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Zeoforming A catalytic process for production of unblended high-octane gasolines

Siberian Technological Company “Zeosit” . Zeoforming A catalytic process for production of unblended high-octane gasolines. « Glimar » Refinery , Poland . The process of Zeoforming is started in February 1997. Rustavi, Georgia . The process of Zeoforming is started in March 2002.

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Zeoforming A catalytic process for production of unblended high-octane gasolines

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  1. Siberian Technological Company “Zeosit” Zeoforming A catalytic process for production of unblended high-octane gasolines «Glimar» Refinery, Poland. The process of Zeoforming is started in February 1997. Rustavi, Georgia. The process of Zeoforming is started in March 2002.

  2. DISTILLATION Zeoforming Naphtha (SRG) Crude oil or gas condensate Diesel High-octane gasoline LPG Fuel oil STORAGE PREHISTORY(1990-1997) The Zeoforming technology is developed and applied in industry in construction of autonomous installations for high-octane (RON 92-96) motor gasoline production of capacity 5 to 350-500thousand tons per year with respect to the raw material – straight-run gasoline fraction (SRG) for a fixed catalyst bed process. For a process using moving catalyst bed, the possibility is proved to increase capacity up to one million tons per year with respect to straight-run gasoline fraction. The industrial technology of Zeoforming and the catalyst production technology are developed by SEC “Zeosit” SB RAS and protected by more than 30 RF patents. SEC “Zeosit” possesses the exclusive right of licensing the use of Zeoforming and develops Basic Engineering for installations of motor fuel production through the Zeoforming process.

  3. THE CHEMICAL PRINCIPLES OF THE PROCESS The process of Zeoforming is based on the reactions of catalytic conversion of paraffins and naphthenes over zeolite-containing catalysts. During the Zeoforming process the reactions of C-C bonds splitting, isomerization, hydrogen redistribution, and alkylation of the initial hydrocarbons and of the intermediate compounds result in conversion of low-octane hydrocarbons (naphthenes and unbranched paraffins) into high-octane components (iso-paraffins, arenes). Due to molecular-sieve properties of the catalyst, the branched high-octane paraffins undergo practically no conversion. The sulphuric compounds of the raw material are also converted into high-octane components during the Zeoforming process, e.g. via demercaptanization, with H2S emission into the gaseous phase. As a results, Zeoforming increases the octane number of the straight-run gasoline from 45-60 MON to 72-86 MON (76-95 RON) and decreases the content of sulphur to 0.02-0.05% wt. The yield of the final products depends on type, quality, and fractional composition of the raw material and on the mode of operation of the installation. For the mode of normalgasoline production, the yield of gasoline reaches 80-92% and in case of regular gasolineit is 70-80% of the raw material fed.The second final product is liquefied gas. Besides straight-run gasoline fractions, olefin-containing gases of cracking and pyrolysis and oxygen-containing organic compounds may also be used as raw material in Zeoforming.

  4. ADVANTAGES As compared with the conventional processes, Zeoforming has a number of considerable advantages : • The catalysts are developed on the basis of an environmentally safe system containing no expensive noble and heavy metals; • The catalyst is insensitive to sulphur content, so no hydrofining of the raw material of sulphur and nitrogen-containing compounds is required; • The reactions converting the sulphuric compounds of the raw material, including demercaptanization, result in the total sulphur content in the liquid products not exceeding 0.02-0.05% wt.; • Through the process of Zeoforming, a wide range of hydrocarbon raw material can be converted; • Zeoforming doesn’t use hydrogen and the related compressor equipment; • The process proceeds under lower pressures (0.5-1.5 MPa) and temperatures (340-450оC) thus decreasing power consumption by 20-30%; • Due to essentially lower content of aromatic hydrocarbons and, particularly, of benzene meeting the modern international standards, the gasolines produced are more ecologically safe; • The gasolines produced don’t require any blending; • The process is profitable for capacities above 5 000 ton/year with respect to the raw material. The said advantages result in a considerable decrease of capital and operational costs.

  5. *) The second desired product is LPG. The ratio of the gasoline and LPG yields is provided according to the market demands.

  6. sulfur benzenearomatic hydrocarbonsolefins 0.01%; 1%;40-42%;5-7%. SEC Zeosit SB RAS has two versions of the technology of Zeoforming. Version I. The main products of the process are high-octane gasoline (HOG, the yield is 65-80%) and liquefied petroleum gas (LPG, the yield is 20-30%). Version II. The main products of the process areHOG (the yield is 85-90%) and LPG (the yield is 8-10%). According to the results of the expertise performed by the American company Purvin & Hertz Inc., in the countries with a high demand for LPG import (e.g. the countries of South America, China, Poland etc.), the first version of Zeoforming has good economical and technological prospects while in the countries with a limited market for LPG, the main product should be HOG and the second version is to be applied. In both versions, HOG meets the international standards which are coming into force since 2003, namely: the content of doesn’t exceed After analysis of the group and fractional composition and other properties of the raw material proposed, SEC Zeosit can determine the possible yields of HOG and LPG for each version of the Zeoforming process. In both cases, desulfurization of the raw material is achieved during the process of Zeoforming without using hydrogen or hydrogen facilities.

  7. R R1–SH R1–S–R2R1–S–S–R2 + H2S + CnH2n+2 S – Orenburggas plant– Urengoygas plant In the course ofhigh-octane gasoline production through Zeoformingtechnology desulphurization of the raw material proceeds simultaneously.

  8. INDUSTRIALIMPLEMENTATION I Since 1992 the first industrial Zeoforming installation of 5 thousand ton/year capacity with regard to raw material is in operation at Nizhnevartovsk Gas-Processing Plant. II In February, 1997 a Zeoforming installation of 40 thousand ton per year capacity was put into operation at GlimarRefinery in Gorlice, Poland. The installation had been designed and constructed by Lurgi Company (Germany) with the use of license and Basic Engineering of SEC “Zeosit” SB RAS. The raw material of the installation is a stable gas gasoline. The final product of the installation is unblended normal-gradegasoline. If the installation is switched to another raw material – straight-run gasoline, the yield of motor gasoline grows up to 82-85% wt. The lifetime of the catalyst is over 1.5 years. The installation is designed to produce unblended motor gasoline “Eurosuper-95” from straight-run gasoline of octane number 45-65 MON. The second desired product of the installation is liquefied gas.

  9. PERFORMANCE CHARACTERISTICS OF ZEOFORMING INSTALLATION AT GLIMAR REFINERY On the basis of analysis of 5-year run factual results, an expert commission made the following conclusions: • The desired products of the process are high-octane motor gasoline ready for use without blending and liquefied gas, the total yield of the desired products being not less 92-95% wt. • The high-octane components of the gasolines produced are iso-paraffins (30-50%) and aromatic hydrocarbons (25-45%), the content of benzene not exceeding 1.5% wt. Such composition meets the modern European quality standards. In the process of conversion, the ON of gasoline increases from 45 MONto 82-86 MON, or 92-95 RON. • The obtained liquefied gas contains 40-42% propane, 30-32% n-butane, and 26-28% wt. isobutane, the content of olefins not exceeding 1%. Such composition of the liquefied gas allows its use as a fuel both for domestic purposes and for automobiles. • Due to simultaneously proceeding reactions of conversion of sulphuric compounds in the raw material including demercaptanisation, the process goes steadily without previous desulphurisation and hydrogen application. • The switching reaction-to-regeneration system is completely automatic at all stages and has proved its high reliability by a 5-year trouble-freeoperation. • The installation meets all the requirements of economical and technological efficiency and reliability. The investments were completely repaid in 1.5 years after starting the installation.

  10. Starting the installation DYNAMICS OF COSTS AND PROFITS DEPENDING ON THE INSTALLATION CAPACITY(the data concern the production of regular to premium gasolines) COMPARATIVE ANALYSIS OF THE NET PRESENT VALUE (NPV) FOR THE INSTALLATIONS OF HIGH-OCTANE GASOLINE PRODUCTION VIA ZEOFORMINGANDREFORMING

  11. Fractioning installation Hydrofining installation Hydro-isomerization installation Gasoline fraction 35% C5-C69% Feed-stock Feed-stock Dieselfuel 35% iso- paraffins 8.5% Gasoline fraction 26% Fuel oil 30% Hydrogen-containing gas Blending unit Hydrogen-containing gas Gasoline 30.5% High-octane component 22% H2 Unit of gas desulphurization Reforming installation Fractioning installation Zeoforming installation High-octane gasoline 24.5% Gasoline fraction 35% Fuel gas 1% Liquefied gas 9% Dieselfuel 35% Dieselfraction 0.5 % Fuel oil30% Diagram of conversion of oil fractions or gas condensate into motor fuels through different processes: Diagram 1. Conventional scheme (Reforming and isomerization) Diagram 2. Zeoforming technology

  12. III An industrial Zeoforming installation of capacity 40 thousand ton/year is started in Rustavi, Georgia in March 2002. IV Industrial production of the catalyst is put into operation at JSC “Novosibirsk Plant of Chemical Concentrates”. Catalyst supply is guaranteed for the whole period of operation.

  13. PROSPECTS An industrial Zeoforming installation of capacity 40 thousand ton/year is designed and constructed by IRV Corporation in Bishkek, Kirghizia using license and Basic Engineering of SEC “Zeosit” and is now prepared for being started. Its feedstock is gasoline fraction of oil or of gas condensate. In November 2001 a demonstrational Zeoforming installation of capacity 0.2 ton/day with respect to the raw material using moving catalyst bed technology was put into operation in Daejeon city, South Korea. The installation was constructed by Samsung Engineering Company, Ltd. (South Korea) with the use of Basic Engineering, technology, and catalyst developed by SEC “Zeosit” SB RAS. Starting this demonstrational installation opens the opportunity to increase the capacity of the Zeoforming process up to 1 million ton/year.

  14. High-octane gasoline Oil base Low-pour diesel fuel Polyfunctional catalyst, H2 Para-xylene + Toluene Para-ethyltoluene + Xylenes CO2 Durene + H2 High-octane gasoline,diesel fuel Coal Bio-wastes CO + 2H2 Dimethyl ether Natural gas Olefins Methanol + Methyl naphthalenes Dimethyl naphthalenes DMC Oil base POLYFUNCTIONAL CATALYSIS I. Petroleum fractions Tboiling= 180-450ОC II. A number of technologies for motor fuels production from non-petroleum raw materials are developed and tested at the pilot level : The above technologies open a possibility to solve a number of problems, both ecological (CO2dischargereduction and wastes utilization) and strategical in the framework of the general GTL (gas to liquid)strategy.

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