CS271740B1 - Method of palladium catalyst preparation - Google Patents
Method of palladium catalyst preparation Download PDFInfo
- Publication number
- CS271740B1 CS271740B1 CS885386A CS538688A CS271740B1 CS 271740 B1 CS271740 B1 CS 271740B1 CS 885386 A CS885386 A CS 885386A CS 538688 A CS538688 A CS 538688A CS 271740 B1 CS271740 B1 CS 271740B1
- Authority
- CS
- Czechoslovakia
- Prior art keywords
- catalyst
- hydrogenation
- palladium
- nitrosodiphenylamine
- aminodiphenylamine
- Prior art date
Links
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000000034 method Methods 0.000 title claims abstract description 6
- 239000003054 catalyst Substances 0.000 title claims description 30
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 12
- OIJHFHYPXWSVPF-UHFFFAOYSA-N para-Nitrosodiphenylamine Chemical compound C1=CC(N=O)=CC=C1NC1=CC=CC=C1 OIJHFHYPXWSVPF-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- ATGUVEKSASEFFO-UHFFFAOYSA-N p-aminodiphenylamine Chemical compound C1=CC(N)=CC=C1NC1=CC=CC=C1 ATGUVEKSASEFFO-UHFFFAOYSA-N 0.000 claims abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 6
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims abstract description 6
- -1 4-nitrosodiphenylamine natrium salt Chemical class 0.000 claims abstract description 5
- 150000003839 salts Chemical class 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 239000000725 suspension Substances 0.000 abstract description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical class [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 abstract 1
- 159000000000 sodium salts Chemical class 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- 239000003245 coal Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910003445 palladium oxide Inorganic materials 0.000 description 2
- JQPTYAILLJKUCY-UHFFFAOYSA-N palladium(ii) oxide Chemical compound [O-2].[Pd+2] JQPTYAILLJKUCY-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- DAZLBCIMRZNCRV-UHFFFAOYSA-N aniline;sodium Chemical compound [Na].NC1=CC=CC=C1 DAZLBCIMRZNCRV-UHFFFAOYSA-N 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Predmetom vynálezu Je spSsob přípravy paládiového katalyzátore pre hydrogenáoiu sodnej aoli 4-nitrózodifenylamínu na 4-amínodifenylamín.SUMMARY OF THE INVENTION The present invention provides a process for preparing a palladium catalyst for the hydrogenation of sodium salt of 4-nitrosodiphenylamine to 4-aminodiphenylamine.
Doposial aa na katalytická hydrogenáoiu sodnej aoli 4-nitrózodifenylamínu na 4-amínodifenylamín používá ako katalyzátor paládiový katalyzátor, v ktorom je paládium nanesená na aktívnom uhlí. Tento katalyzátor aa připravuje v zvláStnom zariadeni a to tak, že aa k uhliu suspendovanému v destilovanej alebo deionizovanej vodě přidá roztok chloridu paladnatáho. Salším prídavkom roztoku alkálie, ktorou je uhličitan alebo hydrogénuhličitan aa na povrohu uhlia vylúči kysličník paladnatý. Z kysllčnika sa následovně vyredukuje kovová paládium účinkom vodného roztoku formaldehydu. Prooes pripravy katalyzátora prebieha pri zvýšenej teplote, ktorú je potřebné presne dodržiavat, nakolko pri jej překročeni sa znižuje aktivita připraveného katalyzátora. Tak isto aj čistota používaných surovin Je dčležitá pre vysokú aktivitu a selektivitu katalyzátora. Po výredukovaní paládia sa připravený katalyzátor premýva na filtri do slabo alkaliokej reakcie destilovanou alebo deionizovanou vodou a nakoniec 0,05 až 0,5%-ným vodným roztokoo uhličitanu alebo hydrogénuhličitanu, aby sa znížilo spatné rozpúštanie paládia do premývacej vody (Pašek, Jarkovanský, Seřábek, Mašek AO 179 618). Hotový katalyzátor, nakolko je pyroforický v euchom stave sa ežte vlhký musí uchovat pod dusíkom v polyetylénových vreciaoh alebo v Speoiálnych konteineroch. Pri hydrogenáoii sa okrem katalyzátora připravovaného podlá AO 179 618 používá aj katalyzátor, paládium na aktívnom uhlí, ktorý sa dováža z KŠ za devízy.To date, for the catalytic hydrogenation of the sodium salt of 4-nitrosodiphenylamine to 4-aminodiphenylamine, the catalyst uses a palladium catalyst in which the palladium is deposited on activated carbon. The catalyst aa is prepared in a separate apparatus by adding aa palladium chloride solution to the carbon suspended in distilled or deionized water. Another addition of an alkali solution, which is a carbonate or bicarbonate, and on the coal surface, precipitates palladium oxide. The palladium metal is subsequently reduced from the oxide by the action of an aqueous formaldehyde solution. The catalyst preparation process proceeds at an elevated temperature which must be strictly adhered to as the activity of the prepared catalyst decreases when it is exceeded. Also the purity of the raw materials used is important for the high activity and selectivity of the catalyst. After the palladium is reduced, the prepared catalyst is washed on the filter into a weakly alkaline reaction with distilled or deionized water and finally a 0.05-0.5% aqueous solution of carbonate or bicarbonate to reduce the poor dissolution of the palladium into the wash water (Pašek, Jarkovanský, Seřábek) , Masek AO 179 618). The finished catalyst, since it is pyrophoric in the dry state, must be kept wet under nitrogen in polyethylene bags or in speoial containers. In hydrogenation, in addition to the catalyst prepared according to AO 179 618, a catalyst, palladium on activated carbon, which is imported from the KS for foreign exchange, is also used.
Pri hydrogenáoii sodnej soli 4-aitrózodiřenylamínu na 4-amínodifenylamín sa do hydrogenačnáho procesu dávkuje pod tlakom suspenzia paládiového katalyzátora v deionizovanej vodě. Vodná suspenzia sodnej soli 4-nitrózodifenylaminu sa dávkuje spolu s toluénom do hydrogenačného reaktora, kde spolu s katalyzátorom a vodíkom vzniká heterogénna sústava, v ktorej prebieha hydrogenácia. Hydrogenáciou vznikajúci 4-amínodifenylamín prechádza z vodnej do toluánovej fázy, z ktorej sa po skončení hydrogenáoie a oddělení vodnej fázy získává destiláoiou. Ha paládiový katalyzátor sú kladené velké požiadavky na aktivitu, nakolko sa ho používá menej ako 1 % vzhladom na sodnú sol 4-nitrózodifenylamínu a tak isto sa musi vyznačovat hydrogenácia vysokou selektivitou a konverziou, minimálně 99,5 % 4-amíaodifenylamínu pričom obsah nezreagovanáho 4-nitrózodifenylaminu je max. 0,08 %.In the hydrogenation of the 4-aminodiphenylamine sodium salt to 4-aminodiphenylamine, a suspension of the palladium catalyst in deionized water is metered into the hydrogenation process under pressure. The aqueous suspension of the sodium salt of 4-nitrosodiphenylamine is fed together with toluene into a hydrogenation reactor, where, together with the catalyst and hydrogen, a heterogeneous system is formed in which the hydrogenation takes place. The 4-aminodiphenylamine formed by hydrogenation passes from the aqueous phase to the toluene phase, from which, after the hydrogenation and separation of the aqueous phase, distillation is obtained. The palladium catalyst is subject to great activity requirements since it is used less than 1% relative to the sodium salt of 4-nitrosodiphenylamine and also has to be characterized by hydrogenation with high selectivity and conversion, at least 99.5% 4-aminodiphenylamine with an unreacted 4- nitrosodiphenylamine is max. 0.08%.
Hevýhodou používaného postupu pripravy katalyzátora je velká prácnost, zvláštna linka na přípravu katalyzátora, nutnost používat na pripravu velké objemy destilovanej alebo deionizovanej vody. Ďalej sa musí používat zásada na vyzrážanie kysllčnika paladnatáho na povrchu uhlia a foraaldehyd na vyredukovanie kovového paládia, ňalšou nevýhodou je závislost aktivity katalyzátora od teploty, pri ktorej sa připravuje, pričom prekročenie teploty má za následek zhoršenie katalytickej účinnosti. Velkou nevýhodou je, ža katalyzátor, ako připravený podlá AO 179 618 tak aj dovážený z NSR Je pyroforický a pri jeho používaní hrozí nebezpečenstvo samozapálenia. Možnost samozapálenia je velmi nebezpečná v prevádzke, kde sa pracuje s toluénom a vodíkom.The disadvantage of the catalyst preparation process used is the high labor demand, a special catalyst preparation line, the need to use large volumes of distilled or deionized water for the preparation. In addition, a base must be used to precipitate palladium oxide on the surface of the coal and foraaldehyde to reduce the palladium metal. A major disadvantage is that the catalyst, both prepared according to AO 179 618 and imported from the Federal Republic of Germany is pyrophoric and there is a danger of self-ignition in its use. The possibility of self-ignition is very dangerous in an operation where toluene and hydrogen are used.
Uvedené nevýhody odstraňuje postup podlá vynálezu, pri ktorom sa katalyzátor připravuje priamo v hydrogenačnom procese a to pSsobeaím vodíka na suspenziu aktívneho uhlia a chloridu paladnatáho v toluéne za přítomnosti vodného roztoku sodnej soli 4-nitrózodifenylaminu. Teplota pri priprave hydrogenačného katalyzátora sa používá v rozmedzí 20 až 100 °0 a tlak vodíka 0,1 až 8 MPa. Katalyzátor je možné pripraviť tiež tak, že sa do toluénu přidá len roztok chloridu paladnatáho a uhlie sa suspenduje v roztoku sodnej soli 4-nitrózodi fenylamínu a potom sa za mieSania účinkom vodíka připraví v hydrogenačnom reaktore paládiový katalyzátor. Katalyzátor připravený podlá vynálezu priamo v hydrogenačnom procese má velmi dobrú selektivitu a aktivitu, čo Je nevyhnutné při hydrogeaácii sodnej soli 4-nitrózodifenylamínu a je srovnatelný s katalyzátorom dováženým za devízy z NSR od firmy Heraus a tiež s katalyzátorom připravovaným podlá AO 179 618.These disadvantages are overcome by the process according to the invention, wherein the catalyst is prepared directly in the hydrogenation process by treating the suspension of activated carbon and palladium chloride in toluene in the presence of an aqueous solution of 4-nitrosodiphenylamine sodium salt. The hydrogenation catalyst preparation temperature is in the range of 20 to 100 ° C and the hydrogen pressure is 0.1 to 8 MPa. The catalyst can also be prepared by adding only palladium (II) chloride solution to toluene and suspending the coal in a solution of 4-nitrosodium phenylamine sodium salt and then preparing a palladium catalyst in a hydrogenation reactor under hydrogen stirring. The catalyst prepared according to the invention directly in the hydrogenation process has very good selectivity and activity, which is necessary in the hydrogenation of the sodium salt of 4-nitrosodiphenylamine and is comparable to the catalyst imported from Germany from Heraus as well as the catalyst prepared according to AO 179 618.
Příprava katalyzátora priamo v hydrogenačnom procese podstatné zjednodušuje jeho přípravu, ako zásada sa využívá vodný roztok sodnej soli 4-nitrózodifenylamínu a na reOS 271 740 B1 dukciu sa používá vodík používaný v hydrogenačnom procese. Lávkováním množstva roztoku chloridu paladnatého a uhlia do procesu sa dá kontinuálně menií konoentrácia paládia na aktívnom uhlí v závislosti na kvalitě používanej sodnej soli 4-nitrózodiíenylamínu.The preparation of the catalyst directly in the hydrogenation process greatly simplifies its preparation, as an aqueous solution of 4-nitrosodiphenylamine sodium is used as the base and the hydrogen used in the hydrogenation process is used for the reOS 271 740 B1. By dosing the amount of palladium chloride solution and coal into the process, the concentration of palladium on activated carbon can be continually reduced, depending on the quality of the 4-nitrosodienylamine sodium salt used.
Tiež Je vylúčené samovznietenie katalyzátora, nakolko tento vzniká priamo v hydrogenačnom reaktore. Na pripravu katalyzátora nie je potřebné osobitné technologické zariadenie.Also, the autoignition of the catalyst is avoided since it is produced directly in the hydrogenation reactor. No special process equipment is required to prepare the catalyst.
V lalSom je predmet vynálezu objasněný na príkladoch bez toho, že by sa na tieto výlučné obmedzoval.In the foregoing, the invention is illustrated by way of example without being limited thereto.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS885386A CS271740B1 (en) | 1988-08-01 | 1988-08-01 | Method of palladium catalyst preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS885386A CS271740B1 (en) | 1988-08-01 | 1988-08-01 | Method of palladium catalyst preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CS538688A1 CS538688A1 (en) | 1990-03-14 |
| CS271740B1 true CS271740B1 (en) | 1990-11-14 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CS885386A CS271740B1 (en) | 1988-08-01 | 1988-08-01 | Method of palladium catalyst preparation |
Country Status (1)
| Country | Link |
|---|---|
| CS (1) | CS271740B1 (en) |
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1988
- 1988-08-01 CS CS885386A patent/CS271740B1/en unknown
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| Publication number | Publication date |
|---|---|
| CS538688A1 (en) | 1990-03-14 |
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