Hubbry Logo
Cativa processCativa processMain
Open search
Cativa process
Community hub
Cativa process
logo
8 pages, 0 posts
0 subscribers
Be the first to start a discussion here.
Be the first to start a discussion here.
Cativa process
Cativa process
Cativa process
View on Wikipedia
from Wikipedia
Space-filling model of the [Ir(CO)2I2]− catalyst used in the Cativa process

The Cativa process is a method for the production of acetic acid by the carbonylation of methanol. The technology, which is similar to the Monsanto process, was developed by BP Chemicals and is under license by BP Plc.[1]: 293–307  The process is based on an iridium-containing catalyst, such as the anionic complex diiododicarbonyliridate(i) [Ir(CO)2I2]− (1).

The Cativa and Monsanto processes are sufficiently similar that they can use the same chemical plant. Initial studies by Monsanto had shown iridium to be less active than rhodium for the carbonylation of methanol.[2] Subsequent research, however, showed that the iridium catalyst could be promoted by ruthenium, and this combination leads to a catalyst that is superior to the rhodium-based systems. The switch from rhodium to iridium also allows the use of less water in the reaction mixture. This change reduces the number of drying columns necessary, decreases formation of by-products, such as propionic acid, and suppresses the water gas shift reaction.

The catalytic cycle of the Cativa process
The catalytic cycle of the Cativa process

The catalytic cycle for the Cativa process, shown above, begins with the reaction of methyl iodide with the square planar active catalyst species (1) to form the octahedral iridium(III) species (2), the fac-isomer of [Ir(CO)2(CH3)I3]−. This oxidative addition reaction involves the formal insertion of the iridium(I) centre into the carbon-iodine bond of methyl iodide. After ligand exchange (iodide for carbon monoxide), the migratory insertion of carbon monoxide into the iridium-carbon bond, step (3) to (4), results in the formation of a square pyramidal species with a bound acetyl ligand. The active catalyst species (1) is regenerated by the reductive elimination of acetyl iodide from (4), a de-insertion reaction.[1]: 94–105  The acetyl iodide is hydrolysed to produce the acetic acid product, in the process generating hydroiodic acid which is in turn used to convert the starting material (methanol) to the methyl iodide used in the first step.

References

[edit]
Revisions and contributorsEdit on WikipediaRead on Wikipedia

Cativa process

View on Grokipedia
from Grokipedia
The Cativa process is an industrial chemical process for the production of acetic acid via the carbonylation of methanol with carbon monoxide, utilizing a promoted iridium-iodide catalyst system that operates efficiently at low water concentrations. Developed by BP Chemicals and first commercialized in 1995 at a plant in Texas City, USA, the process achieves high reaction rates, with methanol selectivity exceeding 99%, and has become the dominant technology for acetic acid manufacture, accounting for a significant portion of the global capacity of over 20 million metric tons annually. Introduced as an advancement over the rhodium-based Monsanto process from the 1970s, the Cativa process employs iridium as the primary catalyst, co-catalyzed by iodide species such as methyl iodide, with promoters like ruthenium carbonyl complexes or metal iodides (e.g., lithium, ruthenium, or indium) to enhance stability and activity under reduced water conditions (typically 0.5–5 wt%). These promoters facilitate iodide abstraction from the iridium center, promoting carbon monoxide coordination and accelerating the migratory insertion step in the catalytic cycle, which involves key intermediates like fac,cis-[Ir(CO)₂I₃Me]⁻ and [Ir(CO)₃I₂Me]. The process's advantages include up to 30% lower energy requirements due to minimized steam usage for water recycling, reduced carbon monoxide emissions by approximately 70%, and lower byproduct formation—such as propionic acid at one-third the levels of the Monsanto process—leading to simplified purification and overall capital cost savings of about 30%. By 2000, multiple world-scale plants were operational, including facilities in Malaysia and South Korea, demonstrating throughput increases of up to 75% in retrofitted units. Ongoing optimizations continue to refine its environmental sustainability and efficiency, solidifying its role in meeting demand for acetic acid in applications like vinyl acetate monomer production and as a precursor in the chemical industry.

History and Development

Origins and Research

The origins of the Cativa process trace back to early investigations into methanol carbonylation during the 1960s and 1970s, when Monsanto researchers developed the rhodium/iodide catalyst system that became the basis for the Monsanto process. During these studies, initial tests of iridium/iodide catalysts revealed them to be effective for the carbonylation reaction but exhibited lower activity compared to rhodium, particularly under the high-water conditions (typically 10-15% w/w) employed in the Monsanto process, where rhodium demonstrated superior performance. In the 1980s, BP Chemicals acquired the licensing rights to the Monsanto technology and initiated extensive research to improve carbonylation efficiency, focusing on alternative catalysts to address limitations such as rhodium precipitation at low water levels and high costs. By the early 1990s, BP's investigations demonstrated that iridium catalysts exhibited greater potential under low-water conditions (around 5% w/w or less), offering higher stability and productivity without the precipitation issues associated with rhodium. This shift was supported by key patents filed between 1992 and 1996, including EP 0643034 (priority date October 1993) outlining improvements in iridium catalysis for acetic acid production. A pivotal advancement in BP's research was the discovery of promoter effects that significantly enhanced iridium activity and stability. Specifically, the addition of ruthenium carbonyl complexes, along with other metal iodides such as those of rhenium and osmium, was found to accelerate the catalytic cycle and prevent deactivation, enabling operation at lower water concentrations with rates up to twice those of unpromoted systems. Studies during this period emphasized catalyst stability, showing that the iridium-ruthenium combination maintained activity over extended periods without significant loss, addressing earlier concerns from Monsanto's tests. These developments culminated in the announcement of the Cativa process by BP Chemicals in 1996, marking the transition from rhodium-dominated technology to a more efficient iridium-based system for industrial methanol carbonylation.

Commercial Introduction

The Cativa process, developed by BP Chemicals, marked a significant advancement in acetic acid production through methanol carbonylation using a promoted iridium catalyst system, announced publicly in 1996 following years of research. This technology was first implemented commercially in November 1995 at the Sterling Chemicals plant in Texas City, USA, where it enabled a 20% increase in throughput from 290,000 to 350,000 metric tonnes per year without major capital investment, demonstrating the iridium catalyst's superior stability over traditional rhodium-based systems. The rapid transition from laboratory to industrial scale highlighted the process's potential for debottlenecking existing facilities, with early operations confirming high methanol selectivity exceeding 99% and reduced byproduct formation, such as propionic acid levels below 400 ppm. Subsequent adoptions accelerated the technology's rollout. In 1997, a 75% throughput increase was achieved at the Samsung-BP joint venture plant in Ulsan, South Korea, further validating the Cativa system's efficiency in low-water environments. By 1998, BP Chemicals retrofitted its own acetic acid plant at Hull, UK, yielding a 25% capacity expansion, followed by another 25% debottleneck at the Sterling Chemicals facility in Texas City in 1999. These implementations collectively boosted global production capacity by approximately 1.2 million tonnes per year by 2000, with the iridium catalyst enabling operations at water concentrations as low as 5 wt%, which minimized energy use for product purification. The first purpose-built Cativa plant came online in November 2000 as a joint venture between BP Chemicals and Petronas in Kertih, Malaysia, with an initial capacity of 500,000 tonnes per year. BP Chemicals, holding exclusive licensing rights to the underlying Monsanto technology since 1986, began offering the Cativa process for broader licensing to support such expansions, including arrangements with partners like Sterling Chemicals under exclusive operational agreements. Early operational data from 2000 to 2002 showed consistent yield improvements, with throughput gains of 20-75% across retrofitted sites translating to substantial cost reductions and enhanced process reliability. As BP Chemicals integrated into BP Plc following the 1998 merger, the technology portfolio remained under BP's control, facilitating further global dissemination. In 2020, INEOS acquired BP's acetyls business, including the Cativa technology, incorporating it into its portfolio for ongoing licensing and development. These milestones underscored the process's successful commercialization, shifting the industry toward more efficient iridium-catalyzed production.

Chemical Reaction

Overall Reaction

The Cativa process involves the catalytic carbonylation of methanol using carbon monoxide to synthesize acetic acid, as depicted in the balanced equation: \ceCH3OH+CO−>CH3COOH\ce{CH3OH + CO -> CH3COOH} This stoichiometric transformation requires equimolar amounts of methanol, which acts as the methyl source, and carbon monoxide, which supplies the carbonyl moiety, to yield one mole of acetic acid per mole of each reactant. The reaction is highly exothermic, with an enthalpy change of ΔH=−135.3\Delta H = -135.3 kJ/mol at 298 K. Under ideal conditions, the process generates minimal by-products, enabling acetic acid production with high purity and no significant formation of impurities such as formic acid. Thermodynamically, the reaction strongly favors product formation, characterized by a large equilibrium constant of K=1.368×1013K = 1.368 \times 10^{13} at 298 K; due to its exothermicity, the constant decreases with temperature but remains sufficiently high (K≫103K \gg 10^3) at typical operating temperatures around 150–200°C to ensure near-irreversible conversion. The Cativa process utilizes an iridium-based catalyst to promote this transformation efficiently.

Catalysts and Promoters

The primary catalyst in the Cativa process is an iridium-based species, most notably the anionic complex [Ir(CO)₂I₂]⁻, which operates within a liquid reaction medium containing methanol, water, acetic acid, and carbon monoxide. This iridium catalyst is typically introduced at concentrations ranging from 100 to 6000 ppm by weight relative to the reaction mixture, with preferred levels between 1000 and 5000 ppm to ensure high activity and stability under low-water conditions. The iridium is added in a form that readily dissolves or converts to the active species in situ, enabling efficient carbonylation without the need for heterogeneous supports. To enhance the performance of the iridium catalyst, particularly in accelerating the reductive elimination step, ruthenium promoters such as Ru(CO)₄I₂ are incorporated at concentrations of 500 to 2000 ppm, often at a molar ratio of greater than 2:1 relative to iridium. These ruthenium species function by interacting directly with iridium intermediates to facilitate iodide abstraction, thereby promoting faster turnover. Optional promoters, including lithium iodide or other alkaline metal iodides, are added at levels sufficient for iodide management, typically maintaining ionic iodide below 500 ppm to avoid inhibiting the catalyst while stabilizing the system against precipitation. The iodide co-catalyst system is integral to the Cativa process, comprising hydrogen iodide (HI) and methyl iodide (CH₃I) as essential components for methyl group activation and oxidative addition to the iridium center. Methyl iodide is maintained at 1 to 20 wt% (preferably 2 to 16 wt%) in the reactor to drive the formation of key iridium-methyl intermediates, while HI arises from the equilibrium with water and iodide species, supporting overall iodide balance without excessive free iodide accumulation. Catalyst preparation in the Cativa process emphasizes in-situ formation to generate the active species directly in the reactor, minimizing handling of sensitive complexes. Common iridium precursors include IrI₃ or H₂IrCl₆, which are dissolved in the reaction medium under carbonylation conditions to form [Ir(CO)₂I₂]⁻; for instance, H₂IrCl₆ is added as an aqueous solution and converts via iodination and carbonylation. Ruthenium promoters are similarly prepared in situ from precursors like Ru₃(CO)₁₂ reacted with iodine under CO pressure at elevated temperatures (e.g., 180°C, 25 barg), yielding Ru(CO)₄I₂. This approach ensures compatibility with the corrosive, iodide-rich environment and allows for precise control of metal loadings during startup or replenishment.

Reaction Mechanism

Key Catalytic Cycle Steps

The Cativa process employs an iridium-based catalyst, primarily the square-planar anion [Ir(CO)₂I₂]⁻, to facilitate the carbonylation of methanol to acetic acid through a series of organometallic transformations involving methyl iodide (CH₃I) as the key alkylating agent. The catalytic cycle begins with the oxidative addition of CH₃I to the Ir(I) center, rapidly forming a six-coordinate Ir(III) methyl complex. This step is notably faster for iridium than for rhodium in the analogous Monsanto process, occurring approximately 150 times more quickly due to the higher nucleophilicity of the iridium species. The reaction proceeds as follows: [\ceIr(CO)2I2−]+\ceCH3I→[\ceIr(CH3)(CO)2I3−][\ce{Ir(CO)2I2}-] + \ce{CH3I} \rightarrow [\ce{Ir(CH3)(CO)2I3}-] Under operating conditions, the methyl complex [\ce{Ir(CH3)(CO)2I3}-] (also denoted as fac,cis-[Ir(CO)₂I₃Me]⁻) is the predominant species. Promoters facilitate iodide abstraction from this complex to form the tricarbonyl intermediate [Ir(CO)₃I₂Me], which undergoes rapid migratory insertion of carbon monoxide (CO) into the Ir–CH₃ bond. This insertion forms the acetyl intermediate, yielding a five-coordinate Ir(III) acyl species. In the unpromoted cycle, the direct insertion from [\ce{Ir(CH3)(CO)2I3}-] is the rate-determining step, governed by the kinetics of CO coordination and migration, and is particularly sensitive to the concentration of free iodide ions, which can inhibit the process by forming stable adducts. The insertion is represented by: [\ceIr(CH3)(CO)2I3−]+\ceCO→[\ceIr(CH3CO)(CO)I3−][\ce{Ir(CH3)(CO)2I3}-] + \ce{CO} \rightarrow [\ce{Ir(CH3CO)(CO)I3}-] The cycle closes with the reductive elimination of acetyl iodide (CH₃COI) from the acyl complex, regenerating the active Ir(I) catalyst and releasing the product precursor. This step is facile for iridium, contributing to the overall efficiency of the process compared to rhodium catalysis. [\ceIr(CH3CO)(CO)I3−]→[\ceIr(CO)I2−]+\ceCH3COI[\ce{Ir(CH3CO)(CO)I3}-] \rightarrow [\ce{Ir(CO)I2}-] + \ce{CH3COI} [\ceIr(CO)I2−]+\ceCO→[\ceIr(CO)2I2−][\ce{Ir(CO)I2}-] + \ce{CO} \rightarrow [\ce{Ir(CO)2I2}-] Finally, CH₃COI undergoes hydrolysis in the aqueous reaction medium to produce acetic acid and hydrogen iodide (HI), which is then recycled by reaction with methanol to regenerate CH₃I, closing the iodide promoter loop essential to the process. \ceCH3COI+H2O−>CH3COOH+HI\ce{CH3COI + H2O -> CH3COOH + HI} \ceHI+CH3OH−>CH3I+H2O\ce{HI + CH3OH -> CH3I + H2O} Promoters such as ruthenium or iodide scavengers accelerate the rate-determining migratory insertion by lowering the effective iodide concentration, thereby enhancing the overall turnover frequency of the catalyst.

Role of Iodide and Promoters

In the Cativa process, iodide serves a dual role in the iridium-catalyzed methanol carbonylation. It acts as a ligand that stabilizes iridium species, such as [Ir(CO)₂I₄]⁻, preventing their precipitation and enabling operation at low water concentrations of 1-5 wt%. At these levels, iodide also suppresses the water-gas shift reaction by limiting the availability of reactive water and iodide-bound intermediates that could otherwise promote CO reduction to hydrogen and CO₂. This stability contrasts with rhodium-based systems, where low water leads to catalyst precipitation and reduced activity. Promoters like ruthenium and lithium iodide further modify the catalytic mechanism to enhance efficiency. Ruthenium, typically introduced as [Ru(CO)₃I₂]₂, promotes the migratory insertion step by forming transient mixed Ru-Ir clusters that abstract an iodide ligand from the key intermediate [Ir(CO)₂I₃(CH₃)]⁻, facilitating CO coordination and insertion into the Ir-CH₃ bond—this accelerates the overall carbonylation by up to 700-fold compared to the unpromoted system. Lithium iodide, meanwhile, elevates iodide ion activity to maintain optimal [I⁻] levels (around 5-15 wt% total iodide) without inducing iridium precipitation, providing synergy with ruthenium under low-water conditions and moderating hydroiodic acid concentrations to favor productive pathways. These modifications result in distinct kinetic effects, with the reaction rate approximated by the expression r=k[\ceIr][\ceCH3I][\ceH2O]0r = k [\ce{Ir}] [\ce{CH3I}] [\ce{H2O}]^0, reflecting first-order dependence on iridium and methyl iodide concentrations but independence from water due to the robust catalyst stability. In the low-water regime, this iodide-promoter system not only sustains high turnover frequencies (>1500 h⁻¹) but also avoids the solubility issues plaguing rhodium catalysts, which exhibit inverse iodide dependence and require >10 wt% water to prevent deactivation.

Industrial Implementation

Process Flow and Equipment

The Cativa process begins with feed preparation, where methanol is mixed with high-purity carbon monoxide (typically greater than 99% pure) and recycle streams containing unreacted methanol, methyl acetate, and methyl iodide from downstream operations. This mixture, along with water and the iridium catalyst system, forms the reaction medium, with careful control to maintain low overall water content in the system. The core reaction occurs in a stirred tank reactor (STR) with gas sparging at the base and jet mixing via an external cooling loop to ensure efficient gas-liquid contact and thorough dispersion without relying on traditional mechanical agitators, promoting high conversion rates under the process conditions. The effluent from the main reactor then passes through a secondary plug-flow reactor to provide additional residence time under plug-flow conditions, enhancing CO utilization before entering the flash tank. Following the reaction, the crude product stream undergoes flash vaporization in an adiabatic flash tank, where volatiles such as methyl acetate, methyl iodide, and dissolved gases are rapidly separated as overhead vapor for recycling. The resulting bottoms liquid, rich in acetic acid, is then fed to a series of distillation columns: a combined light ends and drying column removes residual water and low-boiling impurities, while a heavies column separates higher-boiling components like propionic acid, yielding high-purity acetic acid product with significantly reduced propionic acid levels compared to earlier processes. The homogeneous iridium catalyst remains dissolved in the liquid phase and is recycled directly from the flash tank bottoms back to the reactor, minimizing losses due to its high stability. Iodide levels in the system are maintained through periodic addition of hydrogen iodide (HI) to balance promoter concentrations and compensate for any purges. By-product handling is streamlined, with minimal solid waste generation; gaseous streams from reactor vents and purges, including carbon dioxide formed via side reactions, are vented after scrubbing to recover valuables like methyl iodide. The low-water operation of the Cativa process further simplifies the flow by reducing the need for extensive drying steps in separation.

Operating Conditions

The Cativa process operates under conditions that leverage the high activity and stability of the iridium catalyst, enabling efficient methanol carbonylation at lower water levels than preceding technologies. The reaction temperature is typically maintained between 180 and 195°C to balance kinetic rates and prevent thermal decomposition of components. Total reactor pressure is held at 30 to 40 bar, with the partial pressure of carbon monoxide ranging from 25 to 35 bar to ensure sufficient solubility and reaction driving force while minimizing non-productive gas consumption. Key reactant and promoter concentrations in the liquid phase include water at 0.5 to 5 wt%—significantly lower than the 10 to 15 wt% required in the rhodium-based Monsanto process to sustain catalyst performance—along with methyl acetate at 20 to 30 wt% and methyl iodide at 8 to 12 wt%. The reactor residence time is generally 1 to 2 hours, achieving greater than 99% conversion of methanol to acetic acid. Carbon monoxide efficiency exceeds 94%, supported by low purge rates that reduce waste and enhance overall resource utilization compared to earlier processes. These parameters contribute to the iridium catalyst's robustness, allowing stable operation without precipitation even at reduced water levels.

Advantages and Comparisons

Improvements over Monsanto Process

The Cativa process represents a significant advancement in methanol carbonylation for acetic acid production, primarily through the replacement of rhodium with iridium as the catalyst, enabling operation under more challenging conditions while maintaining high efficiency. Developed by BP Chemicals and commercialized in 1995, it addresses key limitations of the earlier Monsanto process, such as catalyst precipitation and dependency on high water levels, resulting in enhanced overall performance. A primary improvement lies in catalyst stability. The iridium catalyst in the Cativa process exhibits superior resistance to precipitation and decomposition, even at low water concentrations below 5 wt%, conditions that would cause the rhodium catalyst in the Monsanto process to deactivate rapidly. This stability allows for higher iridium concentrations in the reactor—up to five times greater than typical rhodium levels—without risking metal loss, thereby supporting sustained operation over extended periods. As a result, the Cativa process achieves reaction productivities up to 50 mol/L/h, approximately five times higher than the 10 mol/L/h typical of the Monsanto process under standard conditions. By-product formation is also markedly reduced. In the Monsanto process, propionic acid levels often reach 500 ppm due to side reactions like the water-gas shift, complicating downstream purification. The Cativa process minimizes this to less than 200 ppm by operating at lower water levels, which suppresses the water-gas shift reaction and limits acetaldehyde formation—a precursor to propionic acid. This improvement stems from the iridium system's lower propensity for hydrogen production and better selectivity, exceeding 99% for acetic acid based on methanol conversion. Additionally, the ability to maintain water concentrations below 5 wt% eliminates the need for large, energy-intensive drying columns required in the Monsanto process to handle higher water loads (typically >10 wt%). Mechanistically, the Cativa process benefits from faster oxidative addition of methyl iodide to the iridium center—approximately 150 times quicker than with rhodium—which decouples the reaction rate from methyl iodide concentration and enhances overall kinetics. Although the subsequent migratory insertion step is slower for iridium, this is effectively compensated by the use of iodide and metal promoters (such as ruthenium), which accelerate insertion and maintain high turnover rates without altering the core catalytic cycle shared with the Monsanto process. These enhancements collectively enable more robust and efficient operation.

Economic and Environmental Benefits

The adoption of the Cativa process has led to substantial capital cost savings of approximately 30% for new acetic acid plants compared to the rhodium-based Monsanto process, primarily due to simplified plant designs and smaller equipment sizes, such as reduced distillation columns enabled by low-water operation. This elimination of oversized distillation units for extensive water removal further contributes to these capital efficiencies by minimizing the need for additional drying infrastructure.00263-7) Operating costs are reduced by 10-30% through higher reaction yields exceeding 99% selectivity to acetic acid—compared to around 98% in the Monsanto process—and improved carbon monoxide utilization by about 9%, which lowers feedstock consumption. Energy demands are also lowered, with steam and cooling water requirements decreased by 30%, translating to savings of roughly 1-2 GJ per ton of acetic acid produced via reduced drying and processing needs.00263-7) These efficiencies result in a typical payback period for retrofitting existing Monsanto plants to Cativa technology of less than 2 years, as demonstrated in early 2000s implementations that achieved capacity increases of up to 70% with minimal additional investment. Environmentally, the Cativa process reduces aqueous effluent by over 50% through its low-water operation, which limits byproduct formation and simplifies waste streams compared to higher-water rhodium systems.00263-7) Carbon dioxide emissions are lowered due to more efficient CO usage and diminished water-gas shift activity, with total direct gaseous emissions cut by more than 50% in practice. Additionally, the iridium catalyst's high stability enables recycling rates exceeding 99%, minimizing heavy metal discharge into effluents and enhancing overall sustainability.00263-7)

Current Status and Applications

Licensed Facilities

The Cativa process technology is licensed by BP Plc, which transferred ownership of its acetyls business, including Cativa rights, to INEOS in 2020 following a $5 billion acquisition; this enabled INEOS to license the technology for select sites post-2015. The first commercial implementation of the Cativa process occurred at BP's Texas City facility in the United States in 1995, with a capacity of approximately 1 million metric tons per year; a retrofit was later installed at BP's (now INEOS) Hull facility in the United Kingdom as part of a capacity expansion, reaching an annual production capacity of 1.2 million metric tons of acetic acid by 2010. Celanese operates two major Cativa-based facilities. Its Singapore plant, which began operations in 2003, has a capacity of 500,000 metric tons per year. The Nanjing, China, facility started up in 2009 with a capacity of 1.2 million metric tons per year following an expansion that doubled output from an initial 600,000 metric tons. By 2000, additional world-scale plants using Cativa technology were operational in Malaysia and South Korea. As of 2025, the global capacity for Cativa process-based acetic acid production exceeds 10 million metric tons per year, reflecting widespread adoption in major producing regions.

Ongoing Developments

Recent research has focused on optimizing the Cativa process through simulation and reactor design modifications to enhance acetic acid purity and reduce energy consumption. A 2024 study utilized Aspen Plus simulations to replace equilibrium and conversion reactors with a plug flow reactor (PFR), achieving 100% acetic acid purity from an initial 85%, while eliminating the need for a separation unit and minimizing waste generation. This approach lowers operational costs and environmental impact, though validation through pilot-scale experiments remains a key ongoing challenge. Advancements in catalyst formulation continue to improve reaction efficiency and stability. In 2025, investigations into rhodium-based catalysts modified with triethyl phosphine (3EP) and triphenyl phosphine (3PP) ligands demonstrated higher yields (up to 4.62 per hour for Rh-3EP) and better solubility compared to standard rhodium-iodide systems, facilitating easier recycling in methanol carbonylation. Similarly, iridium catalysts promoted by salts like Li+, K+, or Hf+ with aza-crown macrocycles have shown accelerated rates by promoting iodide ligand dissociation, as reported in 2018 studies. These modifications aim to operate under lower water concentrations, enhancing overall process sustainability. Efforts to transition from homogeneous to heterogeneous catalysis represent a major ongoing direction to simplify product separation and catalyst recovery. Single-atom iridium catalysts stabilized by lanthanum on activated carbon (Ir-La/AC) have achieved turnover frequencies of 2200 h⁻¹ with over 90% selectivity for methyl acetate, bridging the gap between Cativa's homogeneous efficiency and heterogeneous practicality. Recent work in 2018-2019 has further explored carbon-supported Ir-La systems and acid-promoted variants, demonstrating comparable reactivity to homogeneous counterparts while reducing metal leaching. Additionally, the adaptation of Cativa-type bimetallic iridium-ruthenium catalysts for self-reductive decarbonylation of carboxylic acids to noralkanes, achieving near-quantitative yields in 2024, highlights expanding applications beyond acetic acid production. Sustainability initiatives include exploring as a surrogate in . Ongoing since has utilized ruthenium-rhodium systems to achieve up to 70% acetic acid yields from CO₂, H₂, and under milder conditions (°C, 80 bar), potentially reducing reliance on and lowering in industrial settings. These developments underscore the Cativa process's toward greener, more versatile catalytic technologies.

References

  1. https://technology.matthey.com/content/journals/10.1595/003214000X44394105
  2. https://www.sciencedirect.com/science/article/abs/pii/S0920586100002637
  3. https://cdn.ihsmarkit.com/www/pdf/RW2018-01-toc.pdf
  4. https://pubs.acs.org/doi/abs/10.1021/ja039464y
  5. https://journal.bcrec.id/index.php/jcerp/article/download/20320/9781
  6. https://books.rsc.org/books/edited-volume/1822/chapter/2142746/Transition-Metal-Catalysed-Methanol-Carbonylation
  7. https://www.ineos.com/news/ineos-group/ineos-announces-the-acquisition-of-the-eastman-texas-city-site-for-c-usd-500-million/
  8. https://www.bp.com/en/global/corporate/news-and-insights/press-releases/bp-agrees-to-sell-its-petrochemicals-business-to-ineos.html
  9. https://patents.google.com/patent/WO2004026805A1/en
  10. https://patents.google.com/patent/US6140535A/en
  11. https://doi.org/10.1021/ja039464y
  12. https://www.technology.matthey.com/article/44/3/94-105/
  13. https://patents.google.com/patent/US5883295A/en
  14. https://onlinelibrary.wiley.com/doi/10.1002/ceat.202100230
  15. https://patents.google.com/patent/US8461379B2/en
  16. https://www.researchgate.net/profile/Rick-Manner/post/Working-on-project-for-the-production-of-acetic-acid-by-methanol-carbonylation-using-cativa-process-and-I-want-kinetic-data-for-this-reaction/attachment/59d648c479197b80779a36b9/AS%253A468360388452352%25401488677226869/download/Captiva%2Bprocess%2Bpmr-v44-i3-094-105.pdf
  17. https://www.ingentaconnect.com/contentone/matthey/pmr/2000/00000044/00000003/art00001
  18. https://www.chem.mtu.edu/chem_eng/current/new_courses/CM3510/AceticAcidPaper.pdf
  19. https://patents.google.com/patent/US8519182B2/en
  20. https://doi.org/10.1016/S0920-5861(00)00263-7
  21. https://www.sciencedirect.com/science/article/abs/pii/S0360056410530013
  22. https://pubs.acs.org/doi/10.1021/om00020a039
  23. https://www.ineos.com/news/ineos-group/ineos-to-acquire-bps-global-aromatics-and-acetyls-business/
  24. https://www.celanese.com/about-us/who-we-are/the-present-days
  25. https://www.sec.gov/Archives/edgar/data/1306830/000095012310012453/d70731e10vk.htm
  26. https://www.globaldata.com/store/report/acetic-acid-market-analysis/
  27. https://www.ijcce.ac.ir/article_721689_a512a556b5f77075efb5a4f0297fb8aa.pdf
  28. https://pubs.rsc.org/en/content/articlelanding/2018/cy/c8cy00829a
  29. https://pubs.acs.org/doi/10.1021/acs.iecr.8b05402
  30. https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/cctc.202401370
  31. https://hal.science/hal-02347651v1/document
Add your contribution
Related Hubs
User Avatar
No comments yet.