PL163857B1 - Method of making catalysts with acid-base and redox properties composed of heteropolanions on a polymer carrier - Google Patents
Method of making catalysts with acid-base and redox properties composed of heteropolanions on a polymer carrierInfo
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- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
- C07C45/39—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups being a secondary hydroxyl group
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
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- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
- C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
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- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
- C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
- C07C45/35—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in propene or isobutene
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- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
- C07C45/38—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups being a primary hydroxyl group
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- C07C2527/16—Phosphorus; Compounds thereof containing oxygen
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- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
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Abstract
Description
Przedmiotem wynalazku jest sposób wytwarzania katalizatorów o właściwościach kwasowo-zasadowych i redoksowych, stanowiących heteropolianiony na nośniku polimerowym. Katalizatory te mogą być użyte do szeregu procesów takich jak konwersja alkoholi, utlenianie olefin itd.The subject of the invention is a process for the preparation of catalysts with acid-base and redox properties, constituting heteropolyanions on a polymer support. These catalysts can be used for a variety of processes such as alcohol conversion, olefin oxidation, etc.
Heteropolikwasy oraz ich sole, związki o specyficznej budowie anionu, ze względu na swoje właściwości kwasowe oraz redoksowe znalazły w ostatnich latach szereg zastosowań w katalizie kontaktowej, zarówno w reakcjach typu kwasowo-zasadowego, jak i w reakcjach utleniania. Z punktu widzenia praktyki przemysłowej ważne jest otrzymywanie katalizatorów na osnowie heteropolikwasów i ich soli o wysokiej aktywności w możliwie niskich temperaturach. Przekroczenie temperatury rzędu 350-400‘C w procesie wytwarzania katalizatorów powoduje bowiem rozkład termiczny anionów heteropolikwasów.Heteropolyacids and their salts, compounds with a specific anion structure, due to their acidic and redox properties, have found a number of applications in contact catalysis in recent years, both in acid-base reactions and in oxidation reactions. From the point of view of industrial practice, it is important to obtain catalysts based on heteropolyacids and their salts with high activity at the lowest possible temperatures. Exceeding the temperature of the order of 350-400'C in the catalyst production process causes thermal decomposition of heteropolyacid anions.
Heteropolikwasy były nanoszone na nośniki nieorganiczne, takie jak SiO? (A. Bielański, J. Późniczek, A. Małecka, React. Kinet. Catal. Lett., 41 , 127 /1990/) lub TiO?.Heteropolyacids have been applied to inorganic supports such as SiO? (A. Bielański, J. Późniczek, A. Małecka, React. Kinet. Catal. Lett., 41, 127 (1990)) or TiO ?.
Metoda ta nie pozwala jednak na molekularne rozproszenie heteropolikwasów. Centra katalityczne aktywne były związane jedynie siłami adsorpcji z podłożem, co ograniczało stabilność katalizatorów.However, this method does not allow for the molecular dispersion of heteropolyacids. Active catalytic sites were bound only by adsorption forces with the substrate, which limited the stability of the catalysts.
Z europejskiego opisu patentowego nr OP 0323351 znana jest metoda otrzymywania polimerów zawierających heteropolianiony polegająca na chemicznym utlenianiu odpowiednich monomerów w medium zawierającym heteropolikwasy. Z punktu widzenia katalizy nie jest to jednak metoda optymalna, gdyż wprowadzanie heteropolianionów do matrycy następuje in situ podczas polimeryzacji, a więc większość centrów katalitycznych znajduje się wewnątrz warstwy polimeru i jest trudno dostępna dla substratów podlegających reakcji katalitycznej. Aktywne katalitycznie pozostają jedynie centra znajdujące się w warstwie przypowierzchniowej. Ilości katalizatora otrzymanego tą metodą są ograniczone i limitowane powierzchnią elektrody.European Patent No. OP 0323351 describes a method of obtaining polymers containing heteropolyanions consisting in the chemical oxidation of appropriate monomers in a medium containing heteropolyacids. From the point of view of catalysis, however, it is not an optimal method, because the introduction of heteropolyanions into the matrix takes place in situ during polymerization, so most of the catalytic centers are inside the polymer layer and are difficult to access for substrates subject to catalytic reaction. Only the centers located in the subsurface layer remain catalytically active. The amounts of the catalyst obtained by this method are limited and limited by the electrode area.
Celem wynalazku jest otrzymanie katalizatorów zawierających heteropolikwas lub jego sól wprowadzony w odpowiedni sposób do półprzewodzących polimerów stanowiących nośniki umożliwiające rozproszenie heteropolikwasu w stopniu molekularnym w warstwach przypowierzchniowych polimeru. Rozproszenie takie w bardzo znacznym stopniu zwiększa aktywność katalizatora w odniesieniu do jednostki wagowej heteropolikwasu.The aim of the invention is to obtain catalysts containing a heteropolyacid or a salt thereof incorporated in an appropriate manner into semiconducting polymers which are carriers enabling the molecular dispersion of the heteropolyacid in the near-surface layers of the polymer. Such dispersion greatly increases the activity of the catalyst based on the weight unit of the heteropolyacid.
Sposób według wynalazku polega na tym, że heteropolianiony pochodzące od heteropolikwasów lub ich soli wprowadza się za pomocą utleniania chemicznego lub elektrochemicznego między łańcuchy polimerów skoniugowanych.The method according to the invention consists in introducing heteropolyanions derived from heteropolyacids or their salts between the chains of conjugated polymers by means of chemical or electrochemical oxidation.
Jako polimery skoniugowane stosuje się poliacetyien, polipirol i jego pochodne, politiofen i jego pochodne, polifuran i jego pochodne, poliparafenylen, poliparafenylenowinylen, polianilinę i jej pochodne i podobne.Conjugated polymers include polyacetiene, polypyrrole and its derivatives, polythiophene and its derivatives, polyfurane and its derivatives, polyparaphenylene, polyparaphenylene vinyl, polyaniline and its derivatives and the like.
Heteropolikwasy lub ich sole utleniają łańcuchy polimeru do polikarbokationów i jednocześnie są wbudowane jako aniony kompensujące ładunki dodatnie matrycy. Reakcje prowadzi się w rozpuszczalnikach organicznych, przy czym mogą być stosowane różne polarne rozpuszczalniki, takie jak acetonitryl, nitrometan, etanol i podobne. Szczegółowe warunki prowadzenia reakcji zależne są od rodzaju użytego heteropolikwasu oraz stosowanego polimeru i objęte są standardową preparatyką organiczną.Heteropolyacids or their salts oxidize the polymer chains to polycarbocations and at the same time are incorporated as anions compensating the positive charges of the matrix. The reactions are performed in organic solvents, and various polar solvents such as acetonitrile, nitromethane, ethanol and the like can be used. Detailed reaction conditions depend on the type of the used heteropolyacid and the polymer used, and are included in the standard organic preparation.
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Ozięki metodzie według wynalazku heteropollaniony zostają wprowadzona poprzez proste reakcje utleniania do uprzenio uformowanej matrycy polimerowej, którą otrzymano wcześniej. W rezultacie dyfuzja heteropolianionów ograniczona jest do warstw przypowierzchniowych polimeru, a więc sposób według wynalazku pozwala na otrzymanie katalizatorów wzbogaconych powierzchniowo w centra katalitycznie aktywne. Molekularne i powierzchniowe rozproszenie heteropolianionów ułatwia dostęp reagentów do centrów katalitycznych. Metoda według wynalazku pozwala na stosowanie matryc polimerowych o różnej morfologii i różnej powierzchni właściwej.With the method according to the invention, the heteropollanions are introduced by simple oxidation reactions into the spherically formed polymer matrix that has been obtained previously. As a result, diffusion of heteropolyanions is limited to the near-surface layers of the polymer, and thus the method according to the invention makes it possible to obtain catalysts enriched in surface with catalytically active sites. Molecular and surface dispersion of heteropolyanions facilitates the access of reagents to catalytic centers. The method according to the invention allows the use of polymer matrices of different morphology and different specific surface area.
Aktywność katalityczną związków otrzymanych sposobem według wynalazku przedstawiono w tablicy.The catalytic activity of the compounds according to the invention is shown in the table.
TablicaBlackboard
Zmiany wydajności katalizatora ^PMo^O^g po wprowadzeniu go do matrycy polimerowej. Wydajność dla krystalicznego heteropolikwasu bez nośnika przyjęto za 1 (reakcja katalitycznej konwersji alkoholu etylowego).Changes in the catalyst jności yd and PMOS ^ ^ O ^ g after its introduction into the polymer matrix. The yield for the crystalline heteropolyacid without carrier was taken as 1 (catalytic conversion of ethyl alcohol).
Katalizator otrzymany w wyniku utleniania pirolu w obecności kwasu 12-nolibdenofosforowego sposobem według patentu nr EP 0323351 wykazuje 2-3-krotnie zmniejszoną aktywność katalityczną w reakcji konwersji etanolu w stosunku do krystalicznego heteropolikwasu Η3ΡΜοΐ2θ40 badanego w tych warunkach. Natomiast katalizator otrzymany w wyniku domieszkowania poliacetylenu kwasem 12-molibdenofosforowym sposobem według wynalazku wykazuje 40-krotny wzrost aktywności redoksowej (aldehyd) i 10-krotny wzrost aktywności kwasowo-zasadowej (eter dietylowy, etylen) w stosunku do krystalicznego heteropolikwasu HjPMo^O^ badanego w tych samych warunkach.The catalyst prepared by oxidation of the pyrrole in the presence of 12-nolibdenofosforowego the method according to the patent EP 0323351 shows a 2-3 fold decrease in catalytic activity in the conversion reaction of ethanol with respect to the heteropolyacid crystalline Η 3Ρ Μο ΐ2θ40 tested under these conditions. On the other hand, the catalyst obtained as a result of the doping of polyacetylene with 12-molybdenum phosphoric acid according to the method of the invention shows a 40-fold increase in redox activity (aldehyde) and a 10-fold increase in acid-base activity (diethyl ether, ethylene) compared to the crystalline heteropolyacid HjPMo ^ O ^ tested in the same conditions.
Katalizatory wytwarzane sposobem według wynalazku stosowane są do konwersji alkoholi do węglowodoru i aldehydu i pozwalają na prowadzenie reakcji w znacznie niższych temperaturach i mają większą selektywność do żądanych produktów reakcji.The catalysts of the invention are used to convert alcohols to a hydrocarbon and an aldehyde and allow the reaction to be carried out at much lower temperatures and have a greater selectivity to the desired reaction products.
Przedmiot wynalazku został bliżej przedstawiony w przykładach stosowania.The subject of the invention is presented in more detail in the examples of use.
Przykład 1. Poliacetylen otrzymany w wyniku polimeryzacji Zieglera-Natty poddawano utlenianiu anodowemu stałoprądowo, przy gęstości prądu 0,045 mA/mg poliacetylenu, w elektrolicie zawierającym nasycony roztwór hataropolikwasu (kwasu 12-wolfranowofosforowago) w acetonitrylu. W procesie utleniania anodowego wprowadzono 45% wagowych hataropolίanionów do polimeru. Otrzymany związek inkluzyjny poliacetylenu i heteropolianionów przemywano czystym acetonitrylem i suszono próżniowo. Wysuszony produkt stanowił gotowy katalizator nadający się do stosowania w procesie konwersji alkoholi i w innych reakcjach.Example 1. Polyacetylene obtained by Ziegler-Natta polymerization was subjected to DC anodic oxidation at a current density of 0.045 mA / mg polyacetylene, in an electrolyte containing a saturated solution of hatopolyacid (12-tungphosphoric acid) in acetonitrile. In the anodic oxidation process, 45% by weight of hataropolyanions were introduced into the polymer. The obtained polyacetylene-heteropolyanion inclusion compound was washed with pure acetonitrile and dried under vacuum. The dried product was a finished catalyst suitable for use in the alcohol conversion process and in other reactions.
Przykład II. Poliacetylen poddawano utlenianiu chemicznemu kwasem ^-molibdenowofosforowym w roztworze acetonitrylu z dodatkiem niewielkiej ilości pirolu katalizującego utlenianie. W procesie utleniania chemicznego wprowadzono 40% wagowych hataropolianionów do polimeru. Otrzymany związek inkluzyjny poliacetylenu i heteropolianionów przemywano czystym acetonitrylem i suszono próżniowo. Wysuszony produkt stanowił gotowy katalizator nadający się do stosowania w procesie konwersji alkoholi i innych reakcjach.Example II. The polyacetylene was subjected to chemical oxidation with β-molybdic phosphoric acid in acetonitrile solution with the addition of a small amount of oxidation-catalyzing pyrrole. In the process of chemical oxidation, 40% by weight of hataropolyanions were introduced into the polymer. The obtained polyacetylene-heteropolyanion inclusion compound was washed with pure acetonitrile and dried under vacuum. The dried product constituted the finished catalyst suitable for use in the alcohol conversion process and other reactions.
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Przykład III . Pol ianillnęj otrzymano w wyniku polimeryzacji 109,5mmola nnliiny w obecności 54,8 mmola (NH*)? S?O8 w rorOworre 1 H kwasu solnego. Polimer przesączono, a następnie przemywano koleano wodą, metanolem i eterem dreOzlowym, po czyn wysuszono w próżni dznamrcznea. Polranlllnę deprotonowano w 1,1 H roztworze NH*OH. Wysuszoną zasadową formą pollanlllny redukowano do stopnia utleniania polileukoemeraldyny. 4,4 mola poOrayrliyz zmieszano ze 111 ml monohydratu hydrazyny w atmosferze gazu oboaςOyego. Redukcaę prowadzono przez 12 godzin w temperaturze 61*C. Wysuszoną ρoOrleut<oemeraldznę utleniano w 1,11 H roztworze kwasu 12-mo0lbdeyowpfpsforpwego w acetonitrylu przez 3 godziny. W procesie utleniania chemicznego wprowadzono 22% wagowych heterppolrayrpnów do polimeru. Otrzymany związek przemywano czystym aceton^^lem i suszono w próżni. Wysuszony produkt stanowił gotowy katalizator yadaaącz się do stosowania w procesie konwersai alkoholi i innych reakcaach.Example III. Polyanillin was obtained by polymerizing 109.5mmol of naniline in the presence of 54.8mmol (NH *) S? O8 in rorOworre 1 H hydrochloric acid. The polymer was filtered then washed with water, methanol and drainage ether and then dried in a manual vacuum. Polranlline was deprotonated in 1.1H NH * OH solution. The dried base polyolyl form was reduced to the degree of oxidation of the polyoxyemeraldine. 4.4 moles of poOrayrliyz were mixed with 111 ml of hydrazine monohydrate in an oboaςOy gas atmosphere. The reduction was carried out for 12 hours at the temperature of 61 ° C. The dried ρoOrleut <oemeraldehyde was oxidized in 1.11 H of a solution of 12-molar acid in acetonitrile for 3 hours. In the process of chemical oxidation, 22% by weight of heteropolyresins were introduced into the polymer. The resulting compound was washed with pure acetone ^ 3 and dried in vacuo. The dried product was a finished catalyst suitable for use in the alcohol conversion process and other reactions.
Przykład IV. Badano właściwości katalityczne kwasu 12-molrbdenofpsfprowego na nośniku poOiacetzleyowzm (zawartość heteropolikwasu wynosiła 21,8% wagowych) w reakcai konwersJI alkoholu etylowego w mikroreaktorze impulsowym· Próbka katalizatora wykazała mierzalną aktywność auż w temperaturze 151*C. Produktami konwe^ai były aldehyd octowy, etylen i eter dretzlρwz. W temperaturze 231’C konwersaa alkoholu wynosiła 26%, a aktywność katalizatora odniesiona do aednostki masy heteropolikwasu wynosiła 2,5 11-3 g C2H5OH/impuls.Example IV. The catalytic properties of 12-molrbdenofpsfpric acid on the Poacetzlean support (the content of heteropolyacids was 21.8% by weight) in the reaction of ethyl alcohol conversion in the impulse microreactor were investigated. The products of the convoy were acetaldehyde, ethylene and dretzlvv ether. At 231'C, the alcohol conversion was 26%, and the catalyst activity based on the mass unit of the heteropolyacid was 2.5-11-3 g C2H5OH / pulse.
Ola porównania w tea samea temperaturze przeprowadzono test katalityczny z czystym kwasem 12-molrbdeypwpfosfprowzm zmieszanym mechanicznie z rozdrobnionym szkłem kwarcowym. Konwersaa alkoholu w tym przypadku wynosiła 17,5%, a aktywność odniesiona do Jednostki masy heteropolikwasu wynosiła 1,425 11-* g C2H5OH/rmpuOs. Zmieniona była również selektywność dehydratacji katalitycznea etanolu, w szczególności uzyskano 55,0% aldehydu octowego, 16,4% etylenu i 27,7% eteru dietylowego stosuaąc w reakcai heOerpppOriwas na nośniku pplraceOyOeyowym.For comparison at the same temperature, a catalytic test was carried out with pure 12-molarbdeypwpphosphorus acid mechanically mixed with crushed quartz glass. The alcohol conversion in this case was 17.5%, and the activity related to the mass unit of the heteropolyacid was 1.425 * g C2H5OH / rmpuOs. The selectivity of the catalytic dehydration of ethanol was also changed, in particular, 55.0% acetaldehyde, 16.4% ethylene and 27.7% diethyl ether were obtained using heOerpppOriwas on the pplraceOyOey carrier in the reaction.
Departament Wydawnictw UP RP. Nakład 90 egz.Publishing Department of the UP RP. Circulation of 90 copies
Cena 10 000 złPrice: PLN 10,000
Claims (1)
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PL90286703A PL163857B1 (en) | 1990-08-31 | 1990-08-31 | Method of making catalysts with acid-base and redox properties composed of heteropolanions on a polymer carrier |
| PCT/PL1991/000006 WO1992004116A1 (en) | 1990-08-31 | 1991-03-19 | The method for fabrication of catalysts with acid-base and redox properties, consisting of heteropolyanions molecularly dispersed in polymer matrices |
| AU74981/91A AU7498191A (en) | 1990-08-31 | 1991-03-19 | The method for fabrication of catalysts with acid-base and redox properties, consisting of heteropolyanions molecularly dispersed in polymer matrices |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PL90286703A PL163857B1 (en) | 1990-08-31 | 1990-08-31 | Method of making catalysts with acid-base and redox properties composed of heteropolanions on a polymer carrier |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| PL286703A1 PL286703A1 (en) | 1992-03-09 |
| PL163857B1 true PL163857B1 (en) | 1994-05-31 |
Family
ID=20052181
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PL90286703A PL163857B1 (en) | 1990-08-31 | 1990-08-31 | Method of making catalysts with acid-base and redox properties composed of heteropolanions on a polymer carrier |
Country Status (3)
| Country | Link |
|---|---|
| AU (1) | AU7498191A (en) |
| PL (1) | PL163857B1 (en) |
| WO (1) | WO1992004116A1 (en) |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2625598B1 (en) * | 1987-12-30 | 1990-05-04 | Commissariat Energie Atomique | ELECTRONIC CONDUCTIVE POLYMERS DOPED BY HETEROPOLYANIONS, PROCESS FOR THEIR PREPARATION AND THEIR USE IN CHEMICAL AND ELECTROCHEMICAL CATALYSIS |
-
1990
- 1990-08-31 PL PL90286703A patent/PL163857B1/en unknown
-
1991
- 1991-03-19 WO PCT/PL1991/000006 patent/WO1992004116A1/en active Application Filing
- 1991-03-19 AU AU74981/91A patent/AU7498191A/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| AU7498191A (en) | 1992-03-30 |
| WO1992004116A1 (en) | 1992-03-19 |
| PL286703A1 (en) | 1992-03-09 |
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