The role of arsine in the deactivation of methanol synthesis catalysts

Quinn, R.; Mebrahtu, Thomas; Dahl, Thomas; Lucrezi, F.A; Toseland, Bernard A.

doi:10.1016/j.apcata.2003.12.034

“…In plants using a coal gasifier for producing synthesis gas, significant amounts of arsenic have been found on deactivated catalysts [207,216]. Studies with controlled addition of contaminants to a synthesis gas gave the following ranking of poisons: C 4 H 4 S = AsH 3 > CH 3 Cl > CH 3 SCN > CS 2 > COS > PH 3 > CH 3 F. Industrial examples of poisoning with fluorine and phosphorus have not been found.…”

Section: Other Poisonsmentioning

confidence: 99%

Methanol Synthesis

Hansen¹,

Nielsen²

2008

Handbook of Heterogeneous Catalysis

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The sections in this article are Introduction Thermodynamics Methanol Synthesis Catalysts Introduction Zn O / Cr 2 O 3 Catalyst Copper‐Based Catalysts Cu / Zn O + Element ( Al , Cr , … ) Promotion of Cu / Zn O / MOx Catalysts Cu / Zr O 2 Other Cu , Cu / Me , Cu / Me Ox Catalysts Pd ‐Based Catalysts Sulfide Catalysts Other Catalysts Activation of Cu / Zn Catalyst Activity as a Function of the Nature of Copper‐Based Catalysts Catalyst Deactivation Sintering Sulfur Poisoning Other Poisons By‐Product Formation Reaction Mechanism(s) and Active Sites Cu + in a Zn O Matrix as the Active Center The S chottky Junction Theory Partly Oxidized Copper Independent of Support as Active Sites Metallic Copper in Dynamic Interaction with the Support Cu –Zinc Surface Alloy Model Water Gas Shift Reaction Kinetics Reaction Rate Equations Diffusion Restrictions Kinetics in Slurry Phase Methanol Synthesis Methanol Synthesis Technology Synthesis Gas Preparation Natural Gas Reforming Adiabatic Pre‐Reforming Tubular, Fired Reforming Autothermal Reforming and Oxygen‐Fired Secondary Reforming Gasification of Heavy Oil, Coal or Biomass Coproduction in Ammonia Plants and Use of Off‐gases Economics of Synthesis Gas Preparation Reactor Systems and Synthesis Loop Layout Slurry Phase Reactor Types Methanol Purification Concepts Circumventing the Equilibrium Limitations Other Methanol Synthesis Routes and Technologies Methanol Synthesis by Methane Activation Conclusion

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“…Arsenic content in energy sources continues to be a challenge to the energy industry because these compounds are potent catalyst poisons, hindering the optimum use of these fuels and their conversion into useful feedstocks [3]. For example, coal-derived syngas (largely CO and H 2 ) contains arsenic species that deactivate the Cu/ZnO/Al 2 O 3 catalyst used for producing methanol, a promising fuel for internal combustion engines, fuel cells, and a source of hydrogen [13]. Moreover, compounds such as p-arsanilic acid (4-aminobenzenearsenic acid, p-AsA) and roxarsone (4-hydroxy-3-nitrobenzenearsenic acid, ROX) are used as feed additives in the poultry industry [14,15] and are introduced into the environment through disposal and land application of contaminated poultry litter [14].…”

Section: Introductionmentioning

confidence: 99%

In situ ATR–FTIR and surface complexation modeling studies on the adsorption of dimethylarsinic acid and p-arsanilic acid on iron-(oxyhydr)oxides

Mitchell

¹

,

Goldberg

²

,

Al‐Abadleh

³

2011

Journal of Colloid and Interface Science

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“…In general, the smelting conditions of yellow phosphorus are micro‐oxygen, and the concentration of AsH 3 in yellow phosphorus tail gas is 6.96 × 10 2 mg/m 3 . On account of its potentially toxicity to noble metal catalysts, electrodes and membranes, AsH 3 gas will also affect the efficiency of subsequent production processes . Therefore, it is of important value to study the removal of AsH 3 from industrial waste gases.…”

Section: Introductionmentioning

confidence: 99%

Superior activity of Ce‐HZSM‐5 catalyst for catalytic oxidation of arsine at low oxygen

Xie

¹

,

Wang

²

,

Ning

³

et al. 2019

Applied Organom Chemis

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A series of Ce modified catalysts were prepared using equivalent‐volumetric ultrasonic impregnation method for AsH3 removal. The performance of catalytic oxidation of AsH3 under dynamic conditions was studied under different synthesis and reaction conditions. Through screening tests, the optimum catalyst was impregnated by 10 wt.% Ce (CH3COO)3 precursor and subsequently calcinated at 550 °C. When the reaction temperature reached 170 °C, the Ce‐HZSM‐5 catalyst could maintain an oxidation efficiency of over 90% in 82 hrs. Furthermore, the chemical structure and properties of the catalyst and its catalytic oxidation mechanism with AsH3 were analyzed using SEM‐EDS, BET, XRD, XPS, H2‐TPR and FT‐IR. The results showed that Ce mainly existed on the catalyst surface in the forms of Ce4+ and Ce3+. In the reaction process, the chemisorbed oxygen played a key role in the transformation between the two valence states. AsH3 was firstly oxidized to elemental As with the participation of lattice oxygen. Then, the elemental As was partially blown into the rear part of the adsorption column along with the air flow and subsequently, de‐sublimed on the column wall. Herein, the elemental As remained on the surface of Ce‐HZSM‐5 catalyst, which would further oxidize to As2O3. For the recovery of As, Ce‐HZSM‐5 proved to be a promising catalyst in AsH3 removal. Highlights The CeOx modified HZSM‐5 catalyst was used to catalytic oxidation of AsH3. The Ce‐HZSM‐5 catalyst could maintain over 90% oxidation efficiency in 82 hrs. AsH3 was catalytic oxidized to elemental As and H2O on the catalyst surface and the As can be collected. The As adsorbed on the catalyst surface can be oxidized to As2O3 but cannot be further oxidized to As2O5.

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The role of arsine in the deactivation of methanol synthesis catalysts

Cited by 34 publications

References 13 publications

Methanol Synthesis

Methanol Synthesis

In situ ATR–FTIR and surface complexation modeling studies on the adsorption of dimethylarsinic acid and p-arsanilic acid on iron-(oxyhydr)oxides

Superior activity of Ce‐HZSM‐5 catalyst for catalytic oxidation of arsine at low oxygen

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