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: zeosit@zeosit.nsc.ru 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.
Naphtha
(SRG)
DISTILLATION
Crude oil
or gas
condensate
Diesel
Fuel oil
Zeoforming
Highoctane
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: zeosit@zeosit.nsc.ru 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 (isoparaffins, 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 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, olefincontaining gases of cracking and pyrolysis and oxygencontaining 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: zeosit@zeosit.nsc.ru 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 (340-450оC) thus decreasing power consumption by 2030%;
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: zeosit@zeosit.nsc.ru URL: http://www.zeosit.nsc.ru/
Parameter
Zeoforming
Reforming
The reaction temperature, оC
350-460
480-550
Pressure, atm.
5-15
3-35
Hydrogen equipment
Is not required
Is required
Hydrofining of the raw
material
Is not required
Is required
Raw material
Hydrocarbon fractions C5 –240оC;
olefin-containing gases; oxygencontaining compounds
Hydrocarbon fractions
C6 –180оC (naphthenebased)
Catalyst
Contains no noble metals;
ecologically safe
Contains Pt, Pd and may
contain other heavy
metals
Final product
High-octane gasoline ready for use
High-octane aromatic
component of gasoline,
needs blending
Benzene content in the
gasoline fraction of the
product
0.6-1.5% vol.
5-10% vol.
Motor gasoline*) :
Yield of final product:
Normal
Regular
«Eurosuper-95»
- for fraction 35-160оC
80-90%
70-85%
68-82%
- for fraction 70-180оC
85-92%
75-90%
72-85%
Yields of gasolines
depend on blending
conditions
Permissible sulphur content
in the raw material
is not limited
less than 0.001% wt.
Sulphur content in the
gasoline produced
no more than 0.05% 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: zeosit@zeosit.nsc.ru 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:
doesn’t exceed
the content of
sulfur
benzene
0.01%;
1%;
aromatic hydrocarbons
olefins
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: zeosit@zeosit.nsc.ru URL: http://www.zeosit.nsc.ru/
In the course of
high-octane gasoline production
through Zeoforming technology
desulphurization of the raw material
proceeds simultaneously.
R1–SH
R1–S–R2
R1–S–S–R2
R
+ H2S + CnH2n+2
S
0,4
100
Octane number (RON)
1.15
0,35
S total, % mass
1.10
0,3
0,25
– Orenburg gas plant
– Urengoy gas plant
0,2
0,15
0,1
90
80
70
60
0,05
50
0
250
300
350
400
450
500
550
о
Temperature, C
Siberian Technological Company “Zeosit” Pr. Ak. Lavrentieva, 6, Novosibirsk 630090, Russia
Tel. /Fax: (383) 330-05-96, 335-62-51 E-mail: zeosit@zeosit.nsc.ru 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.
The raw material of the
installation is a stable gas
gasoline. The final product of the
installation is unblended normalgrade gasoline.
If the installation is switched to
another raw material – straightrun gasoline, the yield of motor
gasoline grows up to 82-85% wt.
The lifetime of the catalyst is over
1.5 years.
II
In February, 1997 a
Zeoforming installation of 40 thousand
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 installation is designed to produce
unblended motor gasoline “Eurosuper95” 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: zeosit@zeosit.nsc.ru 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 isoparaffins (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: zeosit@zeosit.nsc.ru 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)
Costs, rel. units
Profits, rel. units
80 thou. ton/year
40 thou. ton/year
Точечная 3
Starting the installation
0
5
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
NPV, million USD
10
Zeoforming
8
Reforming
6
4
2
0
-2 0
-4
20
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: zeosit@zeosit.nsc.ru 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)
Fractioning
installation
Hydrofining
installation
Gasoline
fraction 35%
Feedstock
Diesel fuel 35%
C5-C6
9%
Hydrogen-containing
gas
Hydrogencontaining gas
H2
isoparaffins
8.5%
Gasoline
fraction
26%
Fuel oil 30%
Unit of gas
desulphurization
Hydro-isomerization
installation
Blending Gasoline
High-octane
30.5%
unit
component 22%
Reforming
installation
Diagram 2. Zeoforming technology
Fractioning
installation
Feedstock
Zeoforming
installation
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: zeosit@zeosit.nsc.ru URL: http://www.zeosit.nsc.ru/
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.
Siberian Technological Company “Zeosit” Pr. Ak. Lavrentieva, 6, Novosibirsk 630090, Russia
Tel. /Fax: (383) 330-05-96, 335-62-51 E-mail: zeosit@zeosit.nsc.ru 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 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.
Siberian Technological Company “Zeosit” Pr. Ak. Lavrentieva, 6, Novosibirsk 630090, Russia
Tel. /Fax: (383) 330-05-96, 335-62-51 E-mail: zeosit@zeosit.nsc.ru URL: http://www.zeosit.nsc.ru/
POLYFUNCTIONAL CATALYSIS
I.
High-octane gasoline
Petroleum fractions Polyfunctional
catalyst,
T boiling = 180-450ОC
H2
II.
Oil base
Low-pour diesel fuel
A number of technologies for motor fuels production
from non-petroleum raw materials are developed and
tested at the pilot level :
+ Toluene
Para-xylene
Para-ethyltoluene
CO2
+ H2
+ Xylenes
High-octane gasoline,
diesel fuel
Coal
Biowastes
Durene
CO + 2H2
Natural gas
Methanol
Dimethyl ether
Olefins
+ Methyl naphthalenes
Dimethyl
naphthalenes
DMC
Oil base
The above technologies open a possibility to solve a number of problems,
both ecological (CO2 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: zeosit@zeosit.nsc.ru URL: http://www.zeosit.nsc.ru/