Transcript Document
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.
Siberian Technological Company “Zeosit” Pr. Ak. Lavrentieva, 6, Novosibirsk 630090, Russia
Tel. /Fax: (383) 330-05-96, 335-62-51 E-mail: [email protected]
URL: http://www.zeosit.nsc.ru/
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 350-500 thousand 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.
Zeoforming
Naphtha (SRG) Crude oil or gas condensate Diesel Fuel oil High octane gasoline LPG STORAGE 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.
Siberian Technological Company “Zeosit” Pr. Ak. Lavrentieva, 6, Novosibirsk 630090, Russia
Tel. /Fax: (383) 330-05-96, 335-62-51 E-mail: [email protected]
URL: http://www.zeosit.nsc.ru/
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 H 2 S 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 normal gasoline production, the yield of gasoline reaches 80-92% and in case of regular gasoline it 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.
Siberian Technological Company “Zeosit” Pr. Ak. Lavrentieva, 6, Novosibirsk 630090, Russia
Tel. /Fax: (383) 330-05-96, 335-62-51 E-mail: [email protected]
URL: http://www.zeosit.nsc.ru/
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 (340-450 о C) 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.
Siberian Technological Company “Zeosit” Pr. Ak. Lavrentieva, 6, Novosibirsk 630090, Russia
Tel. /Fax: (383) 330-05-96, 335-62-51 E-mail: [email protected]
URL: http://www.zeosit.nsc.ru/
Parameter
The reaction temperature, о C Pressure, atm.
Hydrogen equipment Hydrofining of the raw material
Zeoforming
350-460 5-15 Is not required Is not required
Reforming
480-550 3-35 Is required Is required Raw material Catalyst Final product Hydrocarbon fractions C 5 –240 о C; olefin-containing gases; oxygen containing compounds Contains no noble metals; ecologically safe High-octane gasoline ready for use Hydrocarbon fractions C 6 –180 о C (naphthene based) Contains Pt, Pd and may contain other heavy metals High-octane aromatic component of gasoline, needs blending Benzene content in the gasoline fraction of the product 0.6-1.5% vol.
Yield of final product: - for fraction 35-160 о C - for fraction 70-180 о C Permissible sulphur content in the raw material Sulphur content in the gasoline produced Normal Motor gasoline*) : Regular «Euro super-95» 80-90% 70-85% 68-82% 85-92% 75-90% 72-85% is not limited no more than 0.05% wt.
5-10% vol.
Yields of gasolines depend on blending conditions less than 0.001% wt.
no more than 0.001% wt.
Economical characteristics For capacities 80-200 thousand tons/year, the investments are repaid in less than 1.5 – 2.5 years Is profitable for capacities above 600-800 thousand tons/year
*) The second desired product is LPG. The ratio of the gasoline and LPG yields is provided according to the market demands.
Siberian Technological Company “Zeosit” Pr. Ak. Lavrentieva, 6, Novosibirsk 630090, Russia
Tel. /Fax: (383) 330-05-96, 335-62-51 E-mail: [email protected]
URL: http://www.zeosit.nsc.ru/
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 are HOG (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
sulfur benzene aromatic hydrocarbons olefins
0.01%; 1%; 40-42%; 5-7%.
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.
Siberian Technological Company “Zeosit” Pr. Ak. Lavrentieva, 6, Novosibirsk 630090, Russia
Tel. /Fax: (383) 330-05-96, 335-62-51 E-mail: [email protected]
URL: http://www.zeosit.nsc.ru/
In the course of high-octane gasoline production through
Zeoforming
technology desulphurization of the raw material proceeds simultaneously.
R
1
–SH R
1
–S–R
2
R
1
–S–S–R
2
R
+
H
2
S + C
n
H
2n+2 S 0,4 0,25 0,2 0,15 0,1 0,05 0 250 300 350
– Orenburg gas plant – Urengoy gas plant
400
Temperature, о C
450 500 70 60 550 50 100 90 80 Siberian Technological Company “Zeosit” Pr. Ak. Lavrentieva, 6, Novosibirsk 630090, Russia
Tel. /Fax: (383) 330-05-96, 335-62-51 E-mail: [email protected]
URL: http://www.zeosit.nsc.ru/
INDUSTRIAL IMPLEMENTATION
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 Zeoforming installation of 40 thousand a ton per year capacity was put into operation at Glimar Refinery 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 grade gasoline.
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.
Siberian Technological Company “Zeosit” Pr. Ak. Lavrentieva, 6, Novosibirsk 630090, Russia
Tel. /Fax: (383) 330-05-96, 335-62-51 E-mail: [email protected]
URL: http://www.zeosit.nsc.ru/
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 MON to 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-free operation.
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.
Siberian Technological Company “Zeosit” Pr. Ak. Lavrentieva, 6, Novosibirsk 630090, Russia
Tel. /Fax: (383) 330-05-96, 335-62-51 E-mail: [email protected]
URL: http://www.zeosit.nsc.ru/
DYNAMICS OF COSTS AND PROFITS DEPENDING ON THE INSTALLATION CAPACITY
(the data concern the production of regular to premium gasolines) 80 thou. ton/year 40 thou. ton/year Точечная 3 0 5 Starting the installation 10 15 20 25 30 35 40 45 50 55 number of months 60
COMPARATIVE ANALYSIS OF THE NET PRESENT VALUE ( NPV ) FOR THE INSTALLATIONS OF HIGH-OCTANE GASOLINE PRODUCTION VIA ZEOFORMING AND REFORMING
10 8 6 4 2 0 -2 0 -4 20 Zeoforming Reforming 40 60 80 100
Capacity of installation with respect to the gasoline produced, thou. ton/year
Siberian Technological Company “Zeosit” Pr. Ak. Lavrentieva, 6, Novosibirsk 630090, Russia
Tel. /Fax: (383) 330-05-96, 335-62-51 E-mail: [email protected]
URL: http://www.zeosit.nsc.ru/
Diagram of conversion of oil fractions or gas condensate into motor fuels through different processes:
Diagram 1. Conventional scheme (Reforming and isomerization)
Feed stock Fractioning installation Gasoline fraction 35% Hydrofining installation C 5 -C 6 9% Hydro-isomerization installation Diesel fuel 35% Fuel oil 30% Hydrogen-containing gas Hydrogen containing gas Unit of gas desulphurization H 2 Gasoline fraction 26% Reforming installation High-octane component 22% iso paraffins 8.5% Blending Gasoline unit 30.5%
Diagram 2. Zeoforming technology
Fractioning installation Zeoforming installation Feed stock Gasoline fraction 35% High-octane gasoline 24.5% Fuel gas 1% Liquefied gas 9% Diesel fuel 35% Fuel oil 30% Diesel fraction 0.5 %
Siberian Technological Company “Zeosit” Pr. Ak. Lavrentieva, 6, Novosibirsk 630090, Russia
Tel. /Fax: (383) 330-05-96, 335-62-51 E-mail: [email protected]
URL: http://www.zeosit.nsc.ru/
III
An industrial capacity 40 Zeoforming installation of 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.
Siberian Technological Company “Zeosit” Pr. Ak. Lavrentieva, 6, Novosibirsk 630090, Russia
Tel. /Fax: (383) 330-05-96, 335-62-51 E-mail: [email protected]
URL: http://www.zeosit.nsc.ru/
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 Samsung was Engineering constructed Company, by Ltd.
(South Korea) with the use of Basic Engineering, technology, and developed by SEC “Zeosit” SB RAS.
catalyst Starting this demonstrational installation opens the opportunity to increase the capacity of the Zeoforming process up to 1 million ton/year.
Siberian Technological Company “Zeosit” Pr. Ak. Lavrentieva, 6, Novosibirsk 630090, Russia
Tel. /Fax: (383) 330-05-96, 335-62-51 E-mail: [email protected]
URL: http://www.zeosit.nsc.ru/
POLYFUNCTIONAL CATALYSIS
I.
Petroleum fractions T boiling = 180-450 О C
Polyfunctional catalyst, H 2
High-octane gasoline Oil base Low-pour diesel fuel II.
A number of technologies for motor fuels production from non-petroleum raw materials are developed and tested at the pilot level : CO 2
+ H 2
Coal Bio wastes Natural gas CO + 2H 2 Methanol DMC
+ Toluene
Para-xylene Para-ethyltoluene
+ Xylenes
Durene High-octane gasoline, diesel fuel Dimethyl ether Olefins
+ Methyl naphthalenes
Dimethyl naphthalenes Oil base
The above technologies open a possibility to solve a number of problems, both ecological (CO 2 discharge reduction and wastes utilization) and strategical in the framework of the general GTL (gas to liquid) strategy.
Siberian Technological Company “Zeosit” Pr. Ak. Lavrentieva, 6, Novosibirsk 630090, Russia
Tel. /Fax: (383) 330-05-96, 335-62-51 E-mail: [email protected]
URL: http://www.zeosit.nsc.ru/