New Catalysts Emerge

Nov. 14, 2011
A variety of processes will benefit.

Worldwide demand for industrial catalysts is worth $29.5 billion, with robust growth expected into the future, according to "Global Catalyst Market," a June 2011 report from Acmite Market Intelligence, Ratingen, Germany. The company points out that manufacturers rely on catalysis to produce 80% of the most industrially important chemicals, ones involved in $10-trillion worth of goods and services globally every year. The size of the market certainly provides ample incentives for ongoing developments in catalyst technology.

For example, in early September, Des Plaines, Ill.-based UOP, a Honeywell company, announced it will supply C3 Oleflex technology to Fujian Meide Petrochemical Company, Fujian City, China. The 660,000-metric-ton/yr propane dehydrogenation unit will be the largest in the world when it comes onstream in 2014. It was UOP's third major Oleflex announcement in 2011: another is expected before the end of the year.

Oleflex (Figure 1) allows the catalytic dehydrogenation of propane — and entry into the rapidly growing propylene market — independent of a steam cracker or fluid catalytic cracking unit.

"When we are developing catalysts, there are both technical and business milestones to be met," says Mike Cleveland, UOP business director for petrochemical process technology and equipment. "Oleflex has been like this and we are now on the third generation of the catalyst, with the fourth in development. This version has formulation changes to reduce coke formation and increase yield."

Propane-Dehydrogenation Unit
Figure 1. Oleflex technology allows sites without crackers to make propylene.Source: UOP.

For UOP, one of the main challenges is predicting what processes chemical and petrochemical makers will need in the medium and long term. This heavily depends on feedstock supply and location.

"We are always looking at marketing data and laying out plans. It can take 3–5 years to get a technology into practice and you need to be first to the market in our business. Oleflex is interesting because we had no enquiries for many years and suddenly propane dehydrogenation became really important. That's down to the price and availability of natural gas: if you told people five years ago what the difference between the price of crude oil and natural gas would be today, they'd think you were crazy," he adds.

In other markets, such as detergents, the company focuses primarily on improvements in efficiency rather than potential changes in feedstocks.

UOP has launched its fourth-generation Pacol catalyst, which converts C12–C16 normal paraffins into the corresponding mono-olefins used in today's detergents. Coupled with this is the new UOP/CEPSA Detal-Plus process to make linear alkylbenzene (LAB), the precursor to linear alkylbenzene sulfonate, now the most widely used surfactant in biodegradable household detergents. Detal-Plus uses transalkylation of heavy alkylbenzene byproduct to produce up to 5% more LAB, while reducing capital investment and operating costs.

"One of the technical challenges for detergent manufacturers is the need to use hydrogen fluoride (HF), which is heavily regulated. However, Detal-Plus requires less energy because it operates at lower olefin-to-benzene ratios, so we might be able to help manufacturers remove some HF units altogether," notes Cleveland.

Furnace Tube Coating
Figure 2. Micrograph on left shows metallographic cross-section of ∼1,000-μ-thick CAMOL coating, while one on right shows topmost surface of the coating.

UOP always is watching for market trends that set technology needs, such as supply diversification that revealed the growing demand for polyester by the textile sector, notes Jose Carrazza, business director for petrochemical catalysts.

The company is focusing on two main objectives for polyester: increasing the capacity for purification/separation of raw-material paraxylene, and maximizing production of xylene isomers to increase overall process yield.

"The first involves ADS-47, our latest generation Parex adsorbent. It will be demonstrated commercially 4Q11. It offers 20–25% more capacity and/or 5–10% savings in energy consumption compared to our previous generation adsorbent, which was already recognized in the industry as the best performing product," says Carrazza.

To achieve the second objective, UOP has commercialized TA-30 catalyst. It is used in the transalkylation of toluene, C9 aromatics and C10 aromatics to increase the yield of xylenes that then are separated and purified in the Parex section of the complex.

"The main advantages of TA-30 are activity and yield. Activity benefit is reflected in twice the catalyst life (or half the required weight) of conventional catalysts. The yield is reflected in >1% point higher xylene production and/or lower naphtha requirement for the same xylene production," explains Carrazza.

Meanwhile, the company continues to enhance offerings in areas it's been involved in for decades. For instance, it has introduced QZ-2500H, the latest in a family of catalysts for cumene production by benzene alkylation.

"The main criteria for evaluating a cumene catalyst are operating conditions, which [are] reflected in energy savings and lower capital requirement for new units. QZ-2500H's ability to operate at a lower propylene/benzene ratio and 10–20°C lower temperature than previous generations translates to a more than 10% reduction in energy consumption," he adds.

2011 also has been an important year for developments at BASF, Iselin, N.J. It announced three major catalyst-plant expansions in the second half of the year. Then in early September, the company reported that an affiliate, BASF Canada, had joined Quantiam Technologies, Edmonton, Alta., to form BASF Qtech.

Microchannel Reactor
Figure 3. More effective heat dissipation in reactor permits use of more active catalyst.
Source: Velocys.

This startup, which will be run as an independent entity, will focus on commercializing advanced catalytic surface coatings for steam cracker furnace tubes that Quantiam has been developing since 1998.

The coatings — proprietary composites with a metallic matrix (Figure 2) — are designed to reduce both carbon formation and carbon accumulation in petrochemical furnaces, thereby increasing tubes' onstream time and cutting energy expenditure and carbon dioxide emissions.

BASF Qtech's CAMOL (catalyzed-assisted manufacture of olefins) technology works by making coated furnace tubes inert to filamentous coke formation at tube surfaces while at the same time gasifying amorphous coke that would otherwise accumulate from the gas phase.

Commercial furnace trials of first generation (Gen-1) technology have shown major increases in online run lengths with overall reductions in the energy required to produce olefins (ethylene and propylene) and a commensurate reduction in carbon dioxide emissions. Work now is underway on second generation (Gen-2) technology.

Richard Gay, BASF Qtech acting general manager, notes, "In developing the technology, we did not find one coating that would meet the needs of all crackers, all feedstocks, and all operating conditions. So we are advancing two coatings, a low-catalytic gasifier (LCG) and a high-catalytic gasifier (HCG). The LCG coating we believe is what is required in conventional ethane/propane cracking given the coking profile that is observed in the field. For naphtha crackers, we currently use the LCG coating where coking rates are low, and install the HCG coating where they are significantly higher. The Gen-2 products that are under development will build on this foundation."

"The Gen-1-ethane product is expected to be available commercially by year-end with the completion of one lifecycle field testing, and as we complete our assessment of coil samples and operating results, we will undertake any further optimization that may be warranted before commercial introduction."

The Gen-1-ethane product is delivering its expected benefits and Gen-1-naptha and Gen-2 are on target to achieve theirs, too, he adds. Specific results and goals include:

• Furnace run-length — Gen-1 achieved 1–2 years for lighter feedstocks and 100–400 days for heavier feedstocks, much better than the typical run of 10–90 days for uncoated coils; Gen-2 targets are 1,000+ days for lighter feedstocks and 200–500 days for heavier feedstocks;

• Energy and greenhouse-gas reductions — Gen-1 gave a 3–12% decrease for both lighter and heavier feedstocks; Gen-2 aims for a further 5–20% decrease for both feedstocks;

• Furnace coil lifetime: Gen-1-ethane provided one full lifecycle exceeding 4 years, which is on par with uncoated coils, while the Gen1-naptha is still undergoing its first lifecycle field testing, which should be completed in 2013; the goal for Gen-2 is 6–12 years for both feedstocks;

• Process temperature reduction: Gen-1 cut temperature by 20–60°C with both feedstocks; Gen-2 targets a 40–100°C reduction with both feedstocks.

Meanwhile, Velocys, Plain City, Ohio, is working on design and development of Fischer-Tropsch (FT) microchannel reactors (Figure 3) that enable reactions to occur at rates 10–15 times quicker than in conventional systems. The reactors consist of blocks containing thousands of narrow process channels filled with FT catalyst, which are interleaved with water-filled coolant channels. This provides much faster dissipation of the heat produced by the highly exothermic FT reaction than in conventional systems — and thus allows use of more-active FT catalysts, ones made by the proprietary organic matrix combustion (OMX) process of sister company Oxford Catalysts.

"Our OMX method allows us to produce highly controlled particle sizes with narrow distributions. So, therefore, the catalyst is highly active, stable and selective. In FT catalysis, all three are challenges — and especially in the microchannel business where catalysts need to be vastly more productive," says Kai Jarosch, Veolocys' manager, catalyst and material sciences.

"Our catalysts are head-and-shoulders above what is seen anywhere else. For example, in a typical slurry bed you would be looking at a catalyst producing 250 kg/m3/h of product. Our OMX catalyst achieved 1,500 kg/m3/h in a demonstration project," he notes.

This and other demonstration projects are opening up a host of opportunities for microchannel FT, particularly in gas-to-liquid (GTL) related activities, Jarosch adds.

"The growing disconnect between the price of gas and the price of oil is really helping us. The continued increase in gas discoveries, for example the huge recent shale gas find in the U.S., [is] increasing the differential between the two prices. The gas people want to convert their product into oil.

"On offshore GTL, we generate a real bang for the buck because we can achieve high productivity with a compact footprint. For example a 2,000-bbl/d GTL reactor takes up only one-quarter the space on a deck of a floating production vessel. Conventional technologies cannot meet the footprint, weight and height restrictions for floating production."

 In late 2011, the company will start operation of a GTL demonstration plant at a Petrobras facility in Fortaleza, Brazil, that will incorporate microchannel FT and steam reforming reactor and catalysts technologies. The unit, which will run at least six months, will demonstrate the fully integrated GTL process and support initial commercial installations. Velocys already is participating in funded engineering studies for these first plants.

In addition, the company is grooming biomass-to-liquids (BTL) technology. Earlier this year it successfully operated a 1-bbl/d BTL demonstration and pilot plant at a gasification facility [of SGC Energia] in Güssing, Austria.

"At Güssing we demonstrated a skid mounted FT reactor with SGC Energia. We had approximately 2,000 hours onstream using a live feed. It went very well, exceeding our expectations. In that time over 2.8 tons of FT product was produced. We have just sold them two full-scale reactors for use in a subsequent field demonstration," explains Jarosch.

Similar microchannel reactor technology now is set to be deployed in a 50-bbl/d BTL plant planned for Brazil in 2012.

Dow Chemical, Midland, Mich., has introduced Consista C601 polypropylene catalyst, which it calls the first sixth-generation Ziegler Natta catalyst. Using the non-phthalate-based catalyst system reportedly requires no capital expenditures or upgrades to existing facilities. It produces high-performance resins that are lighter, cleaner and clearer, says the company.

Meanwhile, Evonik Industries, Essen, Germany, is expanding its capacity for biodiesel catalysts via a new 60,000-mt/y alcoholates plant in Puerto General San Martin, Argentina. The plant is expected to be operational by the end of 2012.

Axens, Rueil-Malmaison, France, and Gentas, part of the Shoaibi Group, Al Khobar, Saudi Arabia, have signed a letter of intent to build a world-scale hydroprocessing catalyst production plant in Saudi Arabia. The catalysts will be used in the production of clean fuels.

Finally, Materia, Pasadena, Calif., has announced plans to open a catalyst manufacturing and R&D facility in Singapore. The production unit is expected to reach initial 10-mt/yr capacity by the end of 2012.

Seán Ottewell is Chemical Processing's Editor at Large. You can e-mail him at [email protected].

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