Methyl methacrylate (MMA) is an important chemical raw material that can undergo self-polymerization or copolymerization with other monomers under heat, light, or in the presence of catalysts. It is a colorless and transparent substance with excellent weather resistance, UV stability, transparency, and high gloss. MMA is primarily used to produce polymethyl methacrylate (PMMA) and impact modifiers for polyvinyl chloride (PVC), such as ACR and MBS. It is also widely used in coatings, adhesives, textile printing, dyeing auxiliaries, and other fields.
I. Supply and Demand Situation
● From 2019 to 2023, the annual average growth rate of production capacity was 17.8%, while the annual average growth rate of consumption was 9.2%, leading to a continuous improvement in self-sufficiency. After 2021, supply and demand gradually reached a balance..png "MMA Supply and Demand Overview")
Figure 1: MMA Supply and Demand Overview (2019–2023)
● Asia is the world’s largest MMA production and consumption region, accounting for nearly 70% of global capacity, with supply and demand in the region largely balanced. China is the largest consumer globally, representing 29.3% of total consumption.
● North America is the second-largest production and consumption region, with a 14% share of global capacity, where supply and demand are also mostly balanced.
● Western Europe accounts for 8% of global capacity, but the shutdown of Mitsubishi Chemical’s UK plant in 2022 disrupted the region’s supply-demand balance.
● The Middle East has also emerged as an important exporter, featuring ethylene-based plants by Mitsubishi Rayon and SABIC, as well as a C4-based plant jointly operated by Aramco and Sumitomo.
From the demand perspective, here is an overview of MMA’s downstream applications from 2019 to 2023:
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Figure 2: MMA Downstream Industry Demand (2019–2023)
1. PMMA Consumption Sectors:
• Sanitation and Construction: PMMA is widely used in the sanitation and construction sectors, accounting for 32.0% of consumption.
• Automotive: With the increasing push for lightweight vehicles, PMMA shows significant demand potential in the automotive sector, representing 19.7% of consumption.
• Electronics and Appliances: PMMA applications in electronics and appliances account for 28.0%, particularly in areas such as LED/LCP displays, optical materials, optical fibers, and high-end medical materials.
2. MS Resin Application Fields:
• Display Light Guide Plates: MS resin is primarily used in display light guide plates. With the promotion of large-size, narrow-bezel displays, demand for MS resin remains stable.
• Cosmetic Packaging: MS resin is also utilized in cosmetic packaging, and its demand is expected to see slight growth in the future.
3. Impact Modifier ACR/MBS:
• Processing Type Products: Domestic ACR/MBS products are primarily processing types, but the market capacity is relatively small, influenced by competition from low-priced CPE.
• High-End Product Development: Increasing investment in high-end product R&D and focusing on high-quality development will be key opportunities for the growth of the ACR/MBS industry in the future.
4. Coatings Industry:
• Solvent-based Coatings: Currently, the domestic coatings industry is still primarily solvent-based, accounting for over 60% of the market.
• Eco-friendly Coatings: With the push from environmental policies, new water-based eco-friendly coatings are expected to grow rapidly. MMA, as a waterproof coating, has significant development potential.
5. Other Application Fields:
• MMA is also used in the lighting sector, accounting for 6.6%, as well as in emerging fields, accounting for 6.5%.
II. Comparison of Technological Process Routes
1. Main Process Routes:
• C2 Route: Includes the BASF method and the α-MMA method. The BASF method has a simple process but requires large investment and has a short catalyst lifespan. The α-MMA method is environmentally friendly but requires high-purity CO, resulting in high separation costs.
• C3 Route (ACH Method): The technology is mature and reliable with low investment; however, the acid causes high corrosion to equipment, waste liquid treatment costs are high, and the process is influenced by the operating rate of acrylonitrile.
• C4 Route: Includes the traditional isobutene method (three-step method) and the improved isobutene method (two-step method). Raw materials are easily available, but costs are highly influenced by C4 raw material prices, and the preparation of catalysts may be more difficult.
2. Domestic Routes:
• C1 Methanol/Aldehyde - Methyl Acetate Method: Large-scale plants have been put into operation, but the technology and product quality still need improvement.
• C2 Ethylene Method: Pilot-scale plants with capacities in the thousand-ton range have been built, but it is still in the research and development stage.
• C3 ACH Method: Adopted by several companies, with relatively mature technology.
• C4 Isobutene Oxidation Method: Includes both the three-step and two-step methods, with some companies already adopting and putting them into production.
3. Comparison of Different Process Routes:
• Investment Costs: The ACH method has relatively lower investment costs, but it may be significantly affected by fluctuations in raw material prices.
• Production Costs: Production costs for each process route are influenced by various factors, including raw material prices, catalyst efficiency, and energy consumption.
• Environmental and Safety Aspects: The C2 method is environmentally friendly and has high safety; however, the ACH method faces challenges in handling the highly toxic substance hydrogen cyanide.
4. Process Route Selection:
• Petrochemical Companies: Tend to choose the isobutene oxidation process.
• Coal Chemical or CTO Companies: Have clear advantages in choosing the C1 and C2 processes.
• Acrylonitrile Production Companies: The ACH method remains competitive when paired with acrylonitrile production.
Figure 3: Global Distribution of MMA Applications by Different Technological Routes
III. New Process: Bio-based Ethanol Carbonylation Method for MMA Synthesis
The methyl methacrylate process technology developed by DODGEN is an entirely new synthesis route, primarily using CO, ethanol, methanol, and formaldehyde as raw materials, and obtaining MMA through a three-step reaction. The innovation of this process lies in the bio-based nature of its raw materials, aligning with the global trend towards the demand for bio-based materials.
Process Principle and Steps
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1. Ethanol Carbonylation to Synthesize Propionic Acid:
• Raw Materials: Ethanol, CO
• Catalyst: Optimized catalyst system for propionic acid
• Reaction: Under the action of the catalyst, ethanol undergoes a carbonylation reaction with CO to produce propionic acid.
• Conversion Rate: Ethanol conversion rate is 99%, with an overall CO conversion rate of 95%.
2. Esterification of Propionic Acid to Propyl Ester:
• Raw Materials: Propionic acid, methanol
• Technology: Based on mature industrial esterification tower technology
• Reaction: Propionic acid reacts with methanol in the esterification tower to produce propyl ester (methyl propionate).
• Conversion Rate: Propionic acid conversion rate is 99%.
3. Hydroxy Aldol Condensation of Methyl Propionate and Formaldehyde to Produce MMA:
• Raw Materials: Methyl propionate, formaldehyde
• R&D Focus: Improve the single-pass conversion rate and selectivity of methyl propionate
• Reaction: Methyl propionate reacts with formaldehyde under specific conditions to undergo a hydroxy aldol condensation reaction, producing MMA.
• Conversion Rate and Selectivity: Single-pass conversion rate of methyl propionate is 15%, with a selectivity of 95%. Space-time yield is 168g/kg cat.h.
IV. Advantages of DODGEN Bio-based Ethanol Carbonylation Method for MMA Synthesis
1. Bio-based Raw Materials:
Ethanol can be sourced from bio-fermentation processes (such as corn or sugarcane), aligning with the global demand for bio-based materials.
2. Stable Costs:
The price of bio-based ethanol is relatively stable, which ensures that MMA products produced via this route also maintain stable production costs.
3. Environmental Benefits:
Compared to other processes, the ethanol carbonylation method generates fewer and simpler waste products, meeting environmental protection requirements.
4. High Conversion Rate and Selectivity:
The process achieves high ethanol conversion rates and CO conversion rates, while the single-pass conversion rate and selectivity of methyl propionate are also notably high.
5. Intermediate Product Value:
Propionic acid, as an intermediate product, or its derivatives (methyl propionate and propionic salts), can be sold, increasing the added value of the overall product line.
V. Challenges and Difficulties of the Bio-based Ethanol Carbonylation Method for MMA Synthesis
1. Separation Technology:
MMA is a heat-sensitive medium, so separation processes must be conducted under vacuum or low-pressure conditions. This may require specialized equipment, such as falling film evaporators, to ensure efficient separation.
2. Azeotrope Issue:
During production, various substances may form azeotropes, which complicates the separation process. This requires careful integration of techniques like pressure-swing distillation and rotating disk extraction to manage and resolve azeotrope-related issues.
3. Ultra-Low Temperature Melting Crystallization Technology:
To produce optical-grade PMMA, ultra-low temperature melting crystallization technology is essential to achieve the required purity and properties. This adds complexity to the production process and demands advanced equipment.
4. Low-Pressure Steam Consumption:
The MMA distillation process requires substantial low-pressure steam. The key challenge lies in obtaining low-cost low-pressure steam, as this is crucial for reducing overall production costs. Optimizing steam generation and consumption is vital for improving cost efficiency.
DODGEN, based on unit technology, has leveraged its engineering advantages to overcome the challenges outlined above, designing a feasible and reliable MMA process technology. With small-scale test data as a foundation, we have already completed the pilot plant flow diagram (PFD) and material balance calculations. Key equipment selection has been finalized, and the selection of other equipment is in the preliminary stages. Additionally, we have established the basic data for pilot-scale investment, land area requirements, and waste emissions.
To ensure the successful implementation of the engineering process, we plan to scale up to a 1,000-ton pilot plant based on the existing small-scale test technology. The safety evaluation for the first set of processes has already been completed by our experts. We sincerely invite colleagues from various industries who are interested in the bio-based ethanol carbonylation MMA technology to collaborate and help develop the pilot technology, contributing new development momentum to MMA production in China!
