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Automotive Catalyst Materials

Automotive Emissions Catalysts

Gasoline exhaust is often oxygen deficient due to the nature of engine operating regime. The PGM (Platinum group metals) on the catalytic converter need oxygen (O2) to efficiently function and reduce the emissions to acceptable levels. Oxygen storage materials (OSM) are hence used in conjunction with the conventional PGM materials to store O2 when the engine is operating under lean (excess oxygen) conditions. The O2 stored in the OSM is released when the conditions turn rich and there is a deficiency in O2.

Viridis manufactures several grades of OSM (oxygen storage materials) for automotive catalyst applications. OSM are essential components specifically in gasoline catalytic converters where they store O2 during oxygen rich operation (e.g. during light load operation) and release O2 to facilitate reactions during oxygen deficient operation (e.g. during high load operation). The primary reason for loss in performance is due to reduced efficacy of NOx reduction during three-way catalytic converter (TWCC) operation.

Primarily the TWCC consists of Palladium (Pd), Rhodium (Rh) and at times small quantities of Platinum (Pt) depending on the specific application. Palladium is a highly active catalyst when it is in reduced (metallic) form on the surface. During the presence of excess O2, Pd converts to PdO which is inactive for low temperature oxidation towards CO and Hydrocarbons (HCs). On the other hand, Rh is active for NOx reduction only when present in certain oxidation states. Due to the presence of excess O2 or reduced O2, the oxidation state of Rh is modified and this leads to increased NOx emissions.

Viridis’ OSM are specifically designed to handle different oxidation and reduction conditions over wide operating windows of concentrations and temperatures. Viridis offers various OSM materials typically as a solid solution of Ceria and Zirconia with various Rare earth and transition metal additives to improve the thermal stability and overall oxygen storage capacity.

Typical composition of OSM provided by Viridis are as follows:

Grade– V-OSM-52

Grade– V-OSM-6t2

Representative parameters. Actual parameters can vary batch wise

Viridis also offers customers alumina doped OSM with desired levels of viscosity to enable easier coating of materials on the monolith substrate. Please reach out to us at info@viridischemicals.com for additional information.

Petroleum Catalysts

Monolith catalysts can be aged under controlled conditions to end of life conditions (mil-on). We work with the OEMs, catalyst manufacturers to recommend the target aging conditions. Aging conditions of the catalysts vary depending on the desired end state of the catalyst. Hydrothermal aging, cyclic aging and simulated exhaust aging conditions are possible for core and full scale catalysts. Please contact us at info@viridischemicals.com for additional information regarding our aging capabilities.

To satisfy these multifaceted needs by the refineries, Viridis uses its fundamental materials design methodology to classify the hydrocarbon reaction catalysts based on varying levels of acidity and basicity. Viridis uses the catalyst acidity/basicity not only to improve the efficacy of the desired reactions, but also to improve tolerance towards contaminants by affecting the metal interaction with the catalyst support.

Viridis produces all its materials in two of its manufacturing sites near the city of Mumbai, India. Viridis is India’s first light naphtha Isomerization catalyst manufacturer as part of the Atma-Nirbhar Bharat initiative by the Government of India. The highly sophisticated catalysts manufactured at its manufacturing sites are carefully controlled and analyzed with in-situ and ex-situ­­ analytical techniques that maintain the desired target catalyst composition while minimizing batch to batch variations.

Light Naphtha
Isomerization Catalysts

Isomerization of C5/C6 hydrocarbons in naphtha is one of the most efficient methods for production of high-octane components in gasoline. C5/C6 isomerization is a highly popular process in the petroleum industry for production components that can be blended in the motor spirit pool. Viridis’ IV-IZOMaxCAT technology provides a highly efficient route for production of isomerized products whilst providing significant capital and operational efficacy in comparison to other industry solutions. A comparison of IV-IZOMaxCAT technology in comparison to the other industry options is shown below.

Isomerization units are under increasingly high demand due to the stringent regulations on fuel standards and the need for complying with these standards in a relatively quick timeframe. Viridis’ IV-IZOMaxCAT technology is well suited to not only revamp units but also grass-root level constructions to offer high return on investment in relatively short time frame.

Typical IV-IZOMaxCAT technology requires the following sub-units for enabling maximum performance benefits:

 

a. Feed pre treatment to handle moisture and sulphur limits in feed/H2
b.   Distillation columns for recycling C5 and C6 isomers to increase process yield
c.   Main Isomerization reactors typically separated as lead (high temperature) and lag (low temperature) reactors
d.  Stabilizer unit

IV-IZOMaxCAT technology has a high tolerance not only to feed contaminants such as moisture and Sulfur, but also to C7+ and benzene in the feed. This technology has been implemented with C7+ of up to 10% and Benzene of up to 6% in the fresh.

IV-IZOMaxCAT technology is ideally suited as a replacement to Zeolite based Isom units or for replacement of existing sulphated zirconia-based units with minimal design modifications. Significantly higher C5+ RON output is guaranteed in both these scenarios.

Key Highlights of IV-IZOMaxCAT technology

  1. Turnkey solution along with process design is offered for grass root level units or for converted units to increase Isom throughput.
  2. Ideal catalyst candidate for conversion from existing Zeolite or Sulphated Zirconia based technologies owing to its low OPEX. No additional chloride injection is required.
  3. Low operating temperature allows for maximum C5+ RON output with high product yield~ 98 wt%.
  4. Low operating temperature of the process allow isomerization reactions to proceed in thermodynamically favourable conditions. Minimum cracking level in the process provides for tar get product yield of up to 98 wt% per feed.
  5. Catalyst is highly tolerant to feed contaminants such as C7+, Benzene, Moisture, Sulphur and Nitrogen. Further temporary excursions beyond the recommended levels do not lead to any permanent catalyst deactivation.
  6. Minimal feed pre treatment or post-treatment are required reducing the OPEX further
  7. High robustness of the catalytic system. Catalyst service life is typically at least 8 years owing to highly stable catalyst design. Furthermore, temporary increase in feed impurities content does not lead to irreversible loss of the catalyst activity.

IVIZOMaxCAT Technology Configuration options

Depending on theselected product fractionation design, it is possible to produce isomerate withdifferent octane numbers, as well as individual alkanes of iso- or normalstructure without sulfur, nitrogen impurities, chlorine compounds or aromatics.

Comparison of Capital and Operation expenses with IVISOMCAT technology

Viridis conducts a free techno-commercial audit of the light naphtha Isomerization Unit towards implementation of IV-IZOMaxCAT technology for your refinery. Please contact us at info@viridischemicals.com for further information.

 

IV-IZOMaxCAT is a proprietary technology developed by Viridis Chemicals in collaboration with Indian Oil Corporation Limited. IV-IZOMaxCAT has one operational reference in India. It holds patents for the technology in India, Russia, EU and USA. The catalyst is manufactured in India in Viridis’ manufacturing facilities in Mumbai as part of Atma-Nirbhar Bharat initiative by the Government of India.

A modified version of IV-IZOMaxCAT is being developed for reverse isomerization of C5 (n-Pentane from i-Pentane). The n-Pentane is particularly useful as input feed to cracker units in the refinery.

n-Butane (C4)
Isomerization Catalyst

Isomerization of n-butane to iso-butane is a process that is gaining attention due to refineries’ shift towards petrochemical production. Iso-butylene is a popular feed stock for most petrochemicals and iso-butane is its natural precursor. Furthermore, iso-butane is also used a feedstock for alkylation units in the refineries.

Butane Isomerization Unit

Conventionally chlorinated alumina catalysts were used for the isomerization n-butane. The challenges of this catalyst are its dedicated unit operations that entails significant feed treatment and downstream processing that limit the refinery’s ability to adapt to a different product if required. Significant CAPEX and OPEX is required for these catalysts to build and operate dedicated C4 isomerization units.

Viridis offers VC4ISOMaxCAT technology for n-butane isomerization which rivals the conventional chlorinated alumina catalyst. The typical operating conditions and performance parameters are shown below for reference.

Viridis’ VC4ISOMaxCAT technology has significant advantages in comparison to the existing chlorinated alumina option. The following are its key features:
  1. Easy implementation into existing chlorinated alumina-based units for butane isomerization without any revamp
  2. Low OpEx owing to non-requirement of organic chlorine requirement. No downstream processing owing to the lack of any scrubber unit requirement. Cost saving of around 20% would be achieved depending on process conditions in the butane isomerization unit.
  3. High tolerance to feed contaminants such as moisture and sulphur. Temporary excursions of contaminants beyond the recommended levels for short cycles does not result in permanent deactivation of the catalyst
  4.  Long service life of the catalyst ~ 6-8 years

Viridis will conduct a free techno-commercial evaluation of the unit to compare existing chlorinated alumina-based system against VC4ISOMCAT technology upon request. Please contact info@viridischemicals.com for further information.

CRU Catalyst

Catalytic reforming is a major source of petrol in oil refining and aromatics in the petrochemical industries respectively. Its importance is further heightened as it is a major source of Hydrogen production. UOP LLC in the United States and Axens in France are the main catalyst suppliers for this process.

Viridis Chemicals offers reforming catalyst – VRef786 as effective drop-in solutions for reforming units operating in fixed bed reactor setting. VRef786 is a multi-metallic noble metal catalysts with high stability and resistance to feed contaminants. Viridis is currently in the demonstration phase for VRef786 in a refinery setting. The performance metrics of the catalyst is shown below for reference:

The actual performance parameters are a function of feed composition and operational severity. Final guarantees are provided based on feed compositional details provided by the refinery

Viridis will provide a detailed operational model that the user can utilize in the event the process conditions or feed composition changes during operation. Viridis will provide detailed technical evaluations process optimization suggestions based on the unit’s current operation. For additional information please reach out to info@viridischemicals.com

Benzene Saturation Catalyst

The carcinogenic nature of Benzene has strictly the limited its use in MS-pool strictly. The recent BS-VI regulations in India have further necessitated efficient management strategies for refiners to handle Benzene that typically arises from the reformer. The main strategies employed by refiners are to either limit the feed Benzene (and its precursors) in the catalytic reformer feed, or to eliminate Benzene after it is formed by means of hydrogenation. Saturation units operate in both these scenarios to hydrogenate the Benzene effectively.

The Benzene Saturation process involves a single reactor that is operated at elevated pressure and low temperatures to saturate Benzene. A preheater is installed but is primarily used only for start-up. Typical catalyst requirements for Benzene saturation are:

  • High selectivity
  • Controlled exothermicity across the reactor
  • Extended operation stability

Viridis’ VBzCat® is a highly selective drop-in solution for the saturation of Benzene to C6 naphthenes. The catalyst is designed to carefully manage the exothermicity across the reactor. The operating window allows for significantly high space velocity operation to increase the unit’s cost effectiveness.

Typical feeds include hydrotreated LSR naphtha or light reformate streams. VBzCat® is capable of efficiently handling up to 30% Benzene in the feed stream.

Typical feed conditions are shown below for reference:

For feeds with 5-30 vol% benzene,  the C5+ volumetric product yields are 103-105% of the feed. Owing to the high catalyst sensitivity, hydrogen consumption is minimal beyond the stoichiometric level (3 moles of H2 per mole of Benzene). With VBzCat® the saturation of Benzene is accomplished without concomitant increase in the RVP. Viridis can aid the refiners to couple its light naphtha catalyst (IVIZOMaxCAT®)along with its Benzene saturation catalyst (VBzCat®) to isomerize light paraffins while hydrogenating the Benzene. This joint process can mitigate the reduction in the Octane that is inevitable in standalone Benzene saturation process.

Viridis offers VBzCat® in both ready to use form and inert form that would need in-situ ­pre-treatment prior to usage in the reactor depending on the customer requirement.

Viridis will provide detailed technical evaluations process optimization suggestions based on the unit’s current operation. For additional information please reach out to info@viridischemicals.com.

Olefin Saturation Catalyst

VOleSat® is a Nickel based selective hydrogenation catalyst that can be used to convert alkenes and aromatics into alkanes. It is a highly active catalyst that can be provided in both reduced and stabilized formulations. VOleSat® can operate for both liquid and gas feeds. It may also be applied for carbonyl compounds. The catalyst is typically supplied trilobe extrudes, but depending on customer’s requirement for loading density and mass transfer effects, cylindrical extrudes can also be provided.

The primary advantages of this catalyst high selectivity:

Physical Form – Trilobe or Cylindrical Extrudes
Physio – Chemical Data
Active Metal – Ni
Diameter – 1.4 to 1.5 mm
Bulk Density ~ 770 kg/m3

Pharmaceutical Catalysts

Viridis manufactures several grades of PGMs (Platinum Group Metals) on proprietary support materials of varying levels of acidity. The specifically tuned supports provide higher metal reaction sites that are only a few nanometers in size, thus offering increased active surface area for reaction. This directly translates to higher reactivity per unit volume of catalyst. The individual classes of support materials are further modified by additives to increase/reduce acidity/basicity to increase the reactivity as per customer requirements.

VP-PdC501

VP-PdC501 is a 5% Palladium finely dispersed on Carbon catalyst for batch processes. The catalyst shows excellent activity towards hydrogenation chemistries while offering high filtration efficacy.

VP-PdC501

The catalyst is packaged and shipped 60 Litre drums along with PE liner. The catalyst requires no pre-activation step and is ready to use.

Applications – Hydrogenation of C=C and CΞC, Hydrogenation of CN bonds to primary amines and aldehydes, Hydrogenation of C=O to alkyls, Reduction of aldehydes and ketones to amines, Hydrogenation of aromatics to heteroaromatics, CC coupling reactions etc.

VP-PtC502

VP-PtC502 is a 5% Platinum finely dispersed on Carbon catalyst for batch processes. The catalyst shows excellent activity towards hydrogenation chemistries while offering high filtration efficacy.

VP-PtC502

The catalyst is packaged and shipped 60Liter drums along with PE liner. The catalyst requires no pre-activation step and is ready to use.

Applications – Hydrogenation of CN double bonds, Hydrogenation of aliphatic Nitro groups etc.

VP-RuC503

VP-RuC503 is a 5% Ruthenium finely dispersed on Carbon catalyst for batch processes. The catalyst shows excellent activity towards hydrogenation chemistries while offering high filtration efficacy.

VP-RuC503

The catalyst is packaged and shipped 60 Litre drums along with PE liner. The catalyst requires no pre-activation step and is ready to use.

Applications – Hydrogenation of aliphatic aldehydes and ketones, Hydrogenation of Sugars to Sugar Alcohols, Hydrogenation of carboxylic acids, esters and anhydrides, Partial Hydrogenation of aromatics etc.

VP-PdA – 6 Series

Viridis offers Palladium finely dispersed on proprietary activated alumina with varying levels PGM content depending on the application. These catalysts are offered in powder and as shaped extrudates to facilitate better mass transfer characteristics for higher throughput. These catalysts can be utilized both for batch and continuous process applications.

Applications – Various Hydrogenation reactions (Olefins)

Additional Catalysts (Pharma)

Viridis also offers PGM catalysts on its proprietary support formulations depending on the specific customer chemistry requirements. The metal loading, dispersion and support acidity would be tuned to the specific reactant conversion and product selectivity requirements of the customer.

The additional supports (not including additives) include – CaCO3, BaSO4, ZrO2, Al2O3+ZrO2 etc. Please reach out to us at info@viridischemicals.com for additional information.

Rare Earth Chemicals

Viridis provides high purity rare earth solutions for production of various automotive catalysts. The rare earth solutions are available with varying degrees of purity – 2N, 3N or 4N grade respectively.

Lanthanum Nitrate

Lanthanum nitrate is commonly used as a precursor to manufacture Lanthanum Oxide. Lanthanum Oxide (La2O3) is used to deploy desired acidity to γ-Al2O3 that is commonly employed as support material for automotive and refining applications. Lanthanum nitrate is also used as a pre-cursor for manufacture of various perovskite materials such as LaMnO3 for thin film coating on stainless steel substrates and also for manufacture of Lanthanum Oxysulfide La2O2S.

Cerium Nitrate

Cerium nitrate is commonly used as a precursor to manufacture Cerium based catalyst. Ceria Oxide (Ce2O3 or CeO2) is used in conjunction with Zirconia (ZrO2) to store and release O2 in oxygen deficient conditions during three-way catalytic converter operation for gasoline vehicles. Cerium nitrate is also used for the production of gas lamp gauze covering and as an additive in hard alloys.

Neodymium Nitrate

Neodymium nitrate is commonly used as a precursor to manufacture Neodymium compounds. Neodymium Oxide (Nd2O3) is employed as an additive to CeO2-ZrO2 oxygen storage materials to obtain better thermal stability and tune the desired acidity of the support. Neodymium nitrate is also used as a pre-cursor for manufacture of glass, crystals and capacitors. This rare earth nitrate is used in manufacturing of various glass shades ranging from pure violet to wine-red thus providing sharp absorption bands.

Packaging

Viridis supplies Rare earth nitrate in solutions in 50-liter or 200-liter HDPE UN Approved drums.

Pre-shipment QC

Prior to shipment, Viridis will facilitate sampling and testing by external testing agency such as SGS and Intertek if required by the customer.

Viridis QC

All materials are verified with Viridis’ internal QC which include ICP-OES/AAS, UV-Vis and other wet chemistry methods. Please contact at info@viridischemicals.com for more information regarding rare earth solutions.

Other Catalysts – Base Catalysts

Viridis also produces and supplies several base catalysts with varying levels of basicity. Please reach out to us at info@viridischemicals.com with your specific needs and we will get back with the best chemistry suitable for your application.

2-Octanol to 1-Octene Catalyst

2-Octanol is fatty secondary alcohol which is formed as a bi-product during the manufacturing of castor oil. Its primary formation mechanism is by the base-cleavage of the triglycerides of ricinoleic acid that are commonly found in castor oil production. While 2-Octanol can be used as the raw materials for polyethylene plastic plasticizers, synthetic oil agents, pesticide emulsifier agents, conversion of this secondary alcohol to 1-Octene or to 2-ethyl hexanol has significant advantages economically. The current study demonstrates the development of a new catalyst that efficiently converts 2-Octanol to 1-Octene. The catalyst is non-PGM (Platinum group metal) based and has demonstrated stability of operation over several 100s of hours of operation.

Catalyst stability

Catalyst performance stable over 150 hours of operation in the presence of H2 flow at 15 bar even without any Platinum group metal

Conversion

Over 98.5% conversion of 2-Octanol was observed over the entire operating domain

Selectivity

Two main products were seen in the product stream accounting for over 90% of the total outlet, namely, 1-Octene and 2-Octene. A selectivity of 78% was observed towards 1-Octene over the entire operating window of 150 hours

Catalyst Conversion results (selected candidates)

Viridis manufactures VB1-600-7 Catalyst can be used for 1-Octene production. The current throughput for the reactant is around 1 kg per hour per kg of catalyst. Based on the current yield levels this would yield around 0.78 kgs of product per hour per kg of catalyst.

Ethanol dehydration Catalyst

Viridis has developed base catalyzed variant for dehydration of ethanol to ethylene. Ethylene is a fundamental building block for several petrochemicals. Depending on the desired yield levels and available capex requirements, Viridis offers both PGM and non-PGM options for this catalyst.

The catalyst has been tested for longevity of operation under varying levels of feed and carrier gas contamination. Please reach out to us at info@viridischemicals.com to discuss your requirement and how we can help you reach your target conversion levels.

Contact

H-26, 3, MIDC Road,
Taloja, Navi Mumbai,
Maharashtra. 410208

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