ammonia on the active component Pd hinders the carbon monoxide (CO) coupling reaction and the redox cycle between Pd0 and Pd2+; and the other is that the high-boiling nitrogen-containing amine compounds formed by reacting with ammonia have adsorbed on the catalyst, which hinders the progress of the catalytic reaction. The deactivation caused by the latter is irreversible. The catalytic activity can be completely restored by a low-temperature liquid-phase in-situ regeneration treatment. Copyright © 2021 by Authors, Published by BCREC Group. This is an open access article under the CC BY-SA License (https://creativecommons.org/licenses/by-sa/4.0). Keywords: dimethyl oxalate; synthetic catalyst; ammonia poisoning; space-time yield; regeneration How to Cite: H.-W. Liu, S.-T. Qian, E.-F. Xiao, Y.-J. Liu, J. Lei, X.-H. Wang, Y.-H. Kong (2021). Study on Ammo- nia-induced Catalyst Poisoning in the Synthesis of Dimethyl Oxalate. Bulletin of Chemical Reaction Engineering & Catalysis, 16(1), 1-8 (doi:10.9767/bcrec.16.1.9572.1-8) Permalink/DOI: https://doi.org/10.9767/bcrec.16.1.9572.1-8 1. Introduction dimethyl oxalate (DMO) in the presence of Pd/α- Al2O3 catalyst, and then with a copper-based The gas-phase synthesis of ethylene glycol catalyst the refined DMO is converted into eth- based on the oxalate route was firstly industri- ylene glycol (EG) through hydrogenation [5-10]. alized in China [1-2]. At present, an ethylene After more than 50 years of research and more glycol plant with an annual output of nearly 5 than 10 years of industrialization, this process million tons has been conceived, and a promis- has gradually matured [11-14]; however, in- ing plant (under construction) is expected to be depth research on industrial applications and of an annual output as high as more than 10 reaction processes are still needed. It is difficult million tons per year [3-4]. The process mainly for the existing large-scale devices to achieve involves a two-step reaction. First, CO and me- long-term cycles of full load and stable opera- thyl nitrite CH3ONO (MN) are carbonylated to tion, because the main problem lies in two key factors in the catalyst, i.e. DMO synthesis and * Corresponding Author. hydrogenation [15-18]. For instance, how to fur- Email: [email protected] (H.W. Liu); ther reduce operating costs as for Pd-based syn- Telp.: +86-27-87408382 thesis catalyst [19,20], or how to avoid pulveri- bcrec_9572_2021 Copyright © 2021, ISSN 1978-2993; CODEN: BCRECO Bulletin of Chemical Reaction Engineering & Catalysis, 16 (1), 2021, 2 zation and coking as for copper-based hydro- vice: the internal diameter of the stainless genation catalysts in order to extend the cata- steel reaction tube is 8 mm; the catalyst filling lyst life [21]. volume is 1 mL; the reaction space velocity is The catalyst for DMO synthesis is generally 3000 h-1; the reaction temperature is 100~130 a Pd-based catalyst supported by macropores α- ℃; and the carrying gas composition (V/V) is Al2O3 [22-25]. The selectivity of such catalyst is 20%CO+10%CH3ONO+70%N2. We examined usually as high as 99% or above. The activity is the amount of NH3 that is added into the carry- defined by the space-time yield under the con- ing gas and causes catalyst poisoning. ditions of the followings: reaction temperature DMO products were collected through con- of 100~140 ℃, space velocity of 2000~4000 densing the resulting reaction gas and h-1, and the MN content of 10~15%. Since the weighted to calculate the space-time yield carbonylation between CO and MN is a super (STY) index of the catalyst. The composition of exothermic reaction and self-decomposition of reaction gas (pre- and post-reaction) was ana- MN may occur when temperature exceeds 150 lyzed using Agilent 7820 gas chromatography, °C, the focus of the existing research is mainly equipped with TCD and FID dual detector, on the improvement of the catalyst's low- aiming at evaluating the conversion rate of temperature activity, the control of the reaction CH3ONO. process, and the safety of the system [26-30]. There are relatively few basic researches on the 2.3 Characterization of the Catalyst application of catalysts [31,32]. For example, VG Multilab 2000 X-ray photoelectronic en- the study on the influence of ammonia on syn- ergy spectrometer was used to determine the thesis catalysts. Gao and Wu [33,34] have stud- valence state and relative content of the ele- ied on the ammonia poisoning of Pd-based cata- ments on the surface of the catalyst. The test lysts for the synthesis of DMO. It is believed conditions were Al target, power of 300 W, and that 0.54% of ammonia content only causes a pass energy of 25 eV. The specific surface area decrease in catalyst activity but does not cause of the catalyst was measured by Anton-Paar complete deactivation. X-ray photoelectronic Autosorb-1-C-TCD-MS automatic physicochem- energy spectrometer (XPS) and other related ical gas adsorption instrument, adopting a ni- characterization analysis revealed that the trogen adsorption method. The composition of competitive adsorption of ammonia molecules DMO products (by-products, such as: dimethyl on the active Pd2+ hinders the oxidation- carbonate or methyl formate) were qualitative- reduction cycle of the latter, resulting in a de- ly analyzed by Thermo Fisher's Trace DSQ II crease in catalyst activity. Interestingly, we gas chromatography-mass spectrometer. have observed that in an industrial plant set- ting the trace amount of ammonia in the CO 3. Results and Discussions gas source leads to significant catalyst deacti- vation. Furthermore, we combined laboratory 3.1 Catalyst Poisoning simulation and characterization analysis of poi- In the September of 2015, a newly built eth- soned catalyst to reveal the mechanism of the ylene glycol plant with a production capacity of poisoning and regeneration. 200,000 tons per year was commissioned. The plant features a patented technology, i.e. 2. Materials and Methods WHB® Coal to Polymer Grade Ethyl Glycol 2.1 Catalyst Preparation New Technology [36]. Among them, the DMO synthesis system consists of two production The Pd-series catalyst for DMO synthesis lines (A/B, in parallel), each of which was filled was synthesized according to our previous with 50 cubic synthesis catalysts. In the com- method [35], which was used for a commission- missioning test run stage, only production line ing run test of 200,000 tons per year ethylene B was deployed to use. After 20 days, the oper- glycol industrial plant in 2015. Briefly, spheri- ating load was increased to 80%, and the hot cal α-Al2O3 carriers were loaded with PdCl2 spot temperature of the synthesis reactor stabi- through impregnation, and then reduced (by lized at 117 °C. On the 25th day, we observed hydrazine hydrate), rinsed, and dried at 120 that the catalyst activity tended to be declin- ℃. ing. After that, the catalyst hot spot tempera- ture needed to be increased by 1 °C every 1-2 2.2 Catalyst Activity Evaluation days to maintain catalyst activity and produc- tion load. On the 32nd day, the catalyst hot spot The evaluation of catalyst activity was car- temperature was required to be 125 °C, which ried out on atmospheric fixed-bed reaction de- Copyright © 2021, ISSN 1978-2993 Bulletin of Chemical Reaction Engineering & Catalysis, 16 (1), 2021, 3 lasted for the next 4 days. The methyl nitrite respectively. The results are shown in Figure 1 conversion rate continued to decrease. On the (a/b). 36th day, the production load had dropped to As shown in Figure 1, 1200 ppm ammonia 20% of the full load, and the catalyst was near- content can deactivate the DMO synthesis cat- ly deactivated. The system was shut down for alyst within 3 hours. As the ammonia content inspection. is reduced to 20 ppm, the test results showed It appeared that an acute poisoning on the that the catalyst activity can be reduced to be- catalyst was likely attributed to the described low 50% within 12 hours. This indicates that performance and the dysfunction of the cata- ammonia shows more significant impacts on lyst. We had investigated the possible causes to DMO synthesis catalyst than DEO synthesis the catalyst poisoning on-site. The main indica- catalyst, which is consistent with results from tors of raw materials, including carbon monox- industrial plant testing. ide, methanol, nitric acid, and oxygen, ap- peared to meet the process requirements. The 3.2 Evaluation of the Activity of the Poisoning purification unit in the primary process was Catalyst found to contain excessive ammonia.
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