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IN THE NAME OF GOD Mehdi Rashidzadeh First International Catalyst Conference Tehran-IRAN 9 June 2014 1 Outline: Drivers of Catalysis for Social development Market and uses of catalyst The long journey of an idea Catalyst Importance for Iran Examples of success Driven by R&D Concluding Remarks 2 RIPI OVERVIEW Research Institute of Petroleum Industry: Founded in 1959 Affiliated to National Iranian Oil Company (NIOC) Over 700 permanent employees (about 2000 including service contract staff) Nation's Largest research institute 3 Catalyst Preparation Catalytic Reaction Engineering Characterization and Evaluation of Catalysts Development of carbon and Nanotechnology 4 More than 20% of GDP from products made using catalysts > 90% of petro refining and petrochemicals processes use catalysts > 95% of pollution control technologies Catalysts has a strategic importance for the country economy and … 5 Catalysis has a tremendous impact on the human activities as concerns economic development, environment preservation and, more broadly, societal progress. >90% of all molecules of transportation fuels >80% of all chemical products Are manufactured with catalysis The development and scale-up of processes are, by definition, application oriented. Industrial catalysis targeted to make in better processes resulting in : Energy efficiency Economic efficiency Development of Chemical Processes Feedstock efficiency Environmental efficiency 6 Catalytic processes require of a very particular industry for catalyst manufacture. About 100 companies worldwide, <20 are the major ones, produce catalysts on their own technologies or as toll manufacturers. > $ 21000 million in 2011 catalysts sales > $ 7,500 billion yearly induced market of manufactured goods. Oil Refining (29 %) Development of Chemical Processes Chemical Processing (32%) Including polymers & fine chemicals Environmental Impact Control (39 %) Catalyst sales per market sector 7 Over 80 million barrel of crude Oil are processed daily worldwide in >700 refineries. The fundamental drivers determining the refinery mission are : o o o Ensure the energetic security, Reduce the environmental impact: Ensure Operation economics creating value for shareholders. A refinery is an integrated sequence of technologies able to Separate various hydrocarbon fractions, o transform them in molecules suitable for the final use, and remove unwanted impurities. “ Any Part “ of crude oil must be utilized with environmentally friendly technologies. o Reaction technologies for petroleum refining consist almost entirely of catalytic processes designed to modify the components of the fractions in four ways : Breaking big molecules in smaller ones (cracking) • Combining small molecules in larger ones (condensations) • Rearranging “Part” of molecules for getting appropriate “structures” (isomerization) • Breaking carbon-heteroatom bonds (S, N, O, Me) • 8 2% 11% 16% 32% 8% 39% 16% 18% 29% 29% Fcc Environmenta l Refining Hydrotreating Other Hydrocracking Polymers Chemical Alkylation Reforming 9 7% 10% 20% 39% 17% 28% 6% Europe 73% Detergent Builders Japan Other Asia North America Catalysts Adsorbents/Desicants Rest of the World 10 - Qualified staff, experienced in different fields of sciences, Engineering and Technology. - High –tech equipments for physico- chemical characterization and testing the catalytic performance. - Pilot facilities for catalysts production and testing (Scaling-up) - Innovative activity (Patent and legal services) and good commercial partners. 11 An innovative process begins with an idea that is generated in the somebody’s mind. Individual Creativity is the engine of ideas generation. Creativity: Seeing What everyone else has seen And Thinking what no one else has thought (Albert Szent-Gyorgi) Innovativeness implies an application of discoveries. It is always true that “necessity is mother of invention” 12 Human progress has been always based on creativity and innovativeness that reflects the dualsim Science-Technology, two different but strongly connected cultural Worlds. Scale-Up is the conjunction between creativity and innovativeness. Scale up transform the initial idea into innovation, through a long (and dangerous) journey. And there are only few ideas that will cover the entire way ! Definition Check Even in a continuum, the R&D activities, can be grouped into two basic stages: • the “explorative and definition phase”, already oriented, but still looking for a general definition of the process, and • the “intensive and development phase”, strictly finalized to achievement of The complete technology know-how. Optimization Risk analysis Commercialization Front end design Engineering Construction Start-up Realization 13 As a consequence R&D projects undergo very considerable “attrition”, and the majority of explorative projects are ended. About 1 to 3% of ideas for a new process at the early research stage reaches commercialization. Project at the development stage have a probability of about 10 to 25%, and at the pilot plant stage of 40 to 60%. The success rate for marginal modifications of existing technologies will be higher than that of completely new processes. Projects innovation 15 16 University Fundamental and basic research Applied research Product Development Industry More “R” than “D” in Developing Countries 17 R&D and its link with businesses 1. R&D for existing businesses. This will ensure the business is able to exploit all opportunities available to it 2. Drive new businesses. Business opportunities will continually arise. R&D will ensure that these can be exploited 3. Exploratory research. This helps to develop understanding of technology that the business is using or may use 18 € Commercialization investment Sales R&D investment Cash flow Science base Generic Proprietary technologies technologies Time Production scale-up Market penetration 19 Catalysis and catalytic processes development involve skills coming from many complementary, independent disciplines. Industry-Academia collaborations enlarge the cultural basis of the projects, and educate industrial researchers to apply new scientific concepts in their “real-world” and academic researchers to introduce “real problems” in their world. Catalysis needs integration and “bridging the gaps”: between catalyst preparation and performances, between model catalyst and working catalyst, between laboratory and industrial conditions, between reactor engineering and catalyst formulation, between electronic structure calculations at molecular level and experimental results, and not be forgotten, between business and science 20 Geopolitical Context -Iran has huge oil and gas reserves -During the coming decades oil will still be main source of energy. - Some political issues (sanctions) Development in refining and petrochemicals - There are 9 oil refineries throughout the country -7 new refinery are under construction (they would be operational up to 2025) - increasing the capacity of old refineries - investment on new petrochemical complexes. high consumption (by considering the developing plants in refining and petrochemical industry it would be more than 5000 ton/ year). 21 50 45 40 35 32 30 25 21 20 15 10 9 5 5 3 3 3 2 2 2 2 2 2 1 1 1 1 1 0.4 0.4 0.3 0.03 0 22 Developed Know-how item Available to be handed over Gamma alumina as a catalyst support for naphtha reforming 1 catalysts Handed over to industries Naphtha reforming catalyst 2 Catalyst for demercaptanization of distillate and condensate Molecular sieve zeolite 3A 3 One-stepped preparation of Isobutene dehydrogenation catalyst Low temperature water gas shift catalyst 4 Steam reforming catalyst ZnO for sulphur adsorption 5 Gasoil hydrodesulphurization catalyst Naphtha hydrodesulphurization catalyst 6 Shaped different types of molecular sieve zeolite A 7 Precious metal recovery of spent catalysts Gamma alumina as a catalyst support for naphtha HDS catalysts Aromatization catalyst (Pt-Sn/Al2O3) Production technology of carbon nanotubes (single-walled, double8 walled and multi-walled) Production of nanostructured metal oxides 9 Hydro-cracking process Simulator 10 11 Catalytic reforming process Simulator 23 Naphtha Hydrotreating catalyst Naphtha Reforming catalyst Zeolites: 3A & 4A 24 Physical and chemical Specification of the Co-Mo/Al2O3 catalyst Bulk Density (g/mL) Mean Pore Diameter (nm) Pore Volume (mL/g) Surface Area (m2/g) CoO (wt%) MoO3 (wt%) Min.0.6 8-11 Min. 0.6 Min. 190 2-5 12-15 25 . 26 . Feed: Naphtha with 1200 ppm S (Total Sulfur) H2/Oil Pressure LHSV 175 Nlit/lit 15 bar 4.2 hr-1 Temperature ,°C Total Sulfur in Product, ppm (Commercial catalyst) Total Sulfur in Product, ppm (RIPI catalyst( 250 6 4 270 1 1 290 <1 <1 310 <0.5 <0.5 330 <0.5 <0.5 27 •Catalytic reforming of naphtha constitute a very important source of products having high octane numbers which are key components in the production of gasoline. • Catalytic reforming is the process of transforming hydrocarbons with low octane numbers to aromatics and iso-paraffins which have high octane numbers. 28 bulk density (g/ml) Mean pore diameter (Ao) Pore volume (cm3/g) Surface area 0.72-0.74 100-105 0.50-0.55 190-220 (m2/g) Cl Re Pt (wt%) (wt%) (wt%) 0.9-1.1 0.4-0.45 0.20-0.25 29 . 95 100 Syntesized Catalyst Commertial Catalyst 70 100 80 75 85 80 60 70 86 40 20 0 RON of Product (after 40h) RON of Product (after 150h) C5+ wt % in Product (after 40h) C5+ wt % in Product (after 150h) Reaction condition , T:515 °C P:10bar LHSV:2h-1 H2/oil:5Nli/li 30 Synthesized catalyst in nano scale Commercial catalyst Synthesized catalyst by conventional method 31 Applications: Catalysis Gas separation Ion exchange Detergents 32 Zeolite 4A powder Salt Solution Oven Ion Exchanger Crusher Filter Binder Additives Distilled Water Blender Kneader Oven Extruder Screening Furnace Product All ingredients and equipments used are from national sources 33 Specification for Zeolite 4A Powder Na2O Al2O3 SiO2 H2O Blue Density (kgm-3) Mean crystal size (𝝁 m) pH (5% in water) Calcium binding capacity 17 wt% 28 wt% 33 wt% 22 wt% 500-550 2.5 10.5 173.6 mg CaO/g Zeolite Physical Properties of 3A Molecular sieve Shape Size Bulk density, kgm-3 Crush strength, Mpa Water adsorption, % (at 60% relative humidity) Extrudate 3-4 mm length 760 1.0 15.25 34 Novelty… 35 Catalyst preparation (Lab & Pilot scale) Catalyst evaluation Industrial production 36 37 38 39 catalysts performance are evaluated at bench and pilot scale. Major units in this section are for the following processes: Steam Reforming Hydrocracking Hydrotreating(Naphtha, Kerosene, Gasoil) Low temperature shift conversion (LTSC) High temperature shift conversion (HTSC) S-Absorptions Catalytic reforming Isomerization 40 *Used by Permission PP&C. 41 NEW TECHNOLOGIES RIPI P ROJECTS Research Lab Test Bench Scale Commercial Scale Patenting Pilot Plant Industrial Plant Nano Lubricants ULW Cement NANO fuel additives Nanomaterials for oil decontamination Polymer Nanocomposites Nanocatalysts Upgrading oil products quality by Nanomaterials Nanocoatings CNT mass production 42 During the coming decades, oil will still be the main source of energy and so it is necessary to develop the better catalysts for catalytic processes. Industrial catalyst producing is of strategic importance for any developing country and without dubte it belongs to the category of the so-called "high-tech" industries. It should be emphasized that without intensive research and development activities it is impossible to reach and maintain of catalyst production. Industry should play the leading role, which is especially important. It has the provider of founding for R&D teams. The companies which produce catalyst, have to support big research teams and extensive multimillion R&D programs. Catalyst developers must be support the industry and give them suitable guarantees and technical services. 43 44