Department of Organic Technology / ICRI

DEPARTMENT OF ORGANIC TECHNOLOGY NB-2

Head of Department: Dr. Stefan Szarlik, Chem. Eng.,
phone +48 (22) 568 22 66, +48 (22) 568 21 76, fax: +48 (22) 568 21 74
e-mail: stefan.szarlik(at)ichp.pl
Office: Grażyna Radwańska, phone +48 (22) 568 22 30, fax: +48 (22) 568 21 74
e-mail: grazyna.radwanska(at)ichp.pl;

Oxidation and Caprolactam Process Group
Catalytical Processes Group
High-Pressure Processes Group

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Oxidation and Caprolactam Processes Group

Head: Dr. Stefan Szarlik, Chem. Eng.,
phone +48 (22) 568 22 66, +48 (22) 568 21 76, fax: +48 (22) 568 21 74,
e-mail: stefan.szarlik(at)ichp.pl

Research interests

Development of the caprolactam process consisting of the following sub-processes and operations:

Catalytic benzene hydrogenation to cyclohexane,
Cyclohexane oxidation in the liquid phase to cyclohexanol and cyclohexanone,
Separation of cyclohexanol and cyclohexanone from the reaction mixture,
Catalytic cyclohexanol dehydrogenation to cyclohexanone,
Cyclohexanone oxime formation from cyclohexane treated with hydroxylamine sulfate solution (obtained via catalytic nitric oxide hydrogenation in sulfuric acid),
Cyclohexanone oxime rearrangement to caprolactam,
Separation and purification of caprolactam,

Studies for the modernization of the anthraquinone hydrogen peroxide process. Studies are performed on a continuously operating quarter-technical scale installation,
Studies of the cyclohexanol synthesis by partial benzene hydrogenation to cyclohexene step,
Synthesis of adipic acid by cyclohexanol oxidation with nitric acid.

Major achievements
List of licenses sold in the last decade
(co-owners of the processes: "Tarnów-Mościce" SA Chemical Plant, "Puławy" SA Chemical Plant)

1991: GUJARAT STATE FERTILIZERS COMPANY, India (in cooperation with CORA/ENCO Engineering A.G., Switzerland), cyclohexanone from benzene, 45000 t/year
1995: AZOT-Grodno, Byelorussia, cyclohexanone-cyclohexanol mix from cyclohexane, 50000 t/year
1997: PROQUIMED, Spain, cycohexane oxidation tune-up, 60000 t/year
1997: GUJARAT STATE FERTILIZERS COMPANY, India (now GUJARAT STATE FERTILIZERS & CHEMICALS LIMITED), cyclohexanone installation tune-up, 45000 t/year, (in cooperation with ENCO Engineering A.G., Switzerland)
1988: NAN-YA PLASTICS CORP., Taiwan, adipic acid by cyclohexanol-cyclohexane mix oxidation with nitric acid, 40000 t/year (co-owners: ICRI, Institute of Inorganic Chemistry - Gliwice, Design Office "Prosynchem" - Gliwice, and "Chorzów" Chemical Plant).

Experience
The group has experience in hydrogenation and oxidation of organic compounds in the liquid phase, separation and purification of multi-component mixtures of organic compounds, dehydrogenation of alcohols to ketones, elimination of small amounts of organic compounds from non-reactive gases. The group members are highly qualified in apparatus and installation design tasks, implementation of the research results in the industry, and the startup of chemical plants.

Cooperation sought
At present, the Group is in close cooperation with the Caprolactam Research Division of the "Puławy" SA Chemical Plant. The cooperation aims at the modification, modernization, and capacity increase at the site.
Major cooperation interests: manufacture of cyclohexanone, cyclohexanol, and caprolactam.
The Group is constantly seeking cooperation with other caprolactam-producing chemical plants.

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Catalytical Processes Group

Head: Włodzimierz Wójcik, M.Sc., Chem. Eng.,
phone +48 22 568 20 19,
e-mail: wlodzimierz.wojcik(at)ichp.pl

Research interests

Dehydrogenation processes of the light aliphatic hydrocarbons (C3, C4),
Hydrogenation of the alkylarenes,
Multi-phase catalytic processes under increased pressure and temperature - laboratory and half-technical scale.

Experience

Isoparaffinic hydrocarbon solvents technology,
Phosgene-free MDI process on a half-technical scale and methods to obtain amines via nitro compounds reduction with synthesis gas. Modernizations of the existing nitro compounds reduction processes.

Available methods and equipment

laboratory pressure installation using still-bed reactors (100 ml);
Berty's gradient-less reactor to study reaction kinetics in the gas phase (400 ml of catalytic bed volume);
large laboratory pressure installation with pipe reactors of 1000 to 3000 ml volume;
large laboratory vacuum installation to study hydrocarbons dehydrogenation processes at decreased pressure;
FALCON-NET distributed modular control system - industrial automation system, used with the above installations.

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High-Pressure Processes Group

Head: Dr. Robert Brzozowski, Chem.Eng.,
phone +48 22 568 20 20 or 568 24 73,
e-mail: robert.brzozowski(at)ichp.pl

Research interests

Application of supercritical solvents to obtain or modify plastics.
Supercritical extraction of natural compounds from plant and animal material.
Chemistry of ammonia in the supercritical state.
Hydrogenation processes eg.:

hydrogenation of vegetable oils in the presence of a supercritical solvent.

hydrogenation of alfa-methylstyrene to cumene.

hydrogenation of phenolic tar.

High-pressure alkylation of aromatic hydrocarbons with olefins (e.g. benzene, toluene or naphthalene with ethylene or propylene) on solid catalysts, especially shape selectivity zeolites. Alkylation of high temperature melting species (e.g. naphthalene) are carried out without solvent.

Experience

High pressure alkylation on stationary bed of catalyst both in the laboratory and semi-technical scale.
Other high pressure processes like hydrogenation, isomerization, disproportionation, transalkylation, etc., performed in the reactor with a stationary bed of catalyst.
High-temperature supercritical extraction of brown coal, coke oven tar, wood, and other cellulose-containing materials.
Supercritical extraction of plant or animal derived material.
Purification of polymers by supercritical extraction.
Purification (with separation of organic compounds) of industrial water wastes and effluents using supercritical solvents.

Cooperation sought

Application of solid catalysts e.g. zeolites in petrochemical processes,
Study on the separation of biological extracts from natural materials, using supercritical extraction.
Development of polymers by supercritical extraction.
High-temperature oxidation reactions in the supercritical phase.

Available methods and equipment

High-pressure laboratory research unit (1-10 ml) for testing solid catalysts (zeolites) in aromatic hydrocarbons alkylation or other reactions.
High-pressure research units enabling scaling up alkylation, hydrogenation or other processes carried pout on stationary bed of catalyst (zeolite).
Batch-type apparatus of 0.1 to 10 l volume for the extraction in the solid-supercritical gas system in the temperature range from -10 to 150 deg.C and under pressure up to 300 bar,
continuous operation apparatus for extraction in the liquid/suspension-supercritical gas system in the temperature range from 25 to 300 deg.C and under pressure up to 300 bar, up to 20 kg liquid per hour;
batch and continuous operation apparatus to study reactions in the supercritical state in the temperature range from 25 to 300 deg.C and under pressure up to 250 bar,
three-stage fractionating apparatus to separate extracts from supercritical mixtures in the temperature range from -10 to 150 deg.C and under pressure up to 300 bar,

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Publications

Pepłoński R., Kwiatkowski J., Kąkol B., Bełdowicz M., Tęcza W., Lisicki Z.: "Ekstrakcja surowców roślinnych nadkrytycznym dwutlenkiem węgla" Tłuszcze, Środki Piorące, Kosmetyki, 1997, 41 (1), 9
Kwiatkowski J., Borowiak M.: "The Reaction of Benzophenone, 1,2-Diphenylethane and 1,2-Diphenylethylene in Supercritical n-Butanol" Proc. of 6th Meeting on Supercritical Fluids, Nottingham, 10-13 April 1999.
Kwiatkowski J., Lisicki Z., Jarosz M.: "The Study of the Transesterification Reaction Under Supercritical Conditions" Proc. of CHIS '98, Prague, 23-28 August 1998.
Kwiatkowski J., Jarosz M., Tęcza W.: "The Reaction of Ammonia with Alkene Oxide Under Supercritical Conditions" Proc. of CHIS '98, Prague 23-28 August 1998.
Kwiatkowski J., Borowiak M.: "The Reaction of Benzophene, 1,2-Diphenylethane and 1,2-Diphenylethylene in Supercritical n-Butanol" Proc. of 6th Meeting on Supercritical Fluids, Nottingham, 10-13 April 1999.
R. Brzozowski i W. Tęcza, "Shape-selective reactions of naphthalene over zeolites", Appl. Catal. 1998, 166, 21-27.
R. Brzozowski, J. Cz. Dobrowolski, M. H. Jamróz i W. Skupiński: "Studies on diisopropylnaphthalene substitutional isomerism", J. Molec. Catal. A: Chem., 2001, 170 (1-2), 95-99.
R. Brzozowski, W. Skupiński, M. H. Jamróz, M. Skarżyński and H. Otwinowska: "Isolation and Identification of Diisopropylnaphthalene Isomers in the Alkylation Products of Naphthalene", J. Chromatogr., A, 2002, 946(1-2), 221-227.
R. Brzozowski, J. Cz. Dobrowolski, M. H. Jamróz: "Theoretical Estimation of Isomeric Composition of Cymenes in Equilibrium Mixture", Catal. Commun., 2002, 3/4, 141-144.
R. Brzozowski and W. Skupiński: "Zeolite Pore Entrances Effect on Shape-Selectivity in Naphthalene Isopropylation", J. Catal., 2002, 210(2), 313-318.
R. Brzozowski, W.Skupiński: "Shape-Selectivity in Naphthalene Isopropylation", Proc. 15 Intern. Congr. Chem. Proc. Eng., CHISA 2002, Prague, 25 - 29.08.2002.
Stefan Szarlik, Andrzej Gołebiowski, Kazimierz Stołecki "Izobaryczny proces uwodorniania benzenu", Przem.Chem. 85/8-9, (2006), 665-667.
Ewa Jagielska, Ryszard Mostowicz, Stefan Szarlik "Utleniające odwodornienie etanu w obecności sit molekularnych", Przem.Chem. 86/4 (2007), 340-344.
R.Brzozowski, A.Vinu, T.Mori, "Alkylation of naphthalene using propylene over mesopororous Al-MCM-48 catalysis", Catalysis Communications 8(2007) 1681-1683.