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Dr. Sanna Airaksinen Aalto University School of Science and Technology
• What is a catalyst • Preparation methods for supports and bulk catalysts • Preparation methods for supported catalysts • More information from e.g. Handbook in Heterogeneous Catalysis, Ed. Ertl, Knözinger, Schüth, Weitkamp, 2nd edition, vol 2.
What is a catalyst?
• Catalysts are substances that increase the reaction rate by which a chemical system approaches equilibrium without changing or being used up themselves in the process
Figure: Puurunen (2002)
What is a catalyst?
A catalyst 1. Increases the chemical reaction rate (kinetic effect) 2. Does not influence the thermodynamic equilibrium of a chemical reaction 3. Does not change in a chemical reaction
Ammonia synthesis .
Classes of catalysis • Heterogeneous catalysis • Homogeneous catalysis • Photocatalysis • Enzymatic catalysis .
Solid catalysts • Bulk catalysts • Supported catalysts – Support – Active component – Promoter(s) Different catalysts from Süd Chemie .
4 <2 4. SiO2 Alumina.5 Silica. m2/g 450 220 Pore Mean pore volume.72 0.67 0.90 2.Properties of catalyst supports Support Surface area. nm cm3/g 0. Al2O3 Activated carbon 1040 Aluminium silicate 380 .2 5. diameter.71 0.
Preparation of supports and bulk catalysts • Precipitation and co-precipitation – Alumina • Sol-gel synthesis – Silica • Zeolite synthesis • Preparation of skeletal metal catalysts • Other methods also available .
evaporation) or chemically (adding precipitating agent. metal hydroxide [Aging. base) Precipitate e. filtering Filter cake Dry precursor Shaping Preformed precursor Calcination Catalyst/support Calcination Active phase Shaping Catalyst/support .g.g. modification]. modification].Precipitation and coprecipitation [Aging. spraydrying Supersaturated metal salt solution Precipitation physically (e.
isomerization) – SiO2: support – Sn-Sb-oxides: catalyst in selective oxidation (e. catalyst (e.g. isobutene to methacrolein) .Precipitation and coprecipitation • Precipitation – Very pure materials can be obtained – Product needs to be separated from the solution • Coprecipitation – Simultanous precipitation of more than one component – Homogeneous distribution of catalyst components – Difficult to follow product quality during precipitation • Examples – Al2O3 (mostly γ): support.g.
Preparation of alumina by precipitation • Reactants in salt solutions – Aluminium sulphate and ammonium hydroxide – Precipitation and crystallization of Al(OH)3 (pH. high pH → bayerite (Al(OH)3) • Lower pH → pseudoboehmite → boehmite (AlOOH) • Hydrolysis of aluminum alcoholates – Al(OR)3 + (2+x)H2O → 3ROH + AlOOH· xH2O – High-purity pseudoboehmite obtained • Drying • Calcination . T.. time) • pH 7.12 • Elevated T.
Calcination of alumina SA<5 m2/g SA=200-300 m2/g .
gov/str/May05/Satcher.Sol-gel synthesis • • • • • • • Precursor in dissolved state → pH adjustment Conversion (activation) of dissolved precursor to the reactive state Polycondensation of activated molecular precursors into nanoclusters (micelles) → colloidal solution.llnl.html . the sol Gelation Aging → hydrogel Washing Drying → xerogel (evaporation) or aerogel (autoclave) Stabilization • https://www.
6-3. by stirring a precipitate is formed) . SiO2:Na2O=1.9 – Preparation methods quite similar – Precipitation at neutral or alkaline solution – Sol-gel process at acidic solution → real gel is formed (if gel formation is prevented e.Preparation of silica • Can be prepared by – Sol-gel process (silica gel) – Precipitation (precipitated silica) – Flame hydrolysis (fumed silica) • Sol-gel process and precipitation – Starting material sodium silicate (waterglass).g.
pelletization or extrudation) Silica particles .grace.Preparation of silica gel Sodium silicate solution pH adjustment with H2SO4 Silicic acid → polycondensation products → colloidal silica particles (sol) Agglomeration of colloidal silica Colloidal silica www.com Hydrogel Washing Drying (evaporation) Xerogel Formulation (e.g.
0 nm . 0.3-2. pore size = molecule size.Zeolites • Crystalline aluminiumsilicate – M2/nO · Al2O3 · x SiO2 · y H2O Linde Type A (LTA) Zéo boiling Líthos stone • Molecular sieve Faujacite (FAU) • Porous material.
drying and calcination Zeolite Starting materials and synthesis conditions (T. aluminate salts. pseudoboehmite. washing.Hydrothermal zeolite synthesis Si source Al source Base Templating agent . metal powder . quaternary ammonium hydroxide etc. pH) depend on the wanted zeolite (Si/Al ratio) . pyrogenic silica..Si source: colloidal silica. .. waterglass. p.Template/structure-directing agent (SDA): cationic or neutral organic molecules Reaction mixture Low T (<60° C) Synthesis gel T increased to crystallization T (~100.200° C) Silicate and aluminate monomers and oligomers in solution in equilibrium with condensed silicate and aluminate units in the gel phase Zeolite crystallization After induction period Separation. aluminum alkoxides.Base (pH 9.12): alkali metal hydroxide.Al source: gibbsite. silicon alkoxides .
ZEOLITE PLANT (1/2) Sodium Aluminium Sulphate ML-Gel Silicate Sodium Aluminate Seeds Water RECl3 / Beltfilter Aluminium Sulphate Beltfilter NH4-Y / RE-Y Zeolite Beltfilter Effluent Effluent (NH4)2SO4 Na-Y Zeolite Water .
ZEOLITE PLANT (2/2) Bag Filter System Dryer NH4-Y / RE-Y Zeolite Calciner Hot Air CREY / US-Y Zeolite .
org/wiki/File:Dry_Raney_nickel. Cu) • Metal forms an alloy with Al → Al is leached with NaOH → porous metal with high surface area • Used in selective hydrogenation reactions in liquid phase slurry reactors Dry Raney nickel Picture: http://commons.Skeletal metal catalysts • Raney metals: active porous metals – Ni (Fe.wikimedia. Co.jpg .
Supported catalysts • Support • Active component • Promoter(s) .
Pt Pd. hydrogenolysis Isomerization. dehydration Catalyst Fe. ZnO. CuO Cr2O3. Ag NiO. Cu. SiO2. MoS2 Al2O3. Ni. cracking. zeolites SiO2-Al2O3 .Examples of active components of catalysts Active component Metals Semiconductive oxides and sulfides Insulating oxides Reaction hydrogenation hydrogenolysis Selective hydrogenation.
B .Examples of promoters Catalyst Al2O3 Promoter SiO2. Co P. ZrO. P K2O HCl MgO Pt Re ion Pt Re Function Increases thermal stability Prevents coking Increases acidity Prevents sintering of active sites Enhances oxidation of CO Increases acidity and thermal stability Enhances hydrogenation Decreases hydrogenolysis and sintering Enhances C–S and C–N hydrogenolysis Improves dispersion of MoO3 SiO2-Al2O3 Zeolites Pt/Al2O3 MoO3/Al2O3 Ni.
Preparation of supported catalysts • Selection of support • Pretreatment of support • Selection of method to add the active material on the support • Selection of precursor material to produce the active component • Drying • Calcination • Activation .
g. If reactor price determines ⇒ maximize active surface area per volume unit of the catalyst 2. noble metal catalysts) ⇒ maximize active surface area per weight unit of the active phase .Preparation of supported catalysts 1. If catalyst price determines (e.
Methods to deposit the active component • • • • • Deposition-precipitation Impregnation Adsorption Ion exchange CVD / ALD (chemical vapour deposition / atomic layer deposition) .
Deposition-precipitation (1) • Metal hydroxide/carbonate is precipitated on the support surface from metal salt solution when pH is increased Support powder particles Metal hydroxide or carbonate on support Calcination (activation) (shaping) Metal salt solution oxalate nitrate sulfate chloride + Base NaOH KOH NH4OH Na2CO3 etc. small particles Generally used to obtain high loadings with good dispersion Also: low loadings of very small particles of e. not in the bulk of solution Homogeneous distribution of active component. Catalyst • • • • • Support in powder form Rapid mixing essential: nucleation on the surface of the support.g. noble metals .
Deposition-precipitation (2) • Using urea as the OH. etc.source instead of base → better control over uniform precipitation Metal salt solution with urea mixed with support powder T increased to 70-90° C Urea hydrolyzes to form OHPrecursor-support interaction → nucleation at support surface at lower concentration than in the bulk Metal hydroxide precipitates Filtering. drying. washing. on the support .
overnight Drying. e.Impregnation (1) • Incipient wetness/ dry/pore volume impregnation Calcined and dried support Solution with active phase precursor Impregnation Aging.g. calcination. hydrogenation with metal catalysts) – Precursor in salt solution. amount of solution equal to or slightly lower than the pore volume of the support • Wet impregnation – Amount of solution higher than the pore volume .g. activation (e.
Impregnation (2) • Pre-shaped support bodies and powdered supports can both be used • Waste water is not produced • Active phase precursors are not lost • Several impregnation steps might be needed to obtain high loadings (precursor solubility) • Drying important → can result in uneven distribution if not done properly .
+ A.↔ SA.Adsorption • Support material in metal salt solution adsorbs salt ions – Support dehydrated and soaked in the appropriate solution for a suitable time – Cations and anions in the solution react with support surface groups depending on surface properties SOH+ + C+ ↔ SOC+ + H+ S(OH).+ (OH)- • Good method for depositing small amounts – Higher loadings usually require multiple adsorption steps • Results in uniform deposition .
SNa+ + Ni2+ ↔ SNi2+ + Na+ • Useful in removing harmful agents and adding promoters • Zeolites . e.Ion exchange • Similar to adsorption • Lower valency ions exchange with ions having higher charge.g.
Catalyst preparation by Atomic Layer Deposition (ALD) • Materials growth technique allowing coating of complex shapes with a high quality material layer (thin films) • Surface controlled process • Surface saturating gas–solid reaction (chemisorption) .
Catalyst preparation by Atomic Layer Deposition (ALD) • In catalyst preparation – Solid surface is the surface of the catalyst support – Gaseous reactant is a precursor for catalytically active sites • Highly dispersed and active supported metal and oxide catalysts prepared • Tailored support/catalyst modification possible • No waste water formed during the preparation .
HUT 2002 . Doctoral Thesis.Puurunen.
) . PhD Thesis 2002) – ZrO2/Al2O3 (Kytökivi et al. A 351 (2008) 9-15.) • Preparation of catalysts – CrOx/Al2O3 (Hakuli. PhD Thesis 1999) – Pt and Ru on carbon fibres (Plomp et al.. Appl.Catalyst preparation by Atomic Layer Deposition (ALD) • Preparation of modified supports – AlN/Al2O3 (Puurunen. Langmuir 13 (1997) 2717–2725. Catal.
Preparation of chromia/alumina by ALD • Chromia/alumina used in dehydrogenation of propane and isobutane • Chromia ALD precursor Cr(acac)3 Ligand removal. calcination Cr6+ (mono.and/or polychromates) Cr3+ (isolated Cr3+ . Cr2O3) . cryst. amorphous Cr2O3.
Preparation of chromia/alumina by ALD .
Catalyst calcination and activation • Calcination – Salt is converted to oxide – Surface stabilized • Activation – Metals: hydrogenation • Deposited oxide converted to the metal – Sulfides: sulfidation • CoMo and NiMo used in HDS .
Catalyst preparation process .
Catalyst particles .
2nd edition. Schüth. Ertl. van Leeuwen. van Santen. Plenum Press. New York. • Handbook of Heterogenous Catalysis. vol 2. Knözinger. Ed. Weitkamp. Ed. Principles of Catalyst Development. Moulijn. Averill. • Catalysis: An Integrated Approach.Literature • James Richardson. 2nd edition . 1989.
neutral.Properties of supports • Support surface groups important – Interact with the active-phase precursors – Hydroxyl groups (acidic. basic) – Coordinatively unsaturated metal sites (Lewis acids) • E.g. alumina .
or M-OH+H2O ↔ [M-OH2]+ + OH– M-OH + OH.+ H2O • pzc = point of zero charge = pH at which the surface charge is zero • Effect of solution pH – pH>pzc: support surface negatively charged → will attract cations – pH<pzc: support surface positively charged → will attract anions .Properties of supports • Surface OH groups are in equilibrium with the solution depending on solution pH → surface may be charged – M-OH + H+ ↔ [M-OH2]+.↔M-O.
MoO4(2-) molecules present: no interaction with basic alumina OH groups initially (pH>pcz) – With drying: ammonia released.u. pH inside the pores drops. HM ions formed: 7 MoO4(2-) + 4H2O ↔ Mo7O24(6-) + 8 OH– The HM ions formed react with surface groups (mainly reaction (2)) .Preparation of MoO3/Al2O3 by impregnation • • Disproportionation (metathesis) catalyst Impregnation of γ-Al2O3 with – an aqueous solution of ammonium heptamolybdate (AHM) or – ammoniacal solution of ammonium dimolybdate (ADM) • With AHM – (1) HM ions react with most basic OH groups: Mo7O24 (6-) +8 Al-OH -> 4 (Al)2MoO4 + 3 MoO4(2-) + 4 H2O – (2) physisorption of AHM on c.s. Al sites • With ADM – Solution basic.
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