PL139785B1 - Method of obtaining a catalyst for hydrorefining of lubricating oils in particular for refining processes being carried out under mild conditions - Google Patents

Method of obtaining a catalyst for hydrorefining of lubricating oils in particular for refining processes being carried out under mild conditions Download PDF

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PL139785B1
PL139785B1 PL24559784A PL24559784A PL139785B1 PL 139785 B1 PL139785 B1 PL 139785B1 PL 24559784 A PL24559784 A PL 24559784A PL 24559784 A PL24559784 A PL 24559784A PL 139785 B1 PL139785 B1 PL 139785B1
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amount
catalyst
weight
nitrate
astm
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PL24559784A
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Polish (pl)
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PL245597A1 (en
Inventor
Edward Zienkiewicz
Marek Pawelczyk
Jerzy Haber
Jozef Grzeslo
Ludwik Zalewski
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Gdanskie Zaklady Rafineryjne
Inst Katalizy I Fizykochemii P
Politechnika Wroclawska
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Priority to PL24559784A priority Critical patent/PL139785B1/en
Priority to GB08500073A priority patent/GB2152402B/en
Priority to FR8500048A priority patent/FR2557476B1/en
Publication of PL245597A1 publication Critical patent/PL245597A1/en
Publication of PL139785B1 publication Critical patent/PL139785B1/en
Priority to GB08722073A priority patent/GB2194462B/en

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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/06Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • C10G45/08Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85Chromium, molybdenum or tungsten
    • B01J23/88Molybdenum
    • B01J23/881Molybdenum and iron

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Catalysts (AREA)
  • Lubricants (AREA)

Description

Przedmiotem wynalazku jest sposób otrzymywania katalizatora do hydrorafinacji olejów smarowych zwlaszcza przebiegajacej w lagodnych warunkach.Znane dotychczas sposoby otrzymywania katalizatorów do lagodnej hydrorafinacji olejów smarowych polegaja na osadzeniu aktywnych skladników w postaci róznych kombinacji molib¬ denu, kobaltu, niklu, wolframu na nosnik w postaci tlenku glinu zawierajacy lub nie zawierajacy tlenek krzemu. Wymienione katalizatory najczesciej sa aktywowane zwiazkami fluoru, magnezu, chromu, manganu.W polskim opisie patentowym nr 99952 opisanyjest katalizator zelazowy aktywowany solami lantanu, ceru i renu lub jednoczesnie solami ceru i niklu. Osadzenie wymienionych skladników aktywnych odbywa sie w osrodku peptyzujacym, którym jest 0,5% wodny roztwór kwasu azoto¬ wego. Znane sa równiez inne osrodki peptyzujace, w których odbywa sie osadzenie wyzej wymie¬ nionych skladników na katalizator zelazowy. Takimi znanymi osrodkami peptyzujacymi sa 0,5-2% wodny roztwór kwasu azotowego lub 1-6% wodny roztwór kwasu ortofosforowego.Wadakatalizatorów otrzymanych znanymi sposobami jest to,ze w procesie lagodnej hydrora*- finacji olejów smarowych prowadzonej w zakresie temperatur 533-573 K nie podwyzszaja wska¬ znika lepkosci olejów smarowych.Istota wynalazku polega na tym, ze wprowadza sie aktywny gamma — Fe203korzystniewraz ze stabilizatorami na nosnik w postaci tlenku glinu ewentualnie zawierajacy do 5% tlenku krzemu, w osrodku peptyzujacym, którym jest 0,5-6% wodny roztwór kwasu solnego korzystnie zawiera¬ jacy domieszke 0,01-2% kwasu azotowego. W takim osrodkupeptyzujacym nastepuje rozpuszcze¬ nie zanieczyszczen — wodorotlenku zelazawego i siarczanu zelazawego wystepujacych glównie w gamma — Fe^.Znajdujacy sie w tym osrodku kwas solny wiazejednoczesnie protony Fe,przez co wytworzony sposobem wedlug wynalazku katalizator staje sie bardziej aktywny w lagodnych warunkach procesu technologicznego. Jako stabilizatory gamma — FejOa stosuje sie molibdenian amonu lub molibdenianu amonu i kwasny fluorek amonu lub molibdenian amonu i azotan nikluJ t 2 139785 | lub azotan magnezu lub azotan magnezu i molibdenian amoiju lub azotan magnezu i azotan chromu przy czym molibdenian amonu wprowadza sie w takiej ilctóci, aby w gotowym katalizatorze ilosc trójtlenku molibdenianu wynosila 1-4% wagowych, zas molibdenian amonu i kwasny fluorek amonu wprowadza sie w takiej ilosci, aby w gotowym katalizatorze ilosc trójtlenku molibdenu wynosila 1-4% wagowych, a ilosc kwasnego fluorku amonu jwynosila 0,2-9% wagowych, zas molibdenian amonu i azotan niklu wprowadza sie w takiej ilojjci, aby w gotowym katalizatorze ilosc trójtlenku molibdenu wynosila 1-4% wagowych, a ilosc tjenku niklu 1-6% wagowych, zas azotan magnezu wprowadza sie w takiej ilosci, aby w gotowym katalizatorze ilosc tlenku magnezu wynosila 1-10% wagowych, zas azotan magnezu i molibdenian amonu wprowadza sie w takiej ilosci, aby w gotowym katalizatorze ilosc trójtlenku molibdenu wynosila 1-4% wagowych, a ilosc tlenku magnezu wynosila 1-10% wagowych, natomiast azotan magnezu i azotan chromu wprowa¬ dza sie w takiej ilosci, aby w gotowym katalizatorze ilosc tlenku magnezu wynosila 1-10% wagowych a ilosc tlenku chromu wynosila 1-7% wagowych. ^ Zastosowane do stabilizacji katalizatora wyzej wymienione substancje posiadaja takze wlasci¬ wosci aktywujace.Zaleta katalizatora otrzymanego sposobem wedlug wynalazku jest to, ze katalizator ten podczas lagodnej hydrorafinacji prowadzonej w zakresie temperatur 533-573 K pozwala zwiekszyc wskaznik lepkosci olejów smarowych o 17 jednostek. Katalizator moze byc stosowany takze do hydrorafinacji olejów w ostrzejszych warunkach. Katalizator ten nadaje sie równiez do hydroizo- meryzacji olejów napedowych.Inna odmiane katalizatora otrzymuje sie przez wprowadzenie alfa — Fe203 na nosnik w postaci tlenku glinu ewentualnie zawierajacy do 5% tlenku krzemu w osrodku peptyzujacym, którym jest 0,5-6% wodny roztwór kwasu solnego korzystnie zawierajacy domieszke 0,01-1,5% kwasu azotowego.Zaleta tego katalizatora jest to, ze podczas lagodnej hydrorafinacji prowadzonej w temperatu¬ rze 570-580 K pozwala zwiekszyc wskaznik lepkosci oleju smarowego o 9 jednostek.Przedmiot wynalazku przedstawiony jest w przykladach wykonania.Przyklad I. 0,15kg gamma — Fe203 o granulacji 2,3X 10~3m traktuje sie 0,5% wodnym roztworem kwasu solnego w ilosci 0,850 dm3 i pozostawia na przeciag 30 min. Nastepnie wprowa¬ dza sie 1 kg uwodnionego tlenku glinu o granulacji 2,3 X J0~3 m i zarabia na paste, która formuje sie na cylinderki. Cyhnderki te przez 24 h suszy sie w temperaturze 293 K, a nastepnie co 1 h podwyzsza sie temperature az do osiagniecia temperatury 473 K przez 3 K. Nastepnie prazy sie w temperaturze 753 K w ciagu 6h. W ten sposób otrzymany katalizator zawiera 13% Fe203, a reszte stanowi uwodniony tlenek glinu. Katalizator posiada namagnesowanie nasycenia 6,3 X 10°7TmVkg i tem¬ perature Curie 883 K. Katalizator ten zastosowany do lagodnej hydrorafinacji olejów smarowych rafinowanych selektywnie i odrafinowanych o barwie 5 ASTM i o wskazniku lepkosci 85 w temperaturze procesu 533 K, cisnieniu 5MPa, ilosci wodoru 1000 Nm3/m3 i szybkosci objetoscio¬ wej 0l7m3/m3h pozwala otrzymac oleje o barwie 2 ASTM i o wskazniku lepkosci 92 jednostki.Natomiast w temperaturze procesu 573 K, przy pozostalych parametrach procesu bez zmian, pozwala uzyskac oleje o barwie 1,8 ASTM i o wskazniku lepkosci 94jednostki, zas w temperaturze 593 K pozwala uzyskac olej o barwie 1,6 ASTM i o wskazniku lepkosci 97 jednostek.Przyklad II. 0,150kg gamma — Fe203 o granulacji 2,3X 10"3m miesza sie mechanicznie z 1 kg uwodnionego tlenku glinu o granulacji 2,3 X 10~3rn przez 30 min. dodajac stopniowo miesza¬ nine 1,5% wodnego roztworu kwasu solnego i 1,0% wodnego roztworu kwasu azotowego w stosunku objetosciowym 0,70 dm3 i 0,15dm3 i zarabia na paste, która formuje sie na cylinderki, a dalej postepuje jak w przykladzie I. W ten sposób otrzymany katalizator zawiera 13% FeiOa, a reszte stanowi uwodniony tlenk magnezu. Katalizator posiada namagnesowanie nasycenia 7,8 X 10~?TmVkg i temperature Curie 890 K. Katalizator ten zastosowany do lagodnej hydrorafi¬ nacji oleju smarowego o barwie 5 ASTM i o wskazniku lepkosci 85, w temperaturze procesu 533 K, cisnieniu 5MPa5 ilosci wodoru 1000Nm3/m3i szybkosci objetosciowej 0,7mVm3hpozwala otrzy¬ mac olej o barwie 1,8 ASTM i o wskazniku lepkosci 94 jednostek. Natomiast w temperaturze procesu 573 K, przy pozostalych parametrach procesu bez zmian uzyskuje sie olej o barwie 1,6 ASTM i o wskazniku lepkosci 96 jednostek, zas w temperaturze procesu 593 K pozwala otrzymac olej o barwie 1,4 ASTM i o wskazniku lepkosci 99 jednostek.139 785 3 Przyklad III. 0,150kg gamma — Fe203 o granulacji 2,3X 10~3m traktuje sie 2% wodnym roztworem kwasu solnego w ilosci 0,850 dm3, pozostawia na przeciag 30 minut i wprowadza sie 1,0 kg uwodnionego tlenku glinu o granulacji 2,3 X 10~3 m i zarabia na paste, formuje na cylinderki, a dalej postepuje jak w przykladzie I. W ten sposób otrzymany katalizator zawiera 13% Fe203, a resztestanowiuwodnionytlenekglinu.Katalizatorposiada namagnesowanie nasycenia 45X10~7T- m3/kg i temperature Curie 773 K. Katalizator ten zastosowany do lagodnej hydrorafinacji oleju smarowego rafinowanego selektywnie i odparafinowanego o barwie 5 ASTM i o wskazniku lepkosci 83 w temperturze procesu 533 K, cisnieniu 5 MPa, ilosci wodoru 1000 Nm3/m3 i szybkosci objetosciowej 0,7m3/m3h pozwala otrzymac olej o barwie 2,4 ASTM i o wskazniku lepkosci 85 jednostek. Natomiast w temperaturze procesu 573 K przy pozostalych parametrach procesu bez zmian pozwala uzyskac olej o barwie 1,3 ASTM i o wskazniku lepkosci 103 jednostki, zas w temperaturze procesu 593 K uzyskuje sie olej o barwie 1,2 ASTM i o wskazniku lepkosci 107 jednostek.Przyklad IV. 0,150kg gamma — Fe203 o granulacji 2,3X 10"3m traktuje sie 2% wodnym roztworem kwasu solnego w ilosci 0,920dm3 i pozostawia na przeciag 30 min. Nastepnie wprowa¬ dza sie 1,0 kg uwodnionego tlenku glinu z domieszka 4% SiC2 o granulacji 2,5 X 10"3 m i zarabia na paste, która formuje sie na cylinderki, a dalej postepuje tak jak w przykladzie I. Katalizator tak otrzymany zawiera 13% Fe203, a reszte stanowi glinokrzemian. Katalizator posiada namagnesowa¬ nie nasycenia 7,2 X 10~7Tm3/kg i temperature Curie 873 K. Katalizator zastosowany do lagodnej hydrorafinacji oleju smarowego rafinowanego selektywnie i odparafinowanego o barwie 5 ASTM i o wskazniku lepkosci 83 w temperaturze procesu 533 K, cisnieniu 5 MPa, ilosci wodoru 1000Nm3/m3 i szybkosci objetosciowej 0,7m3/m3h pozwala otrzymac olej o barwie 1,3 ASTM i o wskazniku lepkosci 84 jednostek. Natomiast w temperaturze procesu 573 K, przy pozostalych parametrach procesu bez zmian uzyskuje sie olej o barwie 1,6 ASTM i o wskazniku lepkosci 88 jednostek, zas w temperaturze procesu 593 K uzyskuje sie olej o barwie 1,3 ASTM i o wskazniku lepkosci 103 jednostki.Przyklad V. 0,152 kg gamma Fe203 o granulacji 2,3 X 10~3m miesza sie z KO kg uwodnio¬ nego tlenku glinu o granulacji jak wyzej przez 15 min. Nastepnie wprowadza sie 0,058 kg molibdenu amonu rozpuszczonego w 1,5% kwasie azotowym podgrzanym do temperatury 333 K w ilosci 0,1 dm3 i miesza mechanicznie przez 13 min. Tak przygotowana mase traktuje sie wodnym roztworem 2% kwasu solnego w ilosci 0,350 dm3 i zarabia mechanicznie na paste w ciagu 1 h. W ten sposób otrzymana paste formuje sie na cylinderki, a dalej postepuje jak w przykladzie I. Katalizator ten zawiera 12,5% Fe203, 3,9%Mo03 i reszte stanowiaca uwodniony tlenek glinu. Katalizator posiada namagnesowanie nasycenia 6,9 X 10"7TmVkg i temperature Curie 870 K. Katalizator ten zastosowany do lagodnej hydrorafinacji oleju smarowego rafinowanego selektywnie i odparafino¬ wanego o barwie 5 ASTM i o wskazniku lepkosci 85, w temperaturze procesu 593 K, cisnieniu 5 MPa, ilosci wodoru 1000NmVm3i o szybkosci objetosciowej 0,7 m3/m3h pozwala otrzymac olej o barwie 1,2 ASTM i o wskazniku lepkosci 93 jednostek. Natomiast w temperaturze procesu 563 K, cisnieniu 2,3MPa, ilosci wodoru 17NmVm3 i szybkosci objetosciowej 1 m3/m3h pozwala otrzy¬ mac olej o barwie 1,3 ASTM charakteryzujacy sie wskaznikiem lepkosci 91 jednostek, a w tempera¬ turze procesu 583 K pozwala otrzymac olej o barwie 1,1 ASTM i o wskazniku lepkosci 97jednostek.Katalizator ten zastosowany do hydroizomeryzacji oleju napedowego o temperaturze krzepniecia 275 K, w temperaturze procesu 615 K przy cisnieniu 5 MPa, ilosci wodoru 300 Nm3/m3 i szybkosci objetosciowej l,2m3/m3h pozwala uzyskac produkt o temperaturze krzepniecia 266K.Przyklad VI. 0,164 kg gamma — Fe2O3 o granulacji 2,3 X 10"3 miesza sie z 1 kg uwodnionego tlenku glinu o granulacji jak wyzej przez 15 min. Nastepnie wprowadza sie 0,033 kg kwasnego fluorku amonu w roztworze wodnym w ilosci 0,77dm3 i miesza mechanicznie przez 13 min. Do tej masy dodaje sie 0,059 kg molibdenianu amonu rozpuszczonego w 1% kwasie azotowym podgrza¬ nym do 333 K w ilosci 0,1 dm3 i miesza sie mechanicznie przez 28 min. Takprzygotowana mase traktuje sie wodnym roztworem 2% kwasu solnego w ilosci 0,520dm3 i zarabia mechanicznie na paste w ciagu 1 h. Otrzymana paste formuje sie na cylinderki, a dalej postepuje siejak w przykladzie I. Katalizator ten zawiera 13% Fe203,4% M0O3,1,4% F i reszte stanowiaca uwodniony tlenek glinu.Katalizator ten posiada namagnesowanie nasycenia 7,8 X 10~7TmVkg oraz temperature Curie 873 K. Katalizator zastosowany do lagodnej hydrorafinacji oleju smarowego rafinowanego sele-4 139715 tywnie i odparafinowanego o barwie 5 ASTM i o wskazniku lepkosci 83 w temperaturze procesu 533 K, cisnieniu 5MPa, ilosci wodoru 1000NmVm3 oraz szybkosci objetosciowej 097mVm,h pozwala otrzymac olej o barwie 2,5 ASTM i o wskazniku lepkosci 85 jednostek, a w temperaturze procesu 753 K, przy pozostalych parametrach bez zmian, pozwala otrzymac olej o barwie 1,6 ASTM i o wskazniku lepkosci 98jednostek, zas w temperaturze procesu 593 K pozwala uzyskac olej o barwie 1,4 ASTM i o wskazniku lepkosci 105 jednostek. Katalizator ten zastosowany do hydrorafinacji oleju smarowego rafinowanego selektywnie i odparafinowanego o barwie 5 ASTM i 0 wskazniku lepkosci 85 w temperaturze procersu 543 K, cisnieniu 2,3 MPa, ilosci wodoru 17NmVm3 i szybkosci objetosciowej lm3/m3h pozwala otrzymac olej o barwie 2ASTM i o wskazniku lepkosci 94 jednostki. Przy podwyzszeniu temperatury procesu do 563 K katalizator pozwala otrzymac olej o barwie 2 ASTM i o wskazniku lepkosci 96 jednostek, a w temperaturze 603 K otrzymuje sie olej o barwie 1,5 ASTM i o wskazniku lepkosci 97 jednostek. Katalizator ten zastosowny do hydrorafinacji rafinatu selektywnego o wskazniku lepkosci 90 w temperaturze procesu 593 K, cisnieniu 5 MPa, ilosci wodoru 1000Nm3/m3 i szybkosci objetosciowej 0,7 m3/m3 h pozwala otrzymac olej o wskazniku lepkosci 100 jednostek. Natomiast w temperaturze procesu 603 K, cisnieniu 2,3 MPa, ilosci wodoru 17Nm3/m3 i szybkosci 0,7m3/m3h zwieksza wskaznik lepkosci oleju do 104 jednostek.Prz y k l a d VII. 0,152 kg gamma — FeiOj o granulacji 2,3 X KT3m miesza sie z 1,0 kg uwod¬ nionego tlenku glinu o granulacji jak wyzej przez 15 min. Natomiast 0,058 kg molibdenianu amonu rozpuszczonego w 1,5% kwasie azotowym podgrzanym do temperatury 333 K wprowadza sie w ilosci 0,1 dm3 i miesza sie mechanicznie przez 28 min. Do tej masy dodaje sie 0,114kg 6-cio wodnego azotanu niklu rozpuszczonego w 2% kwasie solnym w ilosci 0,12dm3 i miesza sie mechanicznie przez 28 min. Takprzygotowana mase traktuje sie 2% wodnym roztworem kwasu solnego w ilosci 0,3dm3 i zarabia mechanicznie na paste w ciagu 53 min. Otrzymana paste formuje sie na cylinderki a dalej postepuje sie jak w przykladzie I. Katalizator ten zawiera 11,5% FejOj, 3,6% MoOs, 2,1% NiO i reszte stanowiaca uwodniony tlenek glinu. Katalizatorten posiada namag¬ nesowanie nasycenia 9,5 X 10~7TmVkg i temperature Curie 890 K. Katalizatorten zastosowany do lagodnej hydrorafinacji oleju smarowego rafinowanego selektywnie i odparafinowanego o barwie 5 ASTM i o wskazniku lepkosci 85jednostek w temperaturze procesu 593 K, cisnieniu 5 MPa,ilosci wodoru 1000Nm3/m3 i szybkosci objetosciowej 0,7m3/m3h podwyzsza wskaznik lepkoscido 93 jednostek i daje olej o barwie 1,1 ASTM.Przyklad VIII. 0, 153 kg gamma — FeiOio granulacji 2,3 X 10~' miesza sie mechanicznie z 1 kg uwodnionego tlenku glinu o zawartosci 4% SiOa ogranulacjijak wyzej przez 15 min. Nastepnie wprowadza sie 0,371 kg szesciowodnego azotanu magnezu w roztworze wodnym w ilosci 0,550dm3 i miesza sie mechanicznie przez 42 min. Takprzygotowana mase traktuje sie 2% wodnym roztwo¬ rem kwasu solnego w ilosci 0,880dm3 i zarabia mechanicznie na paste w ciagu 63 min. Otrzymana paste formuje sie na cylinderki, a nastepnie postepuje sie jak w przykladzie I. Katalizator ten zawiera 10% FejOa, 4%MgO i reszte stanowiaca uwodniony glinokrzemian. Katalizator ten posiada namagnesowanie nasycenia 8,lxlO~7TmVkg i temperature Curie 879 K. Katalizator zastosowany do lagodnej hydrorafinacji oleju smarowego rafinowanego selektywnie i odparafino¬ wanego o barwie 5 ASTM i o wskazniku lepkosci 83 jednostek w temperaturze procesu 533 K, cisnieniu 5 MPa,ilosci wodoru 1000Nm3/m3 i szybkosci objetosciowej 0t7mVm3h pozwala otrzy¬ mac olej o barwie 2,6 ASTM i o wskaznikulepkosci 88 jednostek, natomiast w temperaturze 573 K przy pozostalych parametrach procesu bez zmian pozwala uzyskac olej o barwie 1,5 ASTM i o wskazniku lepkosci 103 jednostki, zas w temperaturze procesu 593 K daje olej o barwie 1,2 ASTM i 0 wskazniku lepkosci 105 jednostek. Katalizator ten zastosowany do hydrorafinacji oleju smaro¬ wego o barwie 5 ASTM i o wskazniku lepkosci 85 jednostek w temperaturze procesu 543 K, cisnieniu 2,3 MPa, ilosci wodoru 17Nm3/m3 i szybkosci objetosciowej 1 m3/m3h pozwala otrzy¬ mac olej o barwie 1,5 ASTM i o wskaznikulepkosci 92jednostki. Przy podwyzszeniu temperatury procesu do 563 K daje olej o barwie 1,5 ASTM i o wskazniku lepkosci 93 jednostki, a w temperatu¬ rze procesu 603 K otrzymuje sie olej o barwie 1,5 ASTM i o wskazniku lepkosci 94 jednostki.Przyklad IX. 0,170kg gamma — FejOi o granulcji 2,3X 10"3m miesza sie mechanicznie z 1 kg uwodnionego tlenku glinu o zawartosci 4% SiOao granulacjijak wyzej przez 15min. Nastepnie wprowadza sie 0,37 kg szesciowodnego azotanu magnezu w roztworze wodnym w ilosci 0,550dm3139 785 5 i miesza sie mechanicznie przez 20 min., a nastepnie dodaje sie 0,230kg dziewieciowodnego azotanu chromu w roztworze wodnym w ilosci 0,315 dm3 i miesza mechanicznie przez 22 min. W ten sposób przygotowana mase traktuje sie 2% wodnym roztworem kwasu solnego w ilosci 0,678 dm3 i zarabia mechanicznie na paste w ciagu 63 min. Otrzymana paste formuje sie na cylinderki a dalej postepuje jak w przykladzie I. Katalizator ten zawiera 9,6% Fe203, 4%MgO, 2% Cr03 i reszte stanowiaca uwodniony glinokrzemian. Katalizator ten posiada namagnesowanie nasycenia 10,2 X 10~7TmVkg i temperature Curie 930 K. Katalizator zastosowany do lagodnej hydrorafinacji oleju smarowego rafinowanego selektywnie i odparafinowanego o barwie 5 ASTM i o wskazniku lepkosci 85 jednostek w temperaturze 573 K, cisnieniu 5MPa, ilosci wodoru 1000 Nm3/m3 i szybkosci objetosciowej 0,7m3/m3h pozwala otrzymac olej o barwie 1,4 ASTM i o wskazniku lepkosci 102 jednostek.Przyklad X. 0,164 gamma — Fe203o granulacji 2,3 X 10~3m miesza sie mechanicznie z 1 kg uwodnionego tlenku glinu o zawartosci 4%SiO o granulacji jak wyzej przez 15 min. Nastepnie wprowadza sie 0,4kg szesciowodnego azotanu megnezu w roztworze wodnym w ilosci 0,529dm3 i miesza mechanicznie przez 13 min, przy czym dodaje sie 0,59 kg molibdenu amonu rozpuszczonego w 1% wodnym roztworze kwasu azotowego podgrzanym do temperatury 333 K w ilosci 0,1 dm' i nadal miesza mechanicznie przez 28 min. W ten sposób przygotowana mase traktuje sie 2% wodnym roztworem kwasu solnego w ilosci 0,420 dm3 i zarabia mechanicznie na paste w ciagu 1 h, a dalej postepuje sie jak w przykladzie I. Katalizator ten zawiera 10% Fe203, 3%Mo03, 3,8% MgO i reszte stanowiaca uwodniony glinokrzemian. Katalizator ten posiada namagnesowanie nasycenia 7,4X 10"7Tm3/kg i temperature Curie 850 K. Katalizator zastosowany do lagodnej hydrorafinacji oleju smarowego rafinowanego selektywnie i odparafinowanego o barwie 5 ASTM i o wskazniku lepkosci 83 jednostek w temperaturze procesu 533 K, cisnieniu 5 MPa;ilosciwodoru 1000 Nm3/m3i szybkosci objetosciowej 0,7m3/m3h pozwala otrzymac olej o barwie 2,5 ASTM i o wskazniku lepkosci 86 jednostek, a w temperaturze procesu 573 K przy pozostalych parametrach bez zmian pozwala otrzymac olej o barwie 1,9 ASTM i o wskazniku lepkosci 92 jednostki zas w temperaturze 593 K pozwala otrzymac olej o barwie 1,5 ASTM i o wskazniku lepkosci 96 jednostek.Przyklad XI. 0,150kg alfa — Fe203 o granulacji 2,3Xl0~3m traktuje sie 2% wodnym roztworem kwasu solnego i pozostawia na przeciag 30 min. Nastepnie wprowadza sie 1 kg uwod¬ nionego tlenku glinu o granulacji 2,3 X 10"3m i zarabia na paste, która formuje sie na cylinderki, a dalej postepuje sie jak w przykladzie I. Katalizator ten zawiera 13%Fe203 i reszte stanowiaca uwodniony tlenek glinu. Katalizator ten zastosowany do lagodnej hydrorafinacji oleju smarowego rafinowanego selektywnie i odparafinowanego o barwie 5 ASTM i o wskazniku lepkosci 83 jednostek, w temperaturze procesu 573 K, cisnieniu 5 MPa, ilosci wodoru 1000 Nm3/m\ szybkosci objetosciowej 0,7m3/m3h pozwala otrzymac olej o barwie 2 ASTM i o wskazniku lepkosci 90 jednostek.Zastrzezenia patentowe 1. Sposób otrzymywania katalizatora do hydrorafinacji olejów smarowych, zwlaszcza prze¬ biegajacej w lagodnych warunkach, polegajacy na wprowadzeniu aktywnego gamma — Fe^, korzystnie ze stabilizatorami, na nosnik w postaci tlenku glinu ewentualnie zawierajacy do 5% tlenku krzemu, w osrodku peptyzujacym, suszeniu i prazeniu, znamienny tym, ze jako osrodek peptyzujacy stosuje sie 0,5-6% wodny roztwór kwasu solnego korzystnie zawierajacy domieszke 0,01-2% kwasu azotowego, ajako stabilizatory gamma — Fe^stosuje sie molibdenian amonu lub molibdenian amonu i kwasny fluorek amonu lub molibdenian amonu i azotan niklu lub azotan magnezu lub azotan magnezu i molibdenian amonu lub azotan magnezu i azotan chromu przy czym molibdenian amonu wprowadza sie w takiej ilosci, aby w gotowym katalizatorze ilosc trójtlenku molibdenu wynosila 1-4% wagowych, zas molibdenian amonu i kwasny fluorek amonu wprowadza sie w takiej ilosci, aby w gotowym katalizatorze ilosc trójtlenku molibdenu wynosila 1-4% wagowych, a ilosc kwasnego fluorku amonu w7nosila 0,2-9% wagowych, zas molibdenian amonu i azotan niklu wprowadza sie w takiej ilosci, aby w gotowym katalizatorze ilosc trójtlenku molibdenu wynosila 1-4% wagowych, a ilosc tlenku niklu 1-6% wagowych, zas azotan magnezut V ) 6 139785 ( wprowadza sie w takiej ilosci, aby w gotowym katalizatorze ilosc tlenku magnezu wynosila 1-10% wagowych, zas azotan magnezu i molibdenian amonu wprowadza sie takiej ilosci, aby w gotowym katalizatorze ilosc trójtlenku molibdenu wynosila 1-4% wagowych, a ilosc tlenku magnezu wynosila 1-10% wagowych, natomiast azotan magnezu i azotan chromu wprowadza sie w takiej ilosci, aby w gotowym katalizatorze ilosc tlenku magnezu wynosila 1-10% wagowych a ilosc tlenku chromu wynosila 1-7% wagowych. 2. Sposób otrzymywania katalizatora do hydrorafinacji olejów smarowych zwlaszcza prze¬ biegajacej w lagodnych warunkach, polegajacy na wprowadzeniu alfa — FejOjnanosnik w postaci tlenku glinu ewentualnie zawierajacy do 5% tlenku krzemu w osrodku peptyzujacym, suszeniu i prazeniu, znamienny tym, ze jako osrodek peptyzujacy stosuje sie 0,5-6% wodny roztwór kwasu solnego korzystnie zawierajacy domieszke 0,01-1,5% kwasu azotowego.Pracownia Pottgnflcznt UP PRL. Naklad 100 eg*.Cena 130 zl PLThe subject of the invention is a method for the preparation of a catalyst for the hydrotreatment of lubricating oils, especially under mild conditions. The so far known methods of obtaining catalysts for the mild hydrotreating of lubricating oils consist in depositing active components in the form of various combinations of molybdenum, cobalt, nickel, tungsten onto an aluminum oxide carrier. with or without silicon oxide. The above-mentioned catalysts are most often activated with compounds of fluorine, magnesium, chromium, manganese. Polish patent description No. 99952 describes an iron catalyst activated with lanthanum, cerium and rhenium salts or simultaneously with cerium and nickel salts. The deposition of the active ingredients mentioned takes place in a peptizing medium which is a 0.5% aqueous solution of nitric acid. There are also other peptizing agents in which the deposition of the above-mentioned components on the iron catalyst takes place. Such known peptizing agents are 0.5-2% aqueous solution of nitric acid or 1-6% aqueous solution of orthophosphoric acid. The disadvantages of the known methods are that in the process of mild hydrora * - lubricating oils finalization carried out in the temperature range 533-573 K They do not increase the viscosity index of lubricating oils. The essence of the invention is that an active gamma-Fe 2 O 3 is introduced, preferably together with stabilizers on the alumina carrier, possibly containing up to 5% of silicon oxide, in a peptizing agent, which is 0.5-6% an aqueous solution of hydrochloric acid preferably doped with 0.01-2% nitric acid. In such a peptizing center, the impurities - ferrous hydroxide and ferrous sulphate, mainly in gamma - Fe - are dissolved. The hydrochloric acid present in this medium binds Fe protons at the same time, thus the catalyst produced by the method according to the invention becomes more active under mild process conditions. Ammonium molybdate or ammonium molybdate and acid ammonium fluoride or ammonium molybdate and nickel nitrate are used as gamma-FejOa stabilizersJ t 2 139785 | or magnesium nitrate or magnesium nitrate and ammonium molybdate or magnesium nitrate and chromium nitrate, the amount of ammonium molybdate being introduced in such an amount that in the finished catalyst the amount of molybdate trioxide amounts to 1-4% by weight, while ammonium molybdate and acid ammonium fluoride are introduced into such the amount in the finished catalyst is 1-4% by weight and the amount of acid ammonium fluoride is 0.2-9% by weight, and ammonium molybdate and nickel nitrate are added in such an amount that in the finished catalyst the amount of molybdenum trioxide is 1-4% by weight, and the amount of nickel thionide is 1-6% by weight, and the amount of magnesium nitrate is added in such an amount that in the finished catalyst the amount of magnesium oxide is 1-10% by weight, and the amount of magnesium nitrate and ammonium molybdate are added in such an amount that in the finished catalyst the amount of molybdenum trioxide is 1-4% by weight, and the amount of magnesium oxide is 1-10% by weight, and magnesium nitrate and chromium nitrate are introduced The amount is adjusted so that in the finished catalyst the amount of magnesium oxide is 1-10% by weight and the amount of chromium oxide is 1-7% by weight. The above-mentioned substances used to stabilize the catalyst also have activating properties. The advantage of the catalyst obtained according to the invention is that this catalyst allows for the increase of the viscosity index of lubricating oils by 17 units during mild hydrotreating carried out in the temperature range of 533-573 K. The catalyst can also be used for hydrotreating oils under more severe conditions. This catalyst is also suitable for the hydroisomerization of diesel fuels. Another catalyst variation is obtained by introducing alpha-Fe2O3 onto an alumina carrier optionally containing up to 5% silicon oxide in a 0.5-6% aqueous acid peptizing medium salt, preferably containing 0.01-1.5% nitric acid. The advantage of this catalyst is that during mild hydrotreating at a temperature of 570-580 K it allows the viscosity index of the lubricating oil to be increased by 9 units. The subject of the invention is illustrated in the examples Example 1: 0.15 kg of gamma - Fe 2 O 3, granulation 2.3 × 10 ~ 3 m, is treated with 0.5% aqueous solution of hydrochloric acid in the amount of 0.850 dm3 and left for 30 minutes. Then, 1 kg of hydrated alumina, granulation 2.3 × 3 m, is introduced and made into a paste that forms into cylinders. These cyhnderki are dried for 24 hours at the temperature of 293 K, and then, every 1 hour, the temperature is increased until they reach the temperature of 473 K for 3 K. Then they are ironed at the temperature of 753 K for 6 hours. The thus obtained catalyst contains 13% Fe2O3, the rest being hydrated alumina. The catalyst has a saturation magnetization of 6.3 X 10 ° 7 TmVkg and a Curie temperature of 883 K. This catalyst is used for the mild hydrotreating of selectively refined and refined lubricating oils with a color of ASTM 5 and a viscosity index of 85 at the process temperature of 533 K, pressure 5 MPa, and the amount of hydrogen. 1000 Nm3 / m3 and a volumetric velocity of 0l7 m3 / m3h allows to obtain oils with a color of 2 ASTM and a viscosity index of 92 units, while at the process temperature of 573 K, with other process parameters unchanged, it allows to obtain oils with a color of ASTM 1.8 and an index of 94 units of viscosity, while at the temperature of 593 K it allows obtaining an oil with a color of 1.6 ASTM and a viscosity index of 97 units. Example II. 0.150 kg of gamma - Fe 2 O 3, granulation 2.3 × 10 "3 m, is mixed mechanically with 1 kg of hydrated alumina 2.3 × 10-3 m for 30 minutes, adding gradually 1.5% aqueous solution of hydrochloric acid and 1 , 0% aqueous solution of nitric acid in the volume ratio of 0.70 dm3 and 0.15 dm3 and earns the paste, which forms into cylinders, and then proceeds as in example I. The catalyst thus obtained contains 13% FeiOa, and the rest is hydrated magnesium oxide The catalyst has a saturation magnetization of 7.8 X 10 ~ TmVkg and a Curie temperature of 890 K. This catalyst was used for the mild hydrotreatment of lubricating oil of ASTM color 5 and viscosity index 85, at process temperature 533 K, pressure 5 MPa5 Hydrogen 1000Nm3 / m3 and a volumetric velocity of 0.7mVm3h allows obtaining an oil with a color of 1.8 ASTM and a viscosity index of 94 units, while at the process temperature of 573 K, with the remaining process parameters unchanged, an oil with a color of 1.6 ASTM is obtained. It has a viscosity of 96 units, while at the process temperature of 593 K, it is possible to obtain an oil with a color of 1.4 ASTM and a viscosity index of 99 units. 139 785 3 Example III. 0.150 kg of gamma - Fe2 O3, granulation 2.3 × 10 ~ 3 m, is treated with 2% aqueous solution of hydrochloric acid in the amount of 0.850 dm3, left for 30 minutes and 1.0 kg of hydrated alumina 2.3 × 10 ~ 3 is introduced. mi earns a paste, forms it into cylinders, and then proceeds as in example I. The catalyst thus obtained contains 13% Fe2O3, and the rest is hydrated aluminum oxide. The catalyst has 45X10 ~ 7T- m3 / kg saturation magnetization and 773K Curie temperature. mild hydrotreatment of selectively refined and dewaxed lubricating oil with ASTM color 5 and viscosity index 83 at process temperature 533 K, pressure 5 MPa, hydrogen amount 1000 Nm3 / m3 and volumetric speed 0.7 m3 / m3h allows to obtain oil with a color of ASTM 2.4 and viscosity index 85 units. However, at the process temperature of 573 K, with the remaining process parameters unchanged, it allows to obtain an oil with a color of 1.3 ASTM and a viscosity index of 103 units, while at the process temperature of 593 K, an oil with a color of 1.2 ASTM and a viscosity index of 107 units is obtained. . 0.150 kg of gamma - Fe 2 O 3, granulation 2.3 × 10 "3 m, is treated with a 2% aqueous solution of hydrochloric acid in the amount of 0.920 dm3 and left for 30 minutes. Then 1.0 kg of hydrated alumina mixed with 4% SiC 2 is introduced. granulation 2.5 X 10 "3 m and makes a paste, which forms into cylinders, and then proceeds as in example 1. The catalyst thus obtained contains 13% Fe2O3, and the rest is aluminosilicate. The catalyst has a saturation magnetization of 7.2 X 10 ~ 7 Tm3 / kg and a Curie temperature of 873 K. The catalyst used for the mild hydrotreatment of selectively refined and dewaxed lubricating oil with a color of 5 ASTM and a viscosity index of 83 at the process temperature of 533 K, pressure 5 MPa, 1000Nm3 / m3 of hydrogen and a volumetric velocity of 0.7m3 / m3h allows to obtain oil with a color of 1.3 ASTM and a viscosity index of 84 units. However, at the process temperature of 573 K, with the remaining process parameters unchanged, an oil with a color of 1.6 ASTM and a viscosity index of 88 units is obtained, while at the process temperature of 593 K, an oil with a color of 1.3 ASTM and a viscosity index of 103 units is obtained. V. 0.152 kg of gamma Fe 2 O 3, granulation 2.3 × 10-3 m, is mixed with KO kg of hydrated alumina, grain size as above, for 15 minutes. Then 0.058 kg of ammonium molybdenum dissolved in 1.5% nitric acid heated to the temperature of 333 K in the amount of 0.1 dm3 are introduced and mechanically mixed for 13 minutes. The mass prepared in this way is treated with an aqueous solution of 2% hydrochloric acid in the amount of 0.350 dm3 and mechanically earns the paste within 1 hour. The paste obtained in this way is formed into cylinders, and then proceeds as in example I. This catalyst contains 12.5% Fe 2 O 3, 3.9% Mo 3, and the rest was hydrated alumina. The catalyst has a saturation magnetization of 6.9 X 10 "7 TmVkg and a Curie temperature of 870 K. This catalyst is used for the mild hydrotreating of lubricating oil selectively refined and dewaxed with a color of 5 ASTM and a viscosity index of 85, at a process temperature of 593 K, pressure of 5 MPa, 1000NmVm3i amount of hydrogen with a volumetric velocity of 0.7 m3 / m3h allows to obtain an oil with a color of 1.2 ASTM and a viscosity index of 93 units, while at the process temperature of 563 K, pressure of 2.3MPa, hydrogen amount of 17NmVm3 and a volume velocity of 1 m3 / m3h, it allows obtained oil with a color of 1.3 ASTM, having a viscosity index of 91 units, and at the process temperature of 583 K, it allows to obtain an oil of a color of 1.1 ASTM and a viscosity index of 97 units. This catalyst was used for hydroisomerization of diesel oil with a freezing point of 275 K , at a process temperature of 615 K at a pressure of 5 MPa, an amount of hydrogen of 300 Nm3 / m3 and a volumetric velocity of 1,2 m3 / m3h, it allows to obtain a product with a temperature coagulation round 266K. Example VI. 0.164 kg of gamma-Fe2O3 granulation 2.3 X 10 "3 is mixed with 1 kg of hydrated alumina granulation as above for 15 minutes. Then 0.033 kg of acid ammonium fluoride in an aqueous solution in an amount of 0.77 dm3 is introduced and mechanically mixed for 15 minutes. 13 min. To this mass is added 0.059 kg of ammonium molybdate dissolved in 1% nitric acid heated to 333 K in the amount of 0.1 dm3 and mechanically mixed for 28 min. The prepared mass is treated with an aqueous solution of 2% hydrochloric acid in the amount of 0.520 dm3 and mechanically earns the paste within 1 hour. The obtained paste is formed into cylinders, and then the seed is proceeded in example 1. This catalyst contains 13% Fe203.4% MoO3.1.4% F and the rest being hydrated alumina. This catalyst has a saturation magnetization of 7.8 X 10 ~ 7TmVkg and a Curie temperature of 873 K. The catalyst used for the mild hydrotreating of sele-4 refined and dewaxed lubricating oil 139715 with a color of ASTM 5 and a viscosity index of 83 at a temperature of 533 K process, 5MPa pressure, 1000NmVm3 hydrogen quantity and 097mVm volumetric velocity, h allows to obtain oil with a color of 2.5 ASTM and a viscosity index of 85 units, and at the process temperature of 753 K, with other parameters unchanged, it allows to obtain oil with a color of 1, 6 ASTM and a viscosity index of 98 units, while at the process temperature of 593 K it produces an oil with a color of 1.4 ASTM and a viscosity index of 105 units. This catalyst used for the hydrotreatment of selectively refined and dewaxed lubricating oil with the color 5 ASTM and the viscosity index 85 at the temperature of 543 K, the pressure of 2.3 MPa, the amount of hydrogen 17NmVm3 and the volumetric speed of lm3 / m3h allows to obtain the oil with the color 2ASTM and with the viscosity index 94 units. By increasing the process temperature to 563 K, the catalyst allows to obtain an oil with a color of 2 ASTM and a viscosity index of 96 units, and at a temperature of 603 K, an oil with a color of 1.5 ASTM and a viscosity index of 97 units is obtained. This catalyst, used for the hydrotreating of selective raffinate with a viscosity index of 90 at a process temperature of 593 K, a pressure of 5 MPa, a quantity of hydrogen of 1000Nm3 / m3 and a volumetric speed of 0.7 m3 / m3 h, allows to obtain an oil with a viscosity index of 100 units. On the other hand, at the process temperature of 603 K, pressure 2.3 MPa, the amount of hydrogen 17Nm3 / m3 and the rate of 0.7 m3 / m3h, the oil viscosity index increases to 104 units. 0.152 kg of gamma-FeiOj, granulation 2.3 × KT3m, is mixed with 1.0 kg of hydrated alumina, granulation as above, for 15 minutes. On the other hand, 0.058 kg of ammonium molybdate dissolved in 1.5% nitric acid heated to the temperature of 333 K is introduced in the amount of 0.1 dm3 and mechanically mixed for 28 minutes. To this mass is added 0.114 kg of 6-aqueous nickel nitrate dissolved in 2% hydrochloric acid in the amount of 0.12 dm3 and stirred mechanically for 28 minutes. The prepared mass is treated with a 2% aqueous solution of hydrochloric acid in the amount of 0.3 dm3 and mechanically earns the paste within 53 minutes. The resulting paste is formed into cylinders and then the procedure is as in example I. This catalyst contains 11.5% FejOj, 3.6% MoOs, 2.1% NiO and the rest is hydrated alumina. Catalystene has a saturation magnetization of 9.5 X 10 ~ 7 TmVkg and a Curie temperature of 890 K. The catalysatortene is used for the mild hydrotreating of selectively refined and dewaxed lubricating oil with a color of ASTM 5 and a viscosity index of 85 units at a process temperature of 593 K, a pressure of 5 MPa, and an amount of hydrogen. 1000Nm3 / m3 and a volumetric velocity of 0.7 m3 / m3h increases the viscosity index to 93 units and gives an oil with a color of 1.1 ASTM. Example VIII. 0.153 kg gamma - FeiOio granulation 2.3 X 10 'is mixed mechanically with 1 kg of hydrated alumina containing 4% SiOa limitation as above for 15 min. Then 0.371 kg of hexahydrate magnesium nitrate in an aqueous solution in the amount of 0.550 dm3 are introduced and mixed mechanically for 42 minutes. The prepared mass is treated with a 2% aqueous solution of hydrochloric acid in the amount of 0.880 dm3 and mechanically earned for the paste within 63 minutes. The resulting paste is formed into cylinders, and then the procedure is as in Example 1. This catalyst contains 10% FejOa, 4% MgO and the rest is hydrated aluminosilicate. This catalyst has a saturation magnetization of 8,1x10 ~ 7TmVkg and a Curie temperature of 879K. The catalyst used for the mild hydrotreating of selectively refined and dewaxed lubricating oil with a color of 5 ASTM and a viscosity index of 83 units at the process temperature of 533 K, pressure 5 MPa, the amount of hydrogen 1000Nm3 / m3 and a volumetric velocity of 0t7mVm3h allows obtaining an oil with a color of 2.6 ASTM and a viscosity index of 88 units, while at the temperature of 573 K with other process parameters unchanged, it allows to obtain an oil with a color of 1.5 ASTM and a viscosity index of 103 units, while at a process temperature of 593 K gives an oil with a color of 1.2 ASTM and a viscosity index of 105 units. This catalyst, used for the hydrotreating of 5 ASTM lubricating oil with a viscosity index of 85 units, at a process temperature of 543 K, a pressure of 2.3 MPa, an amount of hydrogen of 17 Nm3 / m3 and a volumetric speed of 1 m3 / m3 h, allows to obtain an oil with a color of 1 .5 ASTM and a viscosity index of 92 units. Increasing the process temperature to 563 K yields an oil 1.5 ASTM with a viscosity index of 93 units, and at the process temperature of 603 K an oil having a color of 1.5 ASTM with a viscosity index of 94 units is obtained. 0.170 kg of gamma - FejOi 2.3X10 "3m granulation is mixed mechanically with 1 kg of hydrated alumina with 4% SiOa granulation as above for 15 minutes. Then 0.37 kg of hexahydrate magnesium nitrate in an aqueous solution in the amount of 0.550 dm3139 785 is introduced 5 and mechanically mixed for 20 minutes, then 0.230 kg of chromium nine-hydrate nitrate in an aqueous solution in the amount of 0.315 dm3 is added and mechanically mixed for 22 minutes. The prepared mass is treated in this way with a 2% aqueous solution of hydrochloric acid in the amount of 0.678 dm3 and mechanically earns the paste within 63 minutes The resulting paste is formed into cylinders and then proceeds as in example I. This catalyst contains 9.6% Fe2O3, 4% MgO, 2% Cr03 and the rest being hydrated aluminosilicate. This catalyst has a magnetization saturation 10.2 X 10 ~ 7TmVkg and temperature Curie 930K. Catalyst used for mild hydrotreating selectively refined and dewaxed lubricating oil with ASTM 5 color and index viscosity 85 units at a temperature of 573 K, a pressure of 5MPa, the amount of hydrogen 1000 Nm3 / m3 and a volumetric velocity of 0.7 m3 / m3h allows to obtain an oil of 1.4 ASTM color and a viscosity index of 102 units. Example X. 0.164 gamma - Fe203o granulation 2, 3 X 10 ~ 3m is mixed mechanically with 1 kg of hydrated alumina containing 4% SiO with granulation as above for 15 min. Then 0.4 kg of hexahydrate megnesium nitrate in an aqueous solution in the amount of 0.529 dm3 is introduced and mechanically mixed for 13 minutes, while 0.59 kg of ammonium molybdenum dissolved in 1% aqueous nitric acid solution heated to 333 K in the amount of 0 is added, 1 dm 'and continues to mix mechanically for 28 min. The prepared mass is treated with a 2% aqueous solution of hydrochloric acid in the amount of 0.420 dm3 and the paste is mechanically prepared within 1 hour, and then the procedure is as in example I. This catalyst contains 10% Fe2O3, 3% Mo03, 3.8 % MgO and the remainder hydrated aluminosilicate. This catalyst has a saturation magnetization of 7.4X 10 "7Tm3 / kg and a Curie temperature of 850 K. The catalyst used for the mild hydrotreatment of selectively refined and dewaxed lubricating oil with a color of ASTM 5 and a viscosity index of 83 units at the process temperature of 533 K, pressure 5 MPa; the amount of hydrogen 1000 Nm3 / m3 and a volumetric rate of 0.7 m3 / m3h allows you to obtain an oil with a color of 2.5 ASTM and a viscosity index of 86 units, and at the process temperature of 573 K with other parameters unchanged, it allows you to obtain an oil with a color of 1.9 ASTM and a viscosity index of 92 units and at a temperature of 593 K it allows to obtain an oil with a color of 1.5 ASTM and a viscosity index of 96 units. Example 11 0.150 kg of alpha - Fe2O3, granulation 2.3X10 ~ 3m, are treated with 2% aqueous solution of hydrochloric acid and left for 30 minutes. Then, 1 kg of hydrated alumina, granulation 2.3 × 10 "3 m, is introduced and the paste is made into cylinders, and then proceeds as in Example I. This catalyst contains 13% Fe2O3 with the balance hydrated alumina. This catalyst, used for the mild hydrotreatment of selectively refined and dewaxed lubricating oil, ASTM color 5 and viscosity index 83 units, at the process temperature of 573 K, pressure 5 MPa, hydrogen quantity 1000 Nm3 / m3 \ volumetric speed 0.7 m3 / m3h allows to obtain oil with ASTM color 2 and a viscosity index of 90 units. Claims 1. A method for the preparation of a catalyst for the hydrotreating of lubricating oils, especially under mild conditions, consisting in the introduction of active gamma-Fe, preferably with stabilizers, onto an alumina carrier optionally containing up to 5% silicon oxide in peptizing medium, drying and calcination, characterized in that 0.5-6% aqueous hydrochloric acid solution is used as peptizing medium, preferably containing 0.01-2% nitric acid, as gamma-Fe stabilizers ^ ammonium molybdate or ammonium molybdate and acid ammonium fluoride or ammonium molybdate and nickel nitrate or nitrate are used magnesium or magnesium nitrate and ammonium molybdate or magnesium nitrate and chromium nitrate, the ammonium molybdate being introduced in such an amount that in the finished catalyst the amount of molybdenum trioxide is 1-4% by weight, while ammonium molybdate and acid ammonium fluoride are introduced in such an amount, that in the finished catalyst the amount of molybdenum trioxide is 1-4% by weight, and the amount of acid ammonium fluoride is 0.2-9% by weight, and ammonium molybdate and nickel nitrate are introduced in such an amount that in the finished catalyst the amount of molybdenum trioxide is 1 4% by weight, and the amount of nickel oxide 1-6% by weight, and the amount of magnesium nitrate V) 6 139785 (add such an amount that in the finished catalyst the amount of magnesium oxide is 1-10% by weight, and magnesium nitrate and ammonium molybdate are added such an amount that in the finished catalyst the amount of molybdenum trioxide is 1-4% by weight, and the amount of magnesium oxide is 1-10% by weight, while magnesium nitrate and chromium nitrate are introduced in such an amount that in the finished catalyst the amount of magnesium oxide is 1-10% by weight and the amount of chromium oxide is 1-7% by weight. 2. A method for the preparation of a catalyst for the hydrotreatment of lubricating oils, especially under mild conditions, consisting in introducing alpha-FejOjnanocarb in the form of alumina, possibly containing up to 5% of silicon oxide in a peptizing medium, drying and calcination, characterized in that it is used as a peptizing agent 0.5-6% aqueous hydrochloric acid solution, preferably containing an admixture of 0.01-1.5% nitric acid. Pottgnflcznt UP PRL Laboratory. Mintage 100 eg * Price PLN 130 PL

Claims (2)

Zastrzezenia patentowe 1. Sposób otrzymywania katalizatora do hydrorafinacji olejów smarowych, zwlaszcza prze¬ biegajacej w lagodnych warunkach, polegajacy na wprowadzeniu aktywnego gamma — Fe^, korzystnie ze stabilizatorami, na nosnik w postaci tlenku glinu ewentualnie zawierajacy do 5% tlenku krzemu, w osrodku peptyzujacym, suszeniu i prazeniu, znamienny tym, ze jako osrodek peptyzujacy stosuje sie 0,5-6% wodny roztwór kwasu solnego korzystnie zawierajacy domieszke 0,01-2% kwasu azotowego, ajako stabilizatory gamma — Fe^stosuje sie molibdenian amonu lub molibdenian amonu i kwasny fluorek amonu lub molibdenian amonu i azotan niklu lub azotan magnezu lub azotan magnezu i molibdenian amonu lub azotan magnezu i azotan chromu przy czym molibdenian amonu wprowadza sie w takiej ilosci, aby w gotowym katalizatorze ilosc trójtlenku molibdenu wynosila 1-4% wagowych, zas molibdenian amonu i kwasny fluorek amonu wprowadza sie w takiej ilosci, aby w gotowym katalizatorze ilosc trójtlenku molibdenu wynosila 1-4% wagowych, a ilosc kwasnego fluorku amonu w7nosila 0,2-9% wagowych, zas molibdenian amonu i azotan niklu wprowadza sie w takiej ilosci, aby w gotowym katalizatorze ilosc trójtlenku molibdenu wynosila 1-4% wagowych, a ilosc tlenku niklu 1-6% wagowych, zas azotan magnezut V ) 6 139785 ( wprowadza sie w takiej ilosci, aby w gotowym katalizatorze ilosc tlenku magnezu wynosila 1-10% wagowych, zas azotan magnezu i molibdenian amonu wprowadza sie takiej ilosci, aby w gotowym katalizatorze ilosc trójtlenku molibdenu wynosila 1-4% wagowych, a ilosc tlenku magnezu wynosila 1-10% wagowych, natomiast azotan magnezu i azotan chromu wprowadza sie w takiej ilosci, aby w gotowym katalizatorze ilosc tlenku magnezu wynosila 1-10% wagowych a ilosc tlenku chromu wynosila 1-7% wagowych.Claims 1. A method for the preparation of a catalyst for the hydrotreatment of lubricating oils, especially under mild conditions, consisting in the introduction of active gamma-Fe, preferably with stabilizers, onto an alumina carrier, possibly containing up to 5% silicon oxide, in a peptizing agent , drying and calcination, characterized in that 0.5-6% aqueous hydrochloric acid solution preferably containing 0.01-2% nitric acid is used as peptizing agent, and ammonium molybdate or ammonium molybdate are used as gamma-Fe-stabilizers, and acid ammonium fluoride or ammonium molybdate and nickel nitrate or magnesium nitrate or magnesium nitrate and ammonium molybdate or magnesium nitrate and chromium nitrate, with ammonium molybdate being introduced in such an amount that in the finished catalyst the amount of molybdenum trioxide is 1-4% by weight, and molybdate ammonium and acid ammonium fluoride are introduced in such an amount that in the finished catalyst the amount of molybdenum trioxide u was 1-4% by weight, and the amount of acid ammonium fluoride was 0.2-9% by weight, while ammonium molybdate and nickel nitrate were added in such an amount that in the finished catalyst the amount of molybdenum trioxide was 1-4% by weight, and the amount nickel oxide 1-6% by weight, and magnesium nitrate V) 6 139785 (introduced in such an amount that in the finished catalyst the amount of magnesium oxide is 1-10% by weight, and magnesium nitrate and ammonium molybdate are introduced in such an amount that in the finished catalyst In the catalyst, the amount of molybdenum trioxide was 1-4% by weight, and the amount of magnesium oxide was 1-10% by weight, while magnesium nitrate and chromium nitrate were added in such an amount that in the finished catalyst the amount of magnesium oxide was 1-10% by weight and the amount of oxide chromium was 1-7% by weight. 2. Sposób otrzymywania katalizatora do hydrorafinacji olejów smarowych zwlaszcza prze¬ biegajacej w lagodnych warunkach, polegajacy na wprowadzeniu alfa — FejOjnanosnik w postaci tlenku glinu ewentualnie zawierajacy do 5% tlenku krzemu w osrodku peptyzujacym, suszeniu i prazeniu, znamienny tym, ze jako osrodek peptyzujacy stosuje sie 0,5-6% wodny roztwór kwasu solnego korzystnie zawierajacy domieszke 0,01-1,5% kwasu azotowego. Pracownia Pottgnflcznt UP PRL. Naklad 100 eg*. Cena 130 zl PL2. A method for the preparation of a catalyst for the hydrotreatment of lubricating oils, especially under mild conditions, consisting in the introduction of alpha-FejOjnanocarb in the form of alumina, possibly containing up to 5% of silicon oxide in the peptizing medium, drying and calcination, characterized in that it is used as a peptizing agent 0.5-6% aqueous hydrochloric acid is preferably admixed with 0.01-1.5% nitric acid. Pottgnflcznt UP PRL studio. Mintage 100 eg *. Price PLN 130 PL
PL24559784A 1984-01-03 1984-01-03 Method of obtaining a catalyst for hydrorefining of lubricating oils in particular for refining processes being carried out under mild conditions PL139785B1 (en)

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PL24559784A PL139785B1 (en) 1984-01-03 1984-01-03 Method of obtaining a catalyst for hydrorefining of lubricating oils in particular for refining processes being carried out under mild conditions
GB08500073A GB2152402B (en) 1984-01-03 1985-01-03 Method of obtaining catalyst for hydrorefining of lubricating oils, particularly in mild conditions
FR8500048A FR2557476B1 (en) 1984-01-03 1985-01-03 PROCESS FOR OBTAINING A CATALYST FOR HYDROREFINING OF LUBRICATING OILS, PARTICULARLY IN MODERATE CONDITIONS, AND METHOD FOR MODERN CATALYTIC HYDRORINFINING OF LUBRICATING OILS
GB08722073A GB2194462B (en) 1984-01-03 1987-09-18 Hydrorefining lubricating oils

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US4729980A (en) * 1987-04-27 1988-03-08 Intevep, S.A. Catalyst for the simultaneous hydrodemetallization and hydroconversion of heavy hydrocarbon feedstocks and process for preparing the catalyst
US7491278B2 (en) 2004-10-05 2009-02-17 Aleris Aluminum Koblenz Gmbh Method of heat treating an aluminium alloy member and apparatus therefor
FR2937045B1 (en) * 2008-10-10 2012-11-30 Inst Francais Du Petrole USE OF ZINC FERRITE-BASED SOLIDS IN A PROCESS FOR THE DEEP DEULFURIZATION OF OXYGENIC LOADS

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FR1195544A (en) * 1958-05-02 1959-11-18 British Petroleum Co Process for the treatment of lubricating mineral oils by controlled hydrogenation and catalyst for this process
US3661805A (en) * 1969-11-21 1972-05-09 Universal Oil Prod Co Method of manufacturing an extruded catalyst composition
US3919404A (en) * 1974-06-28 1975-11-11 Dow Chemical Co Hydrothermal process for preparation of alpha iron oxide crystals
US3965045A (en) * 1975-02-20 1976-06-22 Continental Oil Company Iron catalyst
IT1134538B (en) * 1980-12-02 1986-08-13 Euteco Impianti Spa PROCEDURE FOR THE PREPARATION OF CATALYSTS SUITABLE FOR THE PRODUCTION OF FORMALDEHYDE FROM METHANOL

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GB2194462B (en) 1988-12-14
PL245597A1 (en) 1985-07-16
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FR2557476A1 (en) 1985-07-05
GB2152402B (en) 1988-12-14

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