Odzysk metali ze zużytych katalizatorów uwodorniania stosowanych w przemyśle petrochemicznym

• Autorzy: Mulak W. , Szymczycha-Madeja A. , Miazga B.

Warianty tytułu

EN

Metals recivery from spent hydroprocessing catalysts used in the petrochemical industry

• Języki publikacji: PL

Abstrakty

PL

Przedstawiono przegląd wyników badań nad odzyskiem metali ze zużytych katalizatorów uwodorniania stosowanych w procesach rafineryjnych. Uwagę skoncentrowano na procesach hydropirometalurgicznych i hydrometalurgicznych z uwzględnieniem bioługowania, ługowania elektrochemicznego oraz ługowania w mediach w stanie nadkrytycznym. W procesach hydropirometalurgicznych etap ługowania poprzedzony jest prażeniem chlorującym (z CI2, NaCl, NH4CI), kalcynującym (Na2CO3 lub Na2O), lub wypalaniem zużytego katalizatora. Wykazano, że prażenie chlorujące w mieszaninie CI2 + N2 + CO jest wysoce efektywne i pozwala na odzysk metali z katalizatora w ilości: 99 % Mo, 74 % V, 75 % Co oraz 85 % Ni. W przypadku Mo porównywalne wyniki (97 %) można otrzymać stosując kalcynację z dodatkiem Na2COj w 450 °C i czasie 2 godzin i następnie ługowanie NaOH. W procesach hydrometalurgicznych do ługowania stosuje się szereg reagentów nieorganicznych i organicznych lub ich kombinacji. Stosowano takie reagenty, jak: NaOH, Na2CO3, H2SO4, NH3xH2O, H2C2O4 z dodatkiem utleniaczy (Fe3+, H2O2). Najwyższe stopnie wyługowania Mo (90 %) i V (94 %) uzyskano w roztworze 0,5 M H2C2O4 z dodatkiem 3,0 M H2O2 w czasie 4 godzin, w temperaturze 50 °C. Przedstawiono także wyniki lugowań ciśnieniowych w roztworach kwaśnych i alkalicznych. W omówionych procesach bioługowania zużytych katalizatorów stosowano grzyby Aspergillus niger w 2,0 M roztworze H2C2O4 w czasie 30 dni, uzyskano w roztworze 82,3 % Mo, 78,5 % Ni oraz 65,2 % Al. Metoda elektrochemicznego roztwarzania zużytych katalizatorów w przestrzeni anodowej elektrolizera z użyciem jonów Ce4+ jako utleniacza pozwala na całkowite roztworzenie zużytego katalizatora w roztworze zawierającym 0,5 M jonów Ce4+ w 2,0 M HNO3 w temperaturze 110 °C w czasie 14 godzin.

EN

Recycling of spent catalysts has become recently an unavoidable task not only due to catalysts costs but also in order to prevent the environmental pollution. The results of studies on the recovery of metals from spent hydroprocessing catalysts used in the refinery processes have been reviewed. The following processes have been discussed: hydropyrometallurgical, hydrometallurgical, biohydrometallurgical, leaching by supercritical media, as well as electrochemicał dissolution. The hydropyrometallurgical processes reąuire pretreatment of roasting with CI2, NaCl and NH4Cl, calcination with Na2CO3 and Na2O or combustion of spent catalysts followed by water leaching. Generally, chlorination has disadvantages sińce it is connected with corrosion and gas handling problems. It was found that the chlorination with CI2+N2+CO turns to be highly effective and leads to recovery of 99 % Mo, 74 %V, 75 % Co, and 85 % Ni. The comparable results of Mo leaching (97 %) were achieved using the calcination with Na2CO3 at temperaturę 450 °C during 2 hours followed by NaOH leaching. In turn, the hydrometallurgical processes involve leaching with inorganic and organie agents or their combustion. Many reagents such as: NaOH, Na2CO3, H2SO4, NH3xH2O, H2C2O4 in the presence of oxidizing agents (Fe3+, H2O2) were tested. The most promising results have been achieved for the chelating agents being able to form soluble metal complexes. The highest leaching efficiency of Mo (90 %) and V (94 %) were reached after 4 hours leaching in the solution containing 0.5 M H2C2O4 and 3.0 M H2O2- The alkali and acid leaching processes under high pressure have been also presented. Comparing to the conventional techniąues the biohydrometallurgical methods seem to be more attractive for the recovery of metals from spent catalysts. In fact they are simpler, cheaper and more environmentally friendly. In bioleaching one of the most widely used fungus is Aspergillus niger. Its application has advantages over bacterial leaching sińce this particularfungus reveals the ability of metal leaching under higher pH conditions and gives thefaster leaching rate. Bioleaching results of the spent refinery catalysts with Aspergillus niger fungus in 0.2 M H2C2O4 solution showed that 82.3 % Mo, 78.5 % Ni and 65.2 % Al were extracted after 30 days. Another techniąue is the supercritical fluid extraction may provide a clean and efficient method for removing metal species from contaminated solid materials. Conceptually, such a process would entail loading a spent catalyst into a pressure vessel and leaching it with supercritical CO2 containing 5 % methanol and a smali ąuantity ofa chelating reagent. In particularly, the recovery o noble metals from spent catalysts is possible by supercritical water leaching at 400 °C and 250 atm (Aqua Cat process). Finally, the results of experiments investigating the electrochemical dissolution showed that 0.5 M Ce4+ solution as an oxidant in 2.0 M HNO3 at 110 °C would completely dissolve a spent hydrosulphurization catalyst (HDS) in 14 hours.

Słowa kluczowe

PL

odzysk metali; zużyte katalizatory uwodorniania; ługowanie chemiczne; bioługowanie; elektrochemiczne roztwarzanie

EN

metals recovery spent hydroprocessing catalysts; chemical leaching; electrochemical dissolution

• Wydawca: Wydawnictwo SIGMA-NOT
• Czasopismo: Rudy i Metale Nieżelazne
• Rocznik: 2007
• Tom: R. 52, nr 8
• Strony: 482--490
• Opis fizyczny: Bibliogr. 45 poz., tab., wykr., rys.

Twórcy

autor

Mulak W.

autor

Szymczycha-Madeja A.

autor

Miazga B.

• Politechnika Wrocławska, Wydział Chemiczny, Wrocław

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