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1

Oxidative Dehydrogenation of Isobutane on CrOx/Oxide Support Catalysts: Effect of Potassium on Physicochemical and Catalytic Properties

Samson K., Grzybowska B., Grabowski R., Banares M. A., Lozano Diz E.

Polish Journal of Chemistry

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2009

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Vol. 83, nr 11

1977-1992

EN

A series of catalysts containing CrOx (equivalent to 1 theoretical monolayer of Cr2O3) on Al2O3, TiO2, SiO2 and MgO supports, with and with out the potassium additive, have been prepared, characterized by different methods and tested in oxidative dehydrogenation, ODH, of isobutane. Addition of potassium did not affect the structure of the catalysts. It led to a slight decrease in the total activity for all the catalysts and anincrease in the selectivity to isobutene only for the CrOx/TiO2 system. A decrease for CrOx/Al2O3 and Cr/SiO2, on the potassium doping and practically no change in selectivity for CrOx/MgO catalysts, were observed. For all the studied catalysts the K additive decreased the acidity, increased the basicity and decreased the reducibility. No clear correlations between the selectivty and the acid-base properties or reducibility were found. The total activity decreases with the increasing electronegativity of the support cation, except for CrMgO catalyst.

2

Nano- Au/MgF2 and Au/MgO Catalysts in Oxidation of CO

Ruszel M., Grzybowska B., Małecka M. A., Kępinski L., Sobczak J., Wojciechowska M.

Polish Journal of Chemistry

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2009

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Vol. 83, nr 6

1185-1193

EN

Au/MgF2 catalyst is more active in CO oxidation than Au/MgO prepared in the same conditions, in spite of lower efficiency of Au deposition on the MgF2 surface. Its activity decreases (in contrast to Au/MgO) after the hydrogen pre-treatment. Higher activities of Au/MgF2 as compared to Au/MgO prepared in the same conditions, can be due to smaller Au particle size on the MgF2 support as shown by TEM, and to the presence of anionic Au delta– species.

3

Au/Fe3O4 and Au/Fe2O3 Catalysts: Physicochemical Properties and Oxidation of CO and Propane

Grzybowska B., Ruszel M., Samson K., Grabowski R., Spiridis N., Freindl K., Korecki J.

Polish Journal of Chemistry

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2009

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Vol. 83, nr 12

2129-2136

EN

Catalysts containing Au deposited on Fe3O4 (commercial Cerac) and on Fe2O3 were synthesized, characterized by XPS, XRD, Mössbauer spectroscopy, H2TPR, isopropanol decomposition – a probe reaction of acid-base properties, and tested in oxidation of CO and C3H8. Au//Fe3O4 cat a lyst, containing a mixture of magnetite and maghemite (gamma-Fe2O3) phases, was found to be more acidic containing more surface OH groups and less reducible than Au/alfa-Fe2O3 (hematite). The activity in oxidation of CO and propane was higher for Au/alfa-Fe2O3 catalyst as compared with Au/Fe3O4.

4

Sources of innovation in the industrial enterprises of Warmia and Mazury

Grzybowska B.

Management

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2007

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Vol. 11, no 1

97-102

EN

The paper presents the importance of external and internal sources of ideas used in innovation activities of 321 industrial enterprises from Warmia and Mazury voivodship. The studies indicate that ideas of owners and managements are the most important among the internal sources. Ideas of employees, including employees of research and development units, were ranked much lower. The enterprises covered presented diversified opinions on external sources of innovation. Opinions of clients were the most important to them. Cooperation with other enterprises or copying of competitor solutions was mentioned much less frequently. Cooperation with research and development sector had marginal importance as a source of innovation.

PL

W opracowaniu przedstawiono znaczenie wewnętrznych i zewnętrznych źródeł pomysłów wykorzystywanych w działalności innowacyjnej 321 przedsiębiorstw przemysłowych woj. warmińsko-mazurskiego. Z badań wynika, że najważniejsze spośród wewnętrznych źródeł były pomysły właścicieli i kierownictwa firm. Zdecydowanie niżej oceniono pomysły pracowników, w tym pracowników komórek badawczo-rozwojowych. Badane przedsiębiorstwa zróżnicowały ocenę zewnętrznych źródeł innowacji. Najważniejsze ich zdaniem były opinie klientów. Znacznie rzadziej wskazywano na współpracę z innymi przedsiębiorstwami oraz na kopiowanie rozwiązań konkurentów. Jako źródło innowacji znikome znaczenie miała współpraca z podmiotami sektora badawczo-rozwojowego.

5

Supported Vanadia Catalysts with Alkali and Alkaline Earth Additives in Oxidative Dehydrogenation of Propane. Part II. V2O5/SiO2 System

Klisińska A., Gressel I., Grzybowska B., Mikołajczyk M., Stoch J.

Polish Journal of Chemistry

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2006

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Vol. 80, nr 5

835-842

EN

Alkali metals (Li, Na, K, Rb) and Ca were introduced to vanadia dispersed on magnesia: the catalysts obtained were characterized by XRD, XPS isopropanol decomposition (a probe of acido-basic properties) and tested in oxidative dehydrogenation of propane, ODH. No vanadia phase was observed by XRD, vanadium being most probably present in the samples as magnesium orthovanadate dispersed on the MgO surface. Low concentration of acidic and high of basic centres have been observed in the catalysts. Selectivity to propene does not exceed 40%, andCO2 is themain product of total oxidation. The presence of the additives leads to: a) decrease of the acidity and increase the basicity, b) decrease of the total activity in ODH, c) decrease in the selectivity to propene (except for the Ca additive). The effect of additives to VMg catalysts is compared with that reported in Part I for VSi catalysts, and reasons for opposite effect of the additives on the selectivity to propene (increase for VSi and decrease for VMg series) are suggested.

6

Supported Vanadia Catalysts with Alkali and Alkaline Earth Additives in Oxidative Dehydrogenation of Propane. Part I. V2O5/SiO2 System

Klisińska A., Gressel I., Grzybowska B., Mikołajczyk M., Stoch J.

Polish Journal of Chemistry

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2006

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Vol. 80, nr 5

825-833

7

Pozyskiwanie i przepływ informacji wykorzystywanych w działalności innowacyjnej przedsiębiorstw przemysłu spożywczego

Grzybowska B.

Zeszyty Naukowe. Organizacja i Zarządzanie / Politechnika Śląska

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2004

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z. 24

189-195

PL

Z przeprowadzonych badań wynik, że informacje wykorzystywane w działalności innowacyjnej, przedsiębiorstwa pozyskują raczej z łatwo dostępnych źródeł. Wewnętrzny ich przepływ ograniczany jest głównie przez nadmierną liczbę kanałów informacyjnych, w dużym stopniu obciążonych przypływem informacji.

EN

Conducted research show that enterprises gain information used in innovative activity from rather easily accessible sources. Flow of information inside a company was hampered mainly by big number of informative channels, which were loaded by flow of information.

8

Bariery działalności innowacyjnej przedsiębiorstw w Polsce

Grzybowska B.

Management

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2004

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Vol. 8, no 2

17-26

PL

Głównymi czynnikami utrudniającymi realizację projektów innowacyjnych są przyczyny ekonomiczne - najczęściej zbyt wysokie koszty innowacji, zbyt wysokie oprocentowanie kredytów, brak własnych środków oraz ograniczone możliwości dostępu do finansowania zewnętrznego. Czynniki te natomiast okazują się mało istotne w innych krajach UE. Tam najczęściej wskazywaną barierą są przeważnie zbyt wysokie podatki (także poważnie ograniczające działania innowacyjne polskich przedsiębiorców). Działalność innowacyjną przedsiębiorstw w Polsce ograniczają także uregulowania prawne, normy i przepisy oraz czynniki wewnętrzne, takie jak brak rozpoznania potrzeb rynkowych i związany z tym brak informacji na temat technologii czy też "sztywność" organizacyjna. Występowanie tych czynników może wskazywać w dalszym ciągu na brak umiejętności przedsiębiorstw w dostosowywaniu się zmieniających się warunków otoczenia.

EN

The main factors which hamper realisation of innovative projects are economic reasons - mainly too high costs of innovations, too hogh credit rates, lack of own money and limited possibilities to access outside finance. These factors appear less essentional in other countries of EU, where the biggest barrier is mainly too high taxes (this factor also seriously hamper innovative activity of Polish businessmen). Innovative activity in Poland is hampered as well by legislation, standards, regulations and internal factors such as lack of market research and information concerning technology or organisational barriers. These factors may indicate that Polish companies still have difficulties in adaptation to changing environment.

9

Oxidative Dehydrogenation of Propane on Supported Mlybdena Catalysts: Effect of the Support Nature and Additives

Klisińska A., Samson K., Grzybowska B.

Polish Journal of Chemistry

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2003

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Vol. 77 / nr 12

1867-1874

EN

Oxidative dehydrogenation of propane has been studied on molybdena deposited on SiO2, Al2O3, TiO2, and MgO. The catalytic performance depended on the support nature, the selectivity to propene at iso-conversion decreasing in the sequence: MoOx/SiO2 >MoOx/Al2O3 ~ MoOx/TiO2 > MoOx/MgO. Introduction of the K, Cr , Ni and V additives to MoOx/SiO2 and Cr to MoOx/MgO catalysts led to the increase of the total activity. The increase of the selectivity to propene was observed for the Cr and Ni additives, whereas the K and V in the MoOx/SiO2 catalysts decreased the selectivity (K and higher amounts of V), or did not affect it (lower amounts of vanadium).

10

Effect of Additives to VPO System on Its Catalytic Properties in Oxidative Dehydrogenation of Propane and Ethane

Gąsior M., Gressel I., Zazhigalov V. A., Grzybowska B.

Polish Journal of Chemistry

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2003

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Vol. 77 / nr 7

909-915

EN

Oxidative dehydrogenation (ODH) of propane and ethane has been studied on VPO catalysts with additives of Bi, La, Mo and Zr. The catalysts show promising properties in the ethane ODH, with selectivities to ethene of ~85% at 10% conversion of ethane, but are poor in the propane ODH (maximal selectivities to propene of ~40%). For both alkanes introduction of the additives leads to an increase in the overall rate of the reaction. The effect of the additives on the selectivity to olefins is complex and depends on the reaction temperature, the additive content and the type of alkane. The same additive has in several cases an inverse effect on the selectivity for the propane and ethane ODH. The Mo additive and higher amounts of the La additive increase the selectivity to propene, whereas they decrease the selectivity to ethene. Low content of La additive gives rise to the increase of selectivity to ethene and decrease in that to propene. The differences between the selectivities to olefins in ODH of propane and ethane are discussed as being due to different acido-basic properties of the propene and ethene and their different strength of bonding to the catalyst surface.

11

Effect of Thermal Treatment of the Al3O3 and TiO2 supports on Properties of Dispersed Chromium Oxide in Oxidative Dehydrogenation of Isobutane

Grzybowska B., Samson K., Keromnes L., Wcisło K., Duła R., Serwicka E. M.

Polish Journal of Chemistry

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2001

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Vol. 75, nr 2

283-292

EN

Chromium oxide has been dispersed on Al2O3 and TiO2 supports, heated between 500-1200 C, and the catalysts obtained have been tested in oxidative dehydrogenation of isobutane at 280 C. For the CrOx/Al2O3 system the thermal treatment of alumina, which leads to the decrease in the specific surface area and polymorphic transformations of the initial -Al2O3 into , and modifications, does not affect the catalytic performance of the catalysts in the reaction under study. On the other hand, the transformation of anatase-TiO2 into rutile-TiO2, occurring on heating at 1000 C, leads to catalysts of a higher activity and selectivity to isobutene. Amelioration of the catalytic properties for CrOx/rutile-TiO2, as compared with CrOx/anatase-TiO2 catalysts, has been ascribed to changes in the structure of the CrOx active centres, evidenced by ESR.

12

Effect of the Potassium Promoter Content in V2O5/TiO2 Catalysts on Their Physicochemical and Catalytic Properties in Oxidative Dehydrogenation of Propane

Grzybowska B.

Polish Journal of Chemistry

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2001

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Vol. 75, nr 10

1513-1519

EN

To optimize the content of the potassium promoter in V2O5/TiO2 system for oxidative dehydrogenation of propane ODH, the vanadia-titania catalysts of the potassium/vanadium (K/V) ratio ranging from 0.01 to 0.2 were obtained and tested in the title reaction. It has been found that the total rate of the propane consumption decreases considerably already on addition of small amounts of K (K/V = 0.01) to vanadia-titania system and only slightly at higher K content: its value is constant beginning from K/V = 0.05. The distinct increase in the selectivity to propene on addition of K is, on the other hand, observed at higher K content (K/V = 0.05-0.1). Addition of K to vanadia-titania catalysts leads to the decrease in acidity and increase in basicity of the system, as shown by measurements of the isopropanol decomposition, a probe reaction of acido-basic properties.

13

Innowacyjność produktowa przedsiębiorstw przemysłu spożywczego

Pasternak K., Strychalska A., Grzybowska B.

Przemysł Spożywczy

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2000

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T. 54, nr 3

31-33

PL

Przeprowadzono badania (ankietowe) aktywności przedsiębiorstw w rozwoju produktów w wybranych branżach przemysłu spożywczego. Wyniki badań wskazują na ograniczoną skuteczność postępowania rozwojowego oraz na konieczność jego doskonalenia w celu zwiększenia konkurencyjności przedsiębiorstw przetwórczych.

EN

The studies (questionnaire) on the activity of enterprises in respect of product development in the selected branches of food industry, were carried out. The results of the studies indicate a limited efectiveness of the developmental methods and point to the necessity of their improving in order to increase the competitivity of processing enterprises.

14

Efekty i uwarunkowania aktywności innowacyjnej krajowych przetwórców żywności

Pasternak K., Grzybowska B.

Przemysł Spożywczy

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1999

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T. 53, nr 1

16-17

PL

Przedstawiono dane o innowacjach produktowych w polskim oraz w brytyjskim i amerykańskim przemyśle spożywczym. Omówiono też czynniki warunkujące wprowadzenie nowych produktów żywnościowych na rynek.

EN

Product innovation data from Polish, British and American food industries are presented. Factors affecting introduction of new food product to market are also discussed.

15

Oxidative dehydrogenation of isobutane on nickel and chromium oxide systems dispersed on different supports

Moriceau P., Grzybowska B., Barbaux Y.

Polish Journal of Chemistry

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1998

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Vol. 72, nr 5

910-915

EN

Nickel oxide and chromia supported on ThO2, CeO2 and SiO2 have been tested in oxidative dehydrogenation of isobutane. Both NiO- and Cr2O3-based systems have been found active in this reaction already around 300 degree C, the catalytic performance being dependent on the nature of the support. Chromia-based catalysts are more active and selective as compared with the NiO-based ones. The highest activity and selectivity have been observed for CrOX/CeO2 system. The basicity of the catalysts determined by a probe reaction of the isopropanol dehydrogenation follows the same sequence as the total activity in the oxidative dehydrogenation of isobutane, which suggests an activation of theC-H bond on basic centres of the catalysts.

16

Oxidative dehydrogenation of isobutane on chromium oxide-titania catalysts

Grzybowska B., Słoczyński J., Grabowski R., Wcisło K., Kozłowska A., Stoch J., Serwicka E.

Polish Journal of Chemistry

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1998

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Vol. 72, nr 9

2159-2171

EN

Oxidative dehydrogenation of isobutane has been studied at 250 degreeC for a series of chromium oxide-TiO2 (anatase) samples containing 5-50 Cr at per nm(2) of the support surface and for pure chromia. The catalysts have been characterized by XPS, Raman, ESR spectroscopies and by probe reactions for acido-basic properties and the catalyst oxygen reactivity. The maximum activity and selectivity to isobutene have been observed for a catalyst containing 1 theoretical monolayer of the chromia phase on titania. Higher selectivity to isobutene for this catalyst as compared with unsupported chromia or catalysts with higher Cr loading has been ascribed to lower acidity and lover reactivity of oxygen.