Fact-checked by Grok 2 weeks ago

Anthraquinone process

The anthraquinone process, also known as the Riedl–Pfleiderer process, is the dominant industrial method for producing hydrogen peroxide (H₂O₂), accounting for approximately 95% of global production.^[1] It operates as a cyclic autoxidation procedure in which 2-alkylanthraquinones, dissolved in a mixture of organic solvents known as the working solution, serve as hydrogen carriers.^[2] The process begins with the catalytic hydrogenation of the anthraquinone to form anthrahydroquinone using hydrogen gas and a palladium catalyst, followed by oxidation with air or oxygen to regenerate the anthraquinone and release H₂O₂, which is then extracted into water and purified by distillation.^[3] This method enables high-purity H₂O₂ output, typically concentrated to 35–70% by weight, while recycling the organic components with minimal waste.^[2] Developed by chemists Hans-Joachim Riedl and Georg Pfleiderer at IG Farben (now part of BASF) in Ludwigshafen, Germany, between 1935 and 1945, the process was patented in 1940 and first commercialized on a large scale by E.I. du Pont de Nemours in 1953.^[1] Prior to this, H₂O₂ was primarily produced via electrolytic methods or direct synthesis, but the anthraquinone route offered greater efficiency and scalability, supplanting earlier techniques by the mid-20th century.^[2] As of 2024, it supports annual global production exceeding 6.5 million metric tons (as H₂O₂ equivalent) from plants with capacities up to 330,000 tons per year, driven by demand in applications such as pulp bleaching, chemical synthesis, wastewater treatment, and electronics manufacturing.^[1]^[4] Key features of the process include its use of a biphasic working solution—typically comprising non-polar solvents like C9–C10 aromatics for solubility and polar co-solvents like trioctyl phosphate to enhance extraction—along with fixed-bed or slurry reactors for the hydrogenation step at around 40–50°C and 1–5 bar pressure.^[2] The oxidation occurs non-catalytically at similar conditions, yielding crude H₂O₂ at 25–35% concentration before post-treatment to remove organic impurities.^[3] While energy-intensive due to multiple separation steps and solvent handling, ongoing optimizations in catalyst design (e.g., supported palladium) and process integration have improved selectivity above 90% and reduced environmental impact, making it a cornerstone of sustainable chemical manufacturing.^[1]

Overview

Process description

The anthraquinone process is the predominant industrial method for producing hydrogen peroxide, operating as a cyclic autoxidation process in which anthraquinone serves as an organic hydrogen carrier. In this method, anthraquinone is first hydrogenated to form anthrahydroquinone, which then undergoes oxidation in the presence of oxygen to liberate hydrogen peroxide while regenerating the original anthraquinone for reuse. This carrier-mediated approach allows for the safe and efficient indirect combination of hydrogen and oxygen gases under controlled conditions.^[5] The overall reaction facilitated by the process is 2H₂ + O₂ → 2H₂O₂, achieved through the sequential hydrogenation and oxidation steps rather than direct synthesis, which helps mitigate explosion risks associated with mixing hydrogen and oxygen. Developed originally by IG Farben in the 1940s, the process has evolved into a cornerstone of large-scale chemical manufacturing.^[3]^[6] The primary output of the anthraquinone process is an aqueous solution of hydrogen peroxide, typically at concentrations suitable for industrial applications, with the anthraquinone carrier continuously recycled to minimize waste and sustain the cycle. The collective capacity of plants employing this process accounts for over 95% of global hydrogen peroxide production, exceeding 6 million tons annually as of 2025, with individual plants having capacities up to approximately 300,000 tons per year.^[7]^[8]^[9]

Industrial significance

The anthraquinone process dominates global hydrogen peroxide (H₂O₂) production, accounting for over 95% of the world's supply, with an annual output of approximately 6 million metric tons as of 2025.^[7]^[10]^[11]^[8] This method's prevalence stems from its ability to produce H₂O₂ at scale for key applications, including bleaching in the pulp and paper industry, disinfection in water treatment and healthcare, and as an oxidizing agent in chemical synthesis for products like propylene oxide and pharmaceuticals.^[12]^[13]^[14] A major industrial advantage is the process's facilitation of on-site production through integrated facilities, particularly in end-user sectors such as pulp and paper mills and textile manufacturing. These integrated plants allow H₂O₂ to be generated directly at the point of use, minimizing the need for storage and transportation of the unstable compound, which decomposes over time and poses logistical challenges.^[15]^[16] This integration has evolved in modern operations to further reduce costs, with many facilities co-locating H₂O₂ production alongside downstream processes like epoxy resin synthesis, enhancing overall supply chain efficiency.^[17] Economically, the anthraquinone process offers superior performance over legacy methods like electrolytic production, achieving yields up to 99% and energy consumption around 17-18 kWh per kg of H₂O₂—significantly lower than the 25-30 kWh per kg required by electrolysis.^[18]^[19] This efficiency, combined with the cyclic use of anthraquinone as a carrier, supports cost-effective large-scale manufacturing while minimizing waste compared to earlier techniques.^[20]

History

Development origins

The anthraquinone process for hydrogen peroxide production was developed between 1938 and 1940 by chemists Hans-Joachim Riedl and Georg Pfleiderer at IG Farbenindustrie AG in Ludwigshafen, Germany. Initial patents were filed in 1938.^[21]^[22] This innovation stemmed from the company's efforts to create an efficient synthetic route to H₂O₂, leveraging the reversible redox properties of anthraquinone derivatives.^[21] The primary motivation arose during World War II, when Germany required a scalable alternative to the energy-intensive electrolytic methods previously used for H₂O₂ synthesis, such as the electrolysis of sulfuric acid. These traditional approaches consumed significant electricity and were ill-suited for wartime demands, particularly for high-purity H₂O₂. IG Farben's research addressed this by focusing on a cyclic auto-oxidation process that promised lower energy use and higher yields under controlled conditions.^[23] Patents for the process detailed the hydrogenation of anthraquinone in organic solvents using palladium catalysts, followed by oxidation to liberate H₂O₂.^[21] By 1943, IG Farben had constructed the first pilot plant at its Ludwigshafen facility, achieving small-scale production on the order of one metric ton per year to validate the method's feasibility. Early laboratory-scale tests revealed key challenges, including catalyst poisoning by trace impurities in the working solution and unwanted side reactions that degraded anthraquinone, reducing cycle efficiency and yield. Researchers at IG Farben identified these issues through iterative experiments, emphasizing the need for purified feedstocks and optimized reaction conditions to mitigate degradation pathways.

Commercial adoption

Following World War II, the anthraquinone process, originally developed by IG Farben in Germany during the 1930s, saw technology transfer to facilitate industrial reconstruction in the United States and Europe.^[24] The first commercial-scale plant utilizing this process was established by DuPont in the United States, commencing operations in 1953 with an initial capacity focused on high-purity hydrogen peroxide production.^[25] Adoption accelerated rapidly in Europe during the late 1950s and 1960s, driven by rising demand for hydrogen peroxide in bleaching, chemicals, and electronics sectors. Solvay, a Belgian chemical firm, initiated research in 1951 and operated a pilot plant from 1952 to 1954 before scaling to full commercial production, while German companies like BASF—successor to IG Farben's assets—restarted operations leveraging pre-war expertise.^[24]^[26] Key facilities such as Degussa's plant in Rheinfelden, Germany, came online in 1965 to meet expanding European needs.^[27] Significant technological advancements marked the 1970s, including a shift toward alkyl-substituted anthraquinones, such as 2-ethylanthraquinone and mixtures thereof, which improved solubility in working solutions and enhanced process efficiency and stability.^[2] In the 2000s, the anthraquinone process saw further integration with coproduction routes, notably the hydrogen peroxide to propylene oxide (HPPO) process, which uses anthraquinone-derived hydrogen peroxide as the oxidant; the first commercial HPPO plant, licensed by Evonik and thyssenkrupp Uhde, started up in Ulsan, South Korea, in 2008 with a capacity of 100,000 metric tons per year of propylene oxide.^[28] As of 2025, the anthraquinone process dominates global hydrogen peroxide production, accounting for more than 95% of output and operating in numerous plants worldwide, including over 60 in the Asia-Pacific region, with Asia contributing over 50% of global capacity due to rapid industrialization and investments in chemical manufacturing hubs.^[29]^[1]

Chemical principles

Key compounds involved

The anthraquinone process relies on a cyclic redox reaction involving anthraquinone as the primary oxidized form of the mediator. Anthraquinone, with the molecular formula C_{14}H_8O_2, features a fused tricyclic structure consisting of two benzene rings flanking a central quinone ring, with carbonyl groups at the 9 and 10 positions. This compound appears as a yellow, crystalline solid that exhibits low solubility in water but high solubility in hot organic solvents such as toluene and ethylbenzene.^[30] In the process, anthraquinone is reduced to its hydroquinone derivative, specifically 2-alkylanthrahydroquinones, which serve as the key reduced intermediates. A representative example is 2-ethylanthrahydroquinone (C_{16}H_{14}O_2), formed by the addition of hydrogen across the quinone moiety, resulting in hydroxyl groups at positions 9 and 10 along with an ethyl substituent at position 2. This reduced form enhances solubility in organic solvents compared to the parent anthraquinone, facilitating its handling in the non-aqueous working solution. Common alkyl substituents on the anthraquinone scaffold include ethyl, which is the most widely used due to its balance of reactivity and economic availability; tert-butyl, offering improved stability against oxidation; and amyl, which provides enhanced solubility in certain solvent systems. These modifications tune the compounds' solubility, stability, and selectivity in the redox cycle without altering the core quinone functionality.^[5]^[31] Side reactions during the process can generate byproducts such as ring hydroperoxides from incomplete oxidation or degradation products like anthrone, a partially reduced species formed via over-hydrogenation. These impurities are typically minimized through purification steps, such as extraction or distillation, to maintain process efficiency. The key compounds participate in a cyclic redox mechanism to produce hydrogen peroxide industrially.^[32]^[33]

Reaction mechanism

The anthraquinone process relies on a cyclic redox mechanism where anthraquinone (AQ) serves as a carrier to mediate the indirect combination of hydrogen and oxygen into hydrogen peroxide (H₂O₂), avoiding the direct explosive reaction between H₂ and O₂. The overall cycle is thermodynamically favorable, with a negative Gibbs free energy change (ΔG < 0) for the net reaction H₂ + O₂ → H₂O₂, driven by the standard free energy of formation of H₂O₂ (approximately -134 kJ/mol in aqueous solution), but the process is kinetically staged into hydrogenation and oxidation steps to enhance safety and selectivity.^[34] In the hydrogenation stage, AQ is reduced to anthrahydroquinone (AHQ) via the addition of hydrogen across the two carbonyl groups:

\ce{C14H8O2 + H2 -> C14H10O2}

This step proceeds through a surface-catalyzed mechanism, often described by the Rideal-Eley model, where molecular hydrogen dissociates on the catalyst surface (typically palladium or nickel), and the resulting hydrogen atoms sequentially add to the AQ carbonyls, forming intermediates such as acyl species and di-σ complexes before yielding the hydroquinone form (AHQ).^[34]^[35] Alkyl-substituted variants of AQ, such as 2-ethylanthraquinone, are commonly employed to improve solubility in the working medium without altering the core redox chemistry.^[34] The subsequent oxidation stage regenerates AQ while producing H₂O₂:

\ce{C14H10O2 + O2 -> C14H8O2 + H2O2}

This auto-oxidation occurs via a radical chain mechanism initiated by trace radicals, with propagation involving hydrogen abstraction from AHQ by hydroperoxyl radicals (HO₂•) to form an anthraquinonyl radical (AHQ•) and H₂O₂, followed by rapid reaction of AHQ• with molecular oxygen (O₂) to regenerate AQ and HO₂•:

\ce{AHQ + HO2^\bullet -> AHQ^\bullet + H2O2}

\ce{AHQ^\bullet + ^3O2 -> AQ + HO2^\bullet}

The hydroperoxyl radical acts as a chain carrier, with rate constants exceeding 10⁹ M⁻¹ s⁻¹ for the key steps, ensuring efficient peroxide formation through a hydroperoxide-like intermediate pathway. Side reactions can degrade efficiency, including over-hydrogenation of the aromatic rings to form partially saturated species like octahydroanthrahydroquinone, which cannot produce H₂O₂ upon oxidation, or auto-oxidative degradation to anthrones and dianthrones. Carbonyl hydrolysis of AHQ and formation of stable tautomers like oxanthrone also contribute to losses. Under optimized conditions, selectivity for the desired AHQ and H₂O₂ exceeds 98-99%, minimizing these pathways through controlled stoichiometry and mild environments.^[34]

Process steps

Hydrogenation stage

The hydrogenation stage initiates the anthraquinone process by reducing anthraquinone (AQ) to its corresponding anthrahydroquinone (AHQ) using hydrogen gas, forming a key intermediate for subsequent oxidation to hydrogen peroxide. This step occurs in specialized reactors designed to handle the three-phase reaction involving the organic working solution, gaseous hydrogen, and solid catalyst, ensuring efficient mass transfer and heat dissipation.^[36]^[37] Common reactor configurations include fixed-bed reactors, where the working solution flows through a packed bed of catalyst, and slurry-bed reactors, in which fine catalyst particles are suspended in the liquid phase via gas bubbling for enhanced mixing. In slurry-bed systems, the catalyst is subsequently separated by filtration to prevent interference in downstream steps. Fixed-bed systems are suitable for smaller scales but limited to hydrogenation degrees of 30–40% to manage heat and avoid hotspots, while slurry-bed reactors enable higher degrees up to 70% through uniform temperature distribution (radial and axial rise <1°C). Typical operating conditions involve temperatures of 40–70°C and pressures of 0.2–0.5 MPa (2–5 bar) to maintain solubility and reaction kinetics without excessive side reactions.^[37]^[38]^[36] Hydrogen uptake is precisely controlled at approximately 1 mole of H₂ per mole of AQ to achieve selective reduction to AHQ, with monitoring to limit uptake to 1–2 moles and prevent over-reduction to undesired byproducts like dihydroanthracene derivatives. Conversion efficiencies exceed 95%, with selectivities often surpassing 99%, facilitated by recycling unreacted hydrogen to minimize losses. This stage is typically the rate-limiting step in the cyclic process due to mass transfer limitations between gas, liquid, and solid phases, influencing overall throughput when integrated with the oxidation loop.^[39]^[38]

Oxidation stage

In the oxidation stage of the anthraquinone process, the hydrogenated anthraquinone (AHQ), produced in the preceding hydrogenation step, undergoes auto-oxidation with oxygen to regenerate anthraquinone (AQ) and form hydrogen peroxide (H₂O₂). This exothermic reaction occurs without a catalyst and is designed to maximize H₂O₂ yield while minimizing degradation of the working solution.^[40] Air or pure oxygen is sparged into the organic working solution containing AHQ, typically at temperatures between 30–80°C and pressures of 0–1 MPa (gauge), though common industrial conditions favor 50–55°C and 0.2–0.25 MPa to optimize reaction kinetics and safety. The process is conducted in a counter-current oxidation tower, where the gas phase flows upward against the descending liquid, creating intimate contact via microbubble dispersion for efficient oxygen transfer. This setup ensures the oxidation of AHQ to AQ, with H₂O₂ released primarily in the organic phase but facilitated toward the aqueous phase through a co-fed water stream.^[40]^[41]^[42] Yields based on AHQ conversion reach 95–97%, reflecting high selectivity toward H₂O₂ formation, with minimal side products such as trace water from minor hydrolysis or over-oxidation byproducts that do not significantly impact the cycle efficiency. The reaction's mild conditions limit anthraquinone degradation, preserving the mediator's stability over multiple cycles.^[41] Initial separation occurs within or immediately after the tower, where the generated H₂O₂ partitions preferentially into the aqueous co-feed due to its higher solubility in water compared to the organic solvent, forming a crude aqueous H₂O₂ stream at the bottom. The organic phase, now enriched in regenerated AQ, is decanted and recycled to the hydrogenation stage, enabling the cyclic nature of the process with minimal loss of the working solution components.^[41]^[42]

Product extraction and regeneration

Following the oxidation stage, the crude product stream containing dissolved hydrogen peroxide is subjected to counter-current extraction using demineralized water in a sieve-plate extraction tower, yielding a crude aqueous hydrogen peroxide solution typically at 20-40% concentration.^[2] This extraction exploits the solubility difference, separating the hydrogen peroxide into the aqueous phase while retaining the organic working solution. The extracted organic phase, now depleted of hydrogen peroxide, undergoes stripping via distillation to remove residual water and trace hydrogen peroxide, thereby regenerating the pure anthraquinone working solution for recycling to the hydrogenation stage.^[2] This step typically involves vacuum distillation to minimize thermal degradation, ensuring the working solution is dried and ready for reuse.^[2] To maintain process efficiency, the regenerated working solution is purified to remove degradation products such as over-hydrogenated anthraquinones and epoxides, often using adsorption on alkaline alumina or similar agents in a side-stream treatment. Ion exchange resins may also be employed to eliminate acidic or ionic impurities, while activated carbon beds can address polar by-products in some configurations.^[43] This purification enables a high recycle rate for the working solution, exceeding 99% in optimized industrial operations, with only minimal make-up additions required to compensate for losses. Waste generation in this stage is minimal, primarily consisting of vent gases containing volatile organic compounds (VOCs) from the working solution, which are treated via adsorption on activated carbon followed by solvent recovery and reuse.^[2] Liquid effluents, if any, are managed through pH adjustment and external treatment to prevent environmental release.^[2]

Industrial implementation

Working solutions and solvents

The working solution in the anthraquinone process for hydrogen peroxide production typically comprises 10-20% 2-ethylanthraquinone (EAQ) dissolved in an organic solvent mixture to facilitate the cyclic hydrogenation and oxidation reactions.^[43] A representative formulation includes approximately 50% C₉-C₁₀ aromatics, such as trimethylbenzene, and 30% alkyl phosphates like trioctyl phosphate (TOP), which together form the bulk of the solution at 80-90%.^[44] These mixtures ensure effective dissolution of both the quinone and hydroquinone forms, supporting the overall anthraquinone cycling.^[5] Solvent selection prioritizes low volatility to minimize losses during operation, high solubility for EAQ and its derivatives to maximize active component loading, and chemical stability to resist degradation under hydrogenation and oxidation conditions.^[45] Additional criteria include low solubility in water to aid phase separation during product extraction, a density higher than water for efficient settling, and a high distribution coefficient for hydrogen peroxide between the organic and aqueous phases.^[45] These properties collectively enhance process efficiency and reduce byproduct formation, with alkyl phosphates often added to improve hydroquinone solubility without compromising stability.^[46] Higher EAQ concentrations in the working solution boost productivity by increasing the yield of hydrogen peroxide per cycle, as more active quinone is available for reaction; however, concentrations exceeding optimal levels can promote phase separation, complicating extraction and regeneration steps.^[46] For instance, loadings around 120 g/L (roughly 12 wt%) balance solubility and performance in common aromatic-phosphate systems. Common alternatives to traditional petroleum-derived solvents include mixed alkylated benzenes with polar modifiers like tetraalkyl ureas, which further stabilize the solution against degradation.^[47]

Catalysts and conditions

In the hydrogenation stage of the anthraquinone process for hydrogen peroxide production, palladium supported on alumina is the predominant catalyst, typically with a loading of 0.1-0.5 wt% Pd.^[48] This configuration provides high selectivity for the reduction of 2-ethylanthraquinone to 2-ethylanthrahydroquinone, minimizing over-hydrogenation to undesired byproducts.^[49] Alternatively, Raney nickel catalysts have been employed, particularly in earlier implementations, offering cost-effective performance but lower selectivity compared to Pd-based systems. These catalysts exhibit operational lifetimes of 1-4 years in industrial settings, depending on process conditions and maintenance, with Pd/alumina variants demonstrating stability over extended cycles through periodic regeneration.^[5] Operational parameters for hydrogenation are optimized for efficiency and safety, typically conducted at temperatures of 40-70°C and pressures of 1-5 bar to ensure adequate hydrogen solubility in the working solution while controlling exothermicity.^[36] The reaction proceeds under neutral pH conditions to preserve catalyst integrity and anthraquinone stability.^[48] The subsequent oxidation stage requires no dedicated catalyst, relying on molecular oxygen from air to regenerate anthraquinone while liberating hydrogen peroxide. To mitigate radical-induced side reactions and stabilize the produced hydrogen peroxide, phosphoric acid is commonly added as an inhibitor, forming protective complexes that enhance yield and product purity. This step operates at milder conditions, with temperatures of 20-60°C and atmospheric pressure (1 bar), facilitating efficient gas-liquid contact without excessive energy input.^[36] Recent advancements since 2010 have focused on fixed-bed reactor configurations using highly dispersed Pd catalysts, such as Pd on alumina or cordierite monoliths, which enable higher throughput and reduce Pd consumption by up to 50% through improved dispersion and egg-shell distributions that minimize metal leaching.^[48] These innovations, including trickle-bed designs, have enhanced overall process selectivity above 99% while extending catalyst viability in continuous operations.^[5]

Scale and economics

The anthraquinone process operates at large industrial scales, with typical plant capacities ranging from 50,000 to 300,000 metric tons of hydrogen peroxide (H₂O₂) per year, enabling efficient production to meet global demand.^[50]^[51] Greenfield plants in this range require capital expenditures (CAPEX) of $200–400 million, depending on location, technology integration, and infrastructure needs.^[51]^[52] Operating costs for the process average $800–1,200 per metric ton of H₂O₂, with hydrogen feedstock comprising approximately 40% of expenses due to its stoichiometric role in the hydrogenation step, and energy accounting for about 20% amid compression, heating, and separation requirements.^[52]^[53] In integrated facilities, such as those co-located with hydrogen or propylene oxide production, return on investment (ROI) can achieve 10–15%, benefiting from shared utilities and reduced raw material logistics.^[52] The process's energy intensity stands at 60-70 GJ per metric ton of H₂O₂ for direct operations.^[54] As of 2024, global H₂O₂ production via this method was approximately 6.55 million metric tons, expected to reach about 6.9 million metric tons in 2025 and expand to approximately 8 million metric tons annually by 2030, fueled by growth in hydrogen peroxide-based propylene oxide (HPPO) manufacturing.^[4]^[8]

Advantages and challenges

Operational benefits

The anthraquinone process exhibits high selectivity in its core reactions, typically exceeding 98% for the hydrogenation of anthraquinones to anthrahydroquinones and the subsequent oxidation to yield hydrogen peroxide, which minimizes side products and enhances overall efficiency.^[48] This selectivity is achieved through the mediated cycle where anthraquinone acts as a carrier, enabling precise control over the reaction pathways without the need for direct interaction between hydrogen and oxygen.^[37] By avoiding the direct synthesis route, the process eliminates the risks associated with mixing H₂ and O₂, which can lead to explosive conditions in alternative methods.^[55] The process supports continuous operation across industrial scales, utilizing fixed-bed or slurry-bed reactors that allow for steady-state production with minimal downtime.^[48] A key operational strength lies in its high recycle rate of the working solution, typically exceeding 95%, which significantly reduces waste generation and resource consumption by regenerating and reusing the anthraquinone carrier multiple times per cycle.^[37] This closed-loop design ensures that only a small fraction of the working solution requires replenishment, promoting sustainable material utilization. Versatility is another hallmark, as the process can be integrated for coproduction of hydrogen peroxide with other chemicals, such as using the produced H₂O₂ for manufacturing propylene oxide.^[37] Safety is further bolstered by the staged nature of the reactions—hydrogenation and oxidation occur in separate vessels under controlled conditions—which inherently prevents explosive reactions and allows for safe handling even at elevated pressures and temperatures.^[55] Scalability represents a major operational benefit, with the process readily deployable from small-scale units to large facilities producing up to 300 kt/year of hydrogen peroxide, facilitated by robust catalyst systems and reactor designs that maintain performance across varying capacities.^[48] Anthraquinone mediation provides the necessary control for such flexibility, enabling seamless transitions between pilot and commercial operations.^[37]

Limitations and environmental considerations

The anthraquinone process for hydrogen peroxide production, while industrially dominant, faces several operational limitations that impact its efficiency and long-term viability. One primary constraint is the multistep nature of the process, involving sequential hydrogenation, oxidation, extraction, and regeneration stages, which demands significant energy input for operations such as distillation and solvent recovery.^[56] Additionally, degradation of the anthraquinone working solution occurs over cycles, particularly during hydrogenation with palladium catalysts, leading to reduced productivity and the need for frequent replacement of the quinone, thereby increasing operational costs.^[32] These degradation reactions produce side products that complicate purification and lower overall yields. Environmentally, the process is not considered green due to its reliance on organic solvents like alkyl phosphates and the generation of hazardous waste streams from solvent degradation and extraction residues.^[56] Life cycle assessments indicate substantial contributions to global warming potential, with approximately 0.615 kg CO₂ equivalent emitted per kg of 49% H₂O₂ solution, primarily from energy-intensive steps like steam generation for concentration and hydrogen production via natural gas reforming.^[57] Acidification and eutrophication potentials are also notable, at 1.81 × 10⁻³ mol H⁺ eq and 9.29 × 10⁻⁵ kg P eq per kg H₂O₂, respectively, largely attributable to upstream raw material sourcing and direct emissions. Hazardous waste generation stands at about 4.70 × 10⁻³ kg per kg H₂O₂, including spent solvents that require incineration or specialized treatment.^[57] Toxic by-products from anthraquinone degradation, such as ring-hydrogenated or oxidized derivatives, pose risks if not fully contained, contributing to environmental challenges through potential soil and water contamination in case of leaks.^[58] However, modern implementations mitigate some impacts via activated carbon scrubbers for volatile organic compound emissions and wastewater treatment to neutralize residual peroxides at parts-per-million levels, rendering effluents largely benign.^[2] Despite these measures, the overall process's high energy demands and waste profile drive ongoing research into greener alternatives, such as direct electrochemical synthesis, to reduce its environmental footprint.^[56]

References

[1]
Recent Advances in the Direct Synthesis of Hydrogen Peroxide ...
On an industrial scale, the anthraquinone autoxidation (AO) process described by H.J. Riedl and G. Pfleiderer produces H2O2 in a cyclic manner (Scheme 2).<|control11|><|separator|>
[2]
[PDF] The Manufacture of Hydrogen Peroxide
Hydrogen peroxide is manufactured using the anthraquinone process. This process is a cyclic operation where the alkyl anthraquinone is reused. The Synthesis ...
[3]
Computational Exploration of the Mechanism of the Hydrogenation ...
Hydrogen peroxide is produced commercially by the sequential hydrogenation and oxidation of anthraquinone (AQ) and tetrahydroanthraquinone (THAQ).
[4]
Development of an anthraquinone process for the production of ...
In this process, 2-alkylanthraquinone is sequentially hydrogenated and oxidized in different reactors to generate hydrogen peroxide. The alkyl group in 2- ...
[5]
[PDF] An Outlook beyond the Anthraquinone Process - Sci-Hub BOX
May 26, 2006 · Hydrogen peroxide (H2O2) was first recognized by. Thenard in 1818 as the product of the reaction of barium peroxide with nitric acid.<|control11|><|separator|>
[6]
Energy And Carbon Footprint Comparison With Anthraquinone ...
Aug 29, 2025 · The process accounts for over 95% of global hydrogen peroxide production, estimated at approximately 5.5 million tons annually. Energy ...Missing: percentage | Show results with:percentage
[7]
Hydrogen Peroxide Market 2025 Rapidly Growing Dynamics with
Oct 27, 2025 · In 2024, global Hydrogen Peroxide production reached approximately 6194 K MT, with an average global market price of around US$ 742 per MT.
[8]
Hydrogen Peroxide Market Size & Share Report, 2032
The hydrogen peroxide market size achieved USD 5.2 billion in 2023 and will grow at 6% CAGR from 2024 to 2032 driven by increasing demand from the pulp ...
[9]
https://en.kunststoffe.de/a/news/solvay-largest-hydrogen-peroxide-plant-i-267426
[10]
Hydrogen Peroxide - an overview | ScienceDirect Topics
Hydrogen peroxide is used in a large number of applications such as bleaching, disinfecting and oxidation processes. It is such an attractive oxidising ...
[11]
https://www.gminsights.com/industry-analysis/hydrogen-peroxide-market
[12]
China Integrated Chemical Plant Factory & Suppliers - ALLY
The production of hydrogen peroxide (H2O2) by anthraquinone process is one of the most mature and popular production methods in the world.
[13]
Plant for hydrogen peroxide production and a process using it
The new plant design is suitable for manufacturing hydrogen peroxide by the anthraquinone autoxidation process (AO-process). The production of hydrogen ...
[14]
https://alliancechemical.com/blogs/articles/how-to-use-hydrogen-peroxide-a-comprehensive-guide-for-industries-and-consumers
[15]
Electrosynthesis of Hydrogen Peroxide by Phase-Transfer Catalysis
Oct 24, 2019 · In 2015, close to 4.3 Mt of H2O2 was produced via the anthraquinone process, which consumes 17.6 kWh kg−1 H2O2, leading to an aggregate energy ...
[16]
Chemical and engineering bases for green H2O2 production and ...
At present, ∼40% of the total PO production capacity in China is based on the chlorohydrin method, 43% on the co-oxidation method, and 17% on the HPPO method.
[17]
Review Fundamental principles and environmental applications of ...
Jan 15, 2023 · Nowadays, nearly 95 % of H2O2 is produced via indirect anthraquinone process at a cost of high energy input, large infrastructure and ...
[18]
US2369912A - Process for preparing hydrogen peroxide
20, 1945 UNITED STATES PATENT OFFICE PROCESS FOR PREPARING HYDROGEN PEROXIDE Georg Pfleiderer and Hans-Joachim Riedl, Ludwigshafen-on-the-Rhine, Germany ...Missing: history | Show results with:history
[19]
How H₂O₂ is produced: The Anthraquinone Process
Apr 11, 2022 · This process was developed by Georg Pfleiderer and Hans-Joachim Riedl at IG Farben in Ludwigshafen between 1935 and 1945, and since then it has ...Missing: history | Show results with:history
[20]
Science: Surprise legacy of Germany's flying bombs | New Scientist
Jan 29, 1994 · The manufacturing process for hydrogen peroxide was devised by German chemists during the Second World War in order to launch thousands of V-1 ...Missing: II | Show results with:II
[21]
The Era of Diversification and Globalization (1950–2012) (Part 3)
One of the most successful processes, the anthraquinone process ... Pfleiderer during the 1930s and licensed to IG Farben for further industrial development.
[22]
[PDF] direct synthesis of hydrogen peroxide from oxygen and
Sep 24, 2007 · Industrially, H2O2 is produced by an anthraquinone auto-oxidation (AO) process. This process was first commercialized by Du Pont in 1953 and ...
[23]
[PDF] BASF History We create chemistry
I.G. Farben's third Buna plant is built at the Lud- wigshafen site according to the three-step process developed by Walter ...Missing: anthraquinone | Show results with:anthraquinone<|control11|><|separator|>
[24]
Evonik - Facebook
Oct 30, 2025 · To this day, hydrogen peroxide is produced worldwide using the anthraquinone process – a method that has proven its value through outstanding ...
[25]
HPPO Technology - Evonik Active Oxygens
The world's first industrial-scale HPPO plant, licensed jointly by Evonik Industries and thyssenkrupp Uhde, was built by SKC in Ulsan, South Korea, in 2008, ...Missing: commercial | Show results with:commercial
[26]
Industrial Hydrogen Peroxide MarketSize & Share Trends, 2034
Global manufacturers operate over 60 production plants in Asia-Pacific alone as of 2024. ... anthraquinone process. For instance, in North ... Asia-Pacific capacity ...Missing: worldwide | Show results with:worldwide
[27]
Anthraquinone | C14H8O2 | CID 6780 - PubChem - NIH
9,10-anthraquinone is an anthraquinone that is anthracene in which positions 9 and 10 have been oxidised to carbonyls.
[28]
Hydrogenation of alkyl-anthraquinone over hydrophobically ...
Oct 28, 2019 · ... anthraquinone is active and others are identified as degradation products because they cannot be further oxidized to produce H2O2.
[29]
Degradation Reactions in Anthraquinone Process of Hydrogen ...
Aug 6, 2025 · Present research concentrates on the process of anthraquinone degradation in the course of hydrogenation carried out in the presence of palladium catalyst.Missing: percentage | Show results with:percentage
[30]
Phenolic Hydrogen Transfer by Molecular Oxygen and Hydroperoxyl ...
Jan 10, 2020 · Hydrogen peroxide is produced from hydrogen gas and air in industry by using the anthraquinone process. The mechanism for the prodn. of hydrogen ...<|control11|><|separator|>
[31]
https://pubs.rsc.org/en/content/articlehtml/2019/ra/c9ra07351e
[32]
https://www.researchgate.net/publication/239226101_Degradation_Reactions_in_Anthraquinone_Process_of_Hydrogen_Peroxide_Synthesis
[33]
Indirect H2O2 synthesis without H2 | Nature Communications
Jan 26, 2024 · The Riedl-Pfleiderer process relies on H2 gas derived from steam-methane reformation. Steam-methane reformation is an endothermic reaction that ...Missing: history | Show results with:history
[34]
Chemical and engineering bases for green H2O2 production and related oxidation and ammoximation of olefins and analogues
### Summary of Fixed-Bed vs. Slurry-Bed Reactors in Anthraquinone Hydrogenation
[35]
Development and application of slurry–bed production technology of ...
Slurry-bed reactor: the radial and axial temperature rise of industrial reactor is less than 1 °C, and the average hydrogenation selectivity is more than 99% ...
[36]
CN104495756B - The anthraquinone method for hydrogenation ...
... hydrogenation, the pressure of hydrogenation is 0.15～0.35MPa, temperature is 40～75 DEG C, in hydrogenation process, fluid bed keeps bubbling or turbulent ...
[37]
Oxidation method for preparing hydrogen peroxide ... - Google Patents
(a)首先在30～80℃温度和0～1MPa(表压)压力下，将含氧气的气相分散到含氢化蒽醌衍生物的工作液中，得到含微小气泡的气-液混合流体；(a) Firstly, at a temperature of 30-80° C.
[38]
CN103803501A - Oxidation method for producing hydrogen ...
Processing rear oxidation yield through present method is 95%～97%, and tail oxygen level is 2%～4%. Embodiment 2. Enter hydride 50m from I district 3/ h, amount ...
[39]
Experimental investigation and simulation of gas–liquid–liquid ...
The most reported example of this type is the production of H2O2 via hydrogenation of anthraquinones and further oxygenation of hydroanthraquinones, as ...<|control11|><|separator|>
[40]
US2909532A - Treatment of hydrogen peroxide working solution ...
These by-products, or anthraquinone degradation products, are non-volatile i.e. they are not separable from the other components by distillation alone. While ...Missing: anthrone hydroperoxides
[41]
The scheme of the anthraquinone process. - ResearchGate
The primary reactions are represented in Fig. 1, where the AQ is hydrogenated into AHQ, and AHQ is then oxidized into H 2 O 2 and AQ.
[42]
[PDF] Extraction of Byproducts of Hydrogen Peroxide Working Solution ...
Nov 25, 2014 · Byproducts from hydrogen peroxide production, like degradation products, must be extracted to prevent deterioration of the solution's color, ...Missing: hydroperoxides | Show results with:hydroperoxides
[43]
Modeling of the Solubility of 2-Ethyl or 2-tert-pentyl Anthraquinone in ...
Sep 3, 2025 · Hydrogen peroxide production via the Reidl-Pfleiderer process critically depends on the solubility of alkylated anthraquinones in the working ...
[44]
US5662878A - Process for the production of hydrogen peroxide
For example, suitable ranges for 2-ethyl anthraquinone is approximately 3.5 to 6 weight percent. Suitable ranges for the tetrahydro 2-ethyl anthraquinone is ...
[45]
Progress and prospective of heterogeneous catalysts for H2O2 ... - NIH
Jun 16, 2022 · This paper reviews the improvement in the field of catalytic hydrogenation of 2-ethylanthraquinone to 2-ethylanthrahydroquinone for the successful production ...Missing: integrated | Show results with:integrated
[46]
Highly dispersed Pd catalyst for anthraquinone hydrogenation ...
Compared with Pd/Al2O3(OD) catalyst, Pd/Al2O3(PB) catalyst showed higher Pd dispersion and thinner Pd penetration depth which resulted in more catalytically ...
[47]
Hydrogen Peroxide Production | Intratec.us
Plant Cost Breakdowns Breakdown of Hydrogen Peroxide process unit (ISBL) costs and infrastructure (OSBL) costs; plant cost breakdown per discipline.
[48]
Hydrogen Peroxide Market: Global Industry Analysis and Forecast
The Hydrogen Peroxide Market size was valued at USD 3.55 Billion in 2024 and the total Hydrogen Peroxide revenue is expected to grow at a CAGR of 5.2% from ...
[49]
Hydrogen peroxide production costs? - Thunder Said Energy
In stockHydrogen peroxide production costs run at $1,000/Tpa, to generate a 10% IRR at a greenfield production facility, with c$2,000/Tpa capex costs.
[50]
Hydrogen Peroxide Production Cost Analysis Reports 2025
The report involves the cost analysis of production of hydrogen peroxide by the anthraquinone process. Details: Germany - based plant Q1 2025 From $ 2499.00 USD ...
[51]
Industrial feasibility of anodic hydrogen peroxide production through ...
Apr 17, 2020 · This manuscript clearly demonstrates the financial benefits of value-added product formation, such as hydrogen peroxide, over O 2 formation.
[52]
Hydrogen Peroxide Market Size, Share & Growth Research Report
Jun 17, 2025 · The Hydrogen Peroxide Market is expected to reach 6.11 million tons in 2025 and grow at a CAGR of 3.9% to reach 7.40 million tons by 2030.
[53]
Systemic risk control in anthraquinone-based hydrogen peroxide ...
This paper provides a comprehensive review of the safety concerns throughout the anthraquinone-based hydrogen peroxide production process, addressing risks and ...Missing: degradation anthrone
[54]
Hydrogen Peroxide Synthesis: An Outlook beyond the ...
Oct 23, 2006 · Hydrogen Peroxide Synthesis: An Outlook beyond the Anthraquinone Process. Jose M. Campos-Martin Dr., ... Download PDF. back. Additional links ...
[55]
Progress and prospective of heterogeneous catalysts for H2O2 ...
Jun 16, 2022 · This paper reviews the improvement in the field of catalytic hydrogenation of 2-ethylanthraquinone to 2-ethylanthrahydroquinone for the successful production ...
[56]
[PDF] Environmental Product Declaration Hydrogen peroxide (H2O2)
Oct 11, 2023 · The most common method today for producing hydrogen peroxide is the anthraquinone auto-oxidation process. An anthraquinone solution (an ...
[57]
Advances and Challenges in Hydrogen Peroxide Production from ...
Apr 27, 2025 · Traditional production through the anthraquinone process presents environmental and economic challenges due to its toxic by-products and harsh ...