Traditional methods used for catalyst synthesis:

Precipitation, co-precipitation, ion exchange.

University of Antioquia
Environmental catalysis Group
Present by: Tania M. Chanagá
Professors: PhD Aída L Villa & PhD Lina M Gonzalez
February 25, 2015
1
 OUTLINE

• Introduction
• Precipitation and co-precipitation methods
• Deposition-precipitation method
• Impregnation method
• Ion exchange

2
 INTRODUCTION

An heterogeneous catalyst is a composite material, characterized by:

• the relative amounts of different components (active species, physical
and/or chemical promoters, and supports);
• shape;
• size;
• pore volume and distribution;
• surface area.

3
 INTRODUCTION

The optimum catalyst is the one that provides the necessary combination of
properties (activity, selectivity, lifetime, ease of regeneration and toxicity) at an
acceptable cost.
Handbook of heterogeneous catalysts. 4
 INTRODUCTION

Over 80% of the industrial

catalysts are prepared by
(co)precipitation and
impregnation techniques. Due:
• These methods are simpler
• More reproducible
• Easier to scale-up
• More economical than others

5
Designs of heterogeneous catalysts for fuels and chemicals processing: An overview.
 PRECIPITATION AND
CO-PRECIPITATION
Precipitation
• is mainly used for the production of oxidic catalysts and also for the manufacture of
pure support materials (supported and Bulk catalysts).- Ex: aluminum and silicon
oxides, iron oxides, titanium oxides or zirconias.
• Is the process in which the solid formation can be induced by addition of an agent
which initiates a chemical reaction or which reduce the solubility. (favorable ions are
nitrates, carbonates or ammonium, which decompose to volatile products during
calcination).
• Very pure materials can be obtained.
• Product needs to be separated from the solution.
• Generate a large volumes of salt-containing solutions

6
 PRECIPITATION AND
CO-PRECIPITATION
Co-Precipitation

• Simultaneous precipitation of more than one component, (ex: Ni/Al2O3, Cu/Al2O3,

Cu/ZnO/Al2O3 and SN-Sb oxides.
• Homogeneous distribution of catalyst components
• Difficult to follow product quality during precipitation

7
PRECIPITATION AND
CO-PRECIPITATION

• One or more components in

the form of aqueous
solutions are mixed and then
coprecipitated as hydroxides
or carbonates.

• An amorphous or crystalline
precipiate or a gel is
obtained, wich is washed
(until salt free).

Industrial Catalysis. Hagen. 8

 PRECIPITATION AND
CO-PRECIPITATION
The precipitate is the precursor of the catalyst or the final support. Precipitation generally leads to one of
two distinct precursor products:

Lyophobic crystallized precipitates

• Organized particles without significant porosity
and often containing attached molecules (H2O,
NH3).
• Dimensions on the order of a micron to some
tens of microns, and with very small specific
Clusters of hydrated
surfaces. aluminium oxide cristals.
• Take form from a super-saturated solution in
two steps: nucleation and growth.

Applied heterogeneous catalysis. J.F. Le Page.

 PRECIPITATION AND
CO-PRECIPITATION
The precipitate is the precursor of the catalyst or the final support. Precipitation generally leads to one of
two distinct precursor products:

Lyophilic precipitates in the form of gels

• Amorphous or very poorly organized

• Hydrogels and floculates result from a sol formed
of micelles that remain separated.
• The gelation route (sol–gel method) is a
homogeneous process which results in a
continuous transformation of a solution into a
hydrated solid precursor (hydrogel).

Applied heterogeneous catalysis. J.F. Le Page.

 PRECIPITATION AND
CO-PRECIPITATION
Precipitation occurs in three steps: supersaturation, nucleation
and growth.

In the supersaturation region (metastable) the system is

unstable and precipitation occurs with any small perturbation.

The supersaturation region can be approached either by:

• Increasing the concentration through solvent evaporation (A
to C),
• lowering the temperature (A to B) or
• increasing the pH (which moves the solubility curve to D and
A into the supersaturation region). (Adding a Base )
Solubility curve (function of T and pH)
Fundamentals in the preparation of
heterogeneous 11catalysts.
 PRECIPITATION AND
CO-PRECIPITATION
Formation of the solid phase occurs in two elementary steps: (i) nucleation, formation
of the smallest elementary particles of the new phase which are stable under the
precipitation conditions, and (ii) growth or agglomeration of the particles.
Nucleation:
• Corresponds to the appearance of solid seed crystal in the mother liquor, can be
homogeneous and heterogeneous.
Homogeneous nucleation (spontaneously): the seeds are formed from a pure solution
through an interaction between ions or molecules that starts an irreversible
crystallization by forming aglomerates.
Heterogeneous nucleation: the seeds was formed by the contact with any solid that
can lower the energy barrier enough for their formation. (solid can be: an impurity, the
wall, the aparatus or an added product seed).
 PRECIPITATION AND
CO-PRECIPITATION

• The dimension of the crystals depends on the ratio of speeds of nucleation to crystal
growth, the greater this ratio the smaller the crystals but in hight quantity. In this
condition amorphous precipitates can be obtained.

• If crystals are allowed time in contact with the mother solution, the system tends to
evolve toward its most stable thermodynamics state, the small crystals disappear in
favor of large crystals.
 PRECIPITATION AND
CO-PRECIPITATION
Basically, all process parameters influence the quality of the final precipitates, and fine tuning of the
parameters is necessary in order*pH
to produce the required
directly controls the material. *Time for which precipitate
degree of supersaturation. is left in the mother liquor
*When are ions which under precipitation
can be occluded conditions.
repeated washings steps
are necessary. *Most frequently additives
are organic molecules
(pores).
*Precursors are usually
*As nucleation rates are
chosen for the easily to
extremely sensitive to
volatile products.
temperature changes (affect
crystallite sizes, areas, and
phases)
*The concentration and *The use of organic solvents
composition impact the (more expensive than
supersaturation and water), can be good due low
affects the dimension of solubilities of the precursor
the crystals. (low crystallization )
14
Fundamentals in the preparation of heterogeneous catalysts.
PRECIPITATION AND
CO-PRECIPITATION

Handbook of heterogeneous catalysts. 15

 PRECIPITATION AND
CO-PRECIPITATION
EXAMPLE:

16
 PRECIPITATION AND
CO-PRECIPITATION
EXAMPLE:

• The CuO–ZrO2–CeO2–Al2O3
catalysts for production of
hydrogen via methanol steam
reforming were prepared by
the homogeneous precipitation
method using urea hydrolysis.

17
 PRECIPITATION AND
CO-PRECIPITATION
EXAMPLE:
• Catalytic performance tests proved the good practicability and high
stability of synthesized catalysts via the homogeneous precipitation
method for steam reforming of methanol.

The ceria containing catalyst was the best among

samples. The CuO–CeO2– Al2O3 (CCA) catalyst
had better methanol conversion with low CO
production.

The stability test showed that this catalyst was

quite stable for steam reforming of methanol.

18
 DEPOSITION-
PRECIPITATION
Supported catalysts
The method of deposition-precipitation is a modification of the precipitation methods
in solution. It consists of the conversion of a highly soluble metal precursor into
another substance of lower solubility, which specifically precipitates onto a support
and not in solution.

Handbook of heterogeneous catalysts. 19

 DEPOSITION-
PRECIPITATION
Supported catalysts

The precipitation occurs when:

• increase the pH of the solution.
• can also be done by decreasing the pH, or
• changing the valence state of the metal precursor through electrochemical reactions
• using a reducing agent, or
• changing the concentration of a complexing agent

20
 DEPOSITION-
PRECIPITATION
Supported catalysts
Depending upon of the active component, two different types of supported catalyst may
be distinguished.

1. Active component expense (precious metals), the objective is a maximum active

surface area per unit weight of the active component.

Handbook of heterogeneous catalysts. 21

 DEPOSITION-
PRECIPITATION
Supported catalysts

2. With less costly active components (base metal oxides or sulfides), a maximum active surface area per unit
volume is most attractive

A high active surface area causes a relatively small catalytic reactor volume to be sufficient to achieve a
technically satisfactory conversion.
• When the cost of the reactor dominate, is most favorable that the support maximize the active surface
area per unit volume.
• When the costs of the active component are most important, the maximum active surface area per
unit weight of active component is desired.
Handbook of heterogeneous catalysts. 22
 DEPOSITION-
PRECIPITATION
Supported catalysts
CHARACTERISTICS

• Support in powder form.

• Rapid mixing essential: nucleation on the surface of the support, not in the bulk of
solution.
• Homogeneous distribution of active component, small particles.
• The precipitation is the preferred deposition route for loading higher than 20%.
Below this value, impregnation is usually practiced

23
 DEPOSITION-
PRECIPITATION
Supported catalysts
• An effective method to obtain a uniform precipitation is to use urea rather than conventional alkalis.
Urea dissolves in water but decomposes very slowly at 90°C giving a uniform concentration of OH- in
the bulk and in the pores. So precipitation takes place homogeneously over the support surface.

Handbook of heterogeneous catalysts. 24

 DEPOSITION-
PRECIPITATION
Supported catalysts
EXAMPLE:

Anatase TiO2DT-51 was used as support material. The Mn/TiO2 catalysts were prepared by two methods:
impregnation and deposition precipitation.

25
 DEPOSITION-
PRECIPITATION
Supported catalysts
EXAMPLE:

The Mn/TiO2catalysts were prepared by slow addition of solutions of precipitating agents(urea (1 M),
ammonium nitrate (1 M), ammonium hydroxide(20 vol.%) and ammonium carbamate (1 M), Aldrich). The water
of the resulting slurry was slowly evaporated with continuous stirring followed by calcination.
This catalyst show a superior low-temperature SCR (selective catalytic reduction) of NO with NH3. The superior
catalytic activity is probably due to the presence of amorphous phases of manganese oxide, iron oxide, high
surface area, high total acidity, acid strength. 26
 DEPOSITION-
PRECIPITATION
Supported catalysts
EXAMPLE:

The 5MnTi catalysts prepared by DP method exhibited

increased NO conversion in the order: ammonium
carbamate > urea > ammonium nitrate > ammonium
hydroxide.

Such a change in SCR (selective catalytic reduction)

activity with different precipitating agents could be due
to anionic effect. (carbonate as an anion showed higher
NOx conversion).

27
 IMPREGNATION

Impregnation.
In the impregnation process, active components with thermally unstable anions (e. g.,
nitrates, acetates, carbonates, hydroxides) are used. The support is immersed in a
solution of the active component under precisely defined conditions (concentration,
mixing, T, t). Depending on the production conditions, selective adsorption of the active
component occurs on the surface or in the interior of the support.

To achieve the best possible impregnation, the air in the pores of the support is removed
by evacuation, or the support is treated with gases such as CO 2 or NH3 prior to
impregnation. After impregnation, the catalyst is dried and calcined.

Two methods of contacting may be distinguished, depending on the volume of solution:

wet impregnation and incipient wetness impregnation.
28
 IMPREGNATION
In wet impregnation an excess of solution is used. After a certain time the solid is
separated and the excess solvent is removed by drying. The composition of the batch
solution will change and the release of debris can form a mud which makes it difficult to
completely use the solution. The heat of adsorption is released in a short time.

29
Applied heterogeneous catalysis. Design, manufacture use of solid catalysts. J.F. Le Page
 IMPREGNATION
In incipient wetness impregnation the precursor salt is dissolved in a volume of solvent
equal to the catalyst pore volume, and this solution is slowly added to the support in
which capillary forces of up to several hundred atmospheres draw the liquid into the
pores.
For large-scale manufacture the incipient wetness impregnation (also called pore
volume, or dry or capillary impregnation) is the most advantageous method.

30
Fundamentals in industrial catalytic processes. Farrauto
 IMPREGNATION
Stages of the preparation of supported catalyst by impregnation.

wet impregnation

incipient wetness impregnation

31
 IMPREGNATION
After impregnation the catalysts are dried, and the metal salts are decomposed to the corresponding
oxides by heating. The rate of drying (determined by T and flow rate of the gas), affects the deposition of
the active material in the pores.

At low rates of drying, If drying is too fast, a

evaporation occurs at the temperature gradient is set up
meniscus, which retreats and vaporization occurs deep in
down the pore; so, most of the the pores, forcing the precursor
precursor is deposited at the deposit to the pore entrances
deepest end of the pore in the and leading to an eggshell
pellet center. deposit in the pellet.

Fundamentals in industrial catalytic processes. Farrauto

32
 IMPREGNATION

ADVANTAGES
• Relative simplicity
• rapidity and
• capability for depositing the
precursor at high metal loading.
• Waste water is not produced
• Active phase precursors are not
lost
Drying important (can result in uneven distribution if not done properly.
DISADVANTAGES
• Sometimes material is nonuniformly
deposited along pores and through
the pellet,
• Tendency for deposited base metal
precursors to be oxidized in the
aqueous solution to oxides that
interact strongly with alumina or
silica supports and which are difficult
to reduce.
• Several impregnation steps might be
needed.
33
 IMPREGNATION VS
PRECIPITATION
EXAMPLE:

Steam reforming is the most effective method to produce hydrogen from liquid hydrocarbons with a high yield.

34
 IMPREGNATION VS
PRECIPITATION
EXAMPLE:
Al2O3 supported Ni–Al spinel catalysts, prepared by co-
precipitation and wet impregnation, were produced, analysed and
tested on commercial diesel steam reforming.

35
 IMPREGNATION VS
PRECIPITATION
EXAMPLE:

Both preparation methods resulted in catalysts showing a metastable ‘NiAl10O16’ phase supported on alumina.
However, impregnated catalyst showed a second active spinel ‘NiAl2O4’ phase, which grows at the expense of the
metastable phase, under reforming conditions. This spinel phase has been proven to be very active and coke resistant
for several hours as in the case of the Al2O3–YSZ-supported catalyst [10]. Although
the co-precipitation method provided a more homogeneous catalyst with higher surface area than impregnation
method,
the Impr-catalyst exhibited a higher catalytic performance and stability over time than the Copr-catalyst. The main
phenomenological reason for this different behaviour is thought to be the higher carbon formation/deposition
tendency shown by the Coprcatalyst. This tendency is attributed to the way the NiAl10O16 is formed and dispersed 36 in
 IMPREGNATION VS
PRECIPITATION
EXAMPLE:
• Thus, the catalyst produced via the co-precipitation method (Co-precipitation) (a)
suffered rapid deactivation from carbon deposition; (b) produced 5 times more
methane than the catalyst produced via the wet impregnation method
(Impregnation) and (c) showed a decreasing hydrogen production.
• The Impregnation catalyst exhibited a higher stability for diesel steam reforming
with no signs of carbon formation or activity loss.

The difference between Impregnation and Coprecipitation catalyst activities is

related to the Ni-aluminates dispersion: located on the surface for the
Impregnation catalyst, whereas located in the bulk of the Co-precipitation catalyst.

37
 ION EXCHANGE
Ion exchange consists of replacing an ion in an electrostatic interaction with the surface of
a support by another ion species.
The support containing ions A is plunged into an excess volume (compared to the pore
volume) of a solution containing ions B.
Ions B gradually penetrate into the pore space of the support, while ions A pass into the
solution, until equilibrium is established corresponding to a given distribution of the two
ions between the solid and the solution. The solid is then washed, and finally separated.

𝐴 𝑍 + 𝐵𝑆 ↔ 𝐵 𝑍 + 𝐴 𝑆
Where:
z= is the support and
s= the solution Fundamentals in industrial catalytic
processes. Farrauto

38
 ION EXCHANGE

Generally in salt-support systems involving slow adsorbtion or ion exchange, uniform deposition of the
catalytic material is favored.

In salt support systems involving strong and/or rapid adsorbtion or exchange, deposition may not be unifor
along pores and across pellets.

Handbook of heterogeneous catalysts.

39
 ION EXCHANGE

CHARACTERISTICS
• Support material in metal salt solution adsorbs metal salt ions.
• Require a period of time like min or hours.
• Good method for depositing small amounts (maximum of 2-3%wt).
• Efficient and convenient method for obtaining uniformly and strongly deposited
catalyst precursors (ex: low metal loadings are desired, as for expensive noble
metals).
• Useful in removing harmful agents and adding promoters.

40
 ION EXCHANGE

Materials Characteristics
Zeolites Exchange and adsorb cations strongly
Silica Adsorbs cations weakly
Alumina (amphoteric) Adsorbs both cations and anions weakly
Titania (amphoteric) Adsorbs both cations and anions (more acidic than alumina)
Carbon Adsorbs cations weakly
Magnesia Adsorbs anions strongly

41
 ION EXCHANGE
The amount of adsorbed is determine by:

Concentra Number of
adsorbtion
tion of ions sites on the
in solution support
The
amount
adsorbed is
determine
by:

Equilibri
pH um
constant

42
 ION EXCHANGE
Experimental key parameters (for supported catalysts)
• Point of zero charge of the oxide support: essential parameter to
initiate the electrostatic interaction between the metal complex and the
oxide support. One method involves the change of T of the
impregnating solution, and the second method involves selective doping
of the support surface with various types of ions.

• Solution pH and Precursor speciation: pH allows to achieve the desired

ion-support interaction (select the sign of the surface charge and
determine the concentration of charged surface sites.

43
 ION EXCHANGE
Experimental key parameters (for supported catalysts)
• Type of ligand: can affects both the nature and strength of the metal
complex-surface interaction. Some aspects must be considered: its
charged, bulkiness, presence of an adequate element (N, O, Cl, H) favors
the formation of hydrogen bonds with the surface, nature of ligand
(organic, citrated-deposit as amorphous compound).

• Competitive ions: with competitive ions is possible to control and

model the exchange process and the distribution profile of the active
phase along the radius of the grain as a function of time.

44
 ION EXCHANGE
Experimental key parameters (for supported catalysts)
• kinetics: the speciation of the deposited phase may be controller to a
large extent via the parameters that control the kinetics (T, and duration
of the preparation steps).

Handbook of heterogeneous catalysts. 45

 ION EXCHANGE
EXAMPLE:

1-Butene metathesis: process to obtained propene

46
 ION EXCHANGE
EXAMPLE:
• Significant variations in product distribution and catalytic activity
were observed when the exchange degree of mordenite changed. The
acid site density and distribution over the catalysts were directly
related to the degree of ion-exchange of sodium in mordenite.
• The change of support acidity led to different anchoring modes and
dispersion of Mo species on the support which further resulted in the
different reduction behavior of Mo species under olefin atmosphere.

47
 ION EXCHANGE
EXAMPLE:

48
 Supersaturation curve

In the supersaturation region the system is unstable and

precipitation occurs with any small perturbation.

The supersaturation region can be approached either by:

• Increasing the concentration through solvent
evaporation (A to C),
• lowering the temperature (A to B) or
• increasing the pH (which moves the solubility curve to D
and A into the supersaturation region). (Adding a Base )

Particles within the supersaturation region develop in a

two-stage process: nucleation and growth.
Catalysts preparation methods. Catalysis today.
34. 281-305. 1997.
49
 Supersaturation curve.

• Supersaturation is reached by
means of physical
transformations (change in
temperature or solvent
evaporation) or chemical
processes (addition of bases or
acids, use of complex forming
agents).

Solubility curve (function of T and pH)

50of
Fundamentals in the preparation
 What is the complexing agent

Complexing agents prevent the

metals from being precipitated;
some weak complexing agents
like citrate and tartrate may not
interfere with hydroxide
precipitation, others complexing
agents modify the precipitation
performance.

51
 What is the Point of zero
charge of the oxide support?
Most oxide supports develop a surface charge when immersed in
aqueous solution. Involving H+ and OH- ions, and are therefore
controlled by the pH.
• Low pH, the suface is positivily charged and preferentially adsorbs
anions.
• Hight pH, the suface is negativily charged and preferentially adsorbs
cations.
• At intermediate pH, a zero net charge will result (called point of zero
charge or isoelectric point).
The PZC is a useful criterion for classification of oxides into acidic (silica, silica-
alumina, zeolites), basic (MgO, ZnO) or amphoteric (alumina, titania).
52
 REFERENCES

• Fundamentals in the preparation of heterogeneous catalysts. M. Campanati, G. Fornasari, A.

Vaccari.
• http://
www.reactor-resources.com/performance-products/alumina-overview/claus-catalyst-alumina
.html

• Handbook of heterogeneous catalysts. Wiley-VCH Verlag GmbH & Co. KGaA. 2008.
• Applied heterogeneous catalysis. Design, manufacture use of solid catalysts. J.F. Le Page.
Institut francais du petrole publications. 1987.
• Heterogeneous catalysis in industrial practice. Charles Satterfield. McGraw-hill. 1991
• Mn/TiO2and Mn–Fe/TiO2catalysts synthesized by depositionprecipitation—promising for
selective catalytic reduction of NO withNH3at low temperatures. Siva Sankar Reddy Putlurua,
Leonhard Schilla,b, Anker Degn Jensenb, Bernard Siretc,Franck Tabariesc, Rasmus Fehrmanna.
Applied catalyst B. Environmental. 165, pag. 628-635. 2015.
53
 REFERENCES

• Diesel steam reforming: Comparison of two nickel aluminate catalysts

prepared by wet-impregnation and co-precipitation. Ines Esma
Achouri, Nicolas Abatzoglou, Clemence Fauteux, and Nadi Braidy.
Catalysis today. Vol 207, pag. 13-20. 2013.
• 1-Butene metathesis over Mo/mordenite-alumina catalyst: Effect of
sodium exchange degree in mordenite zeolite. Xiujie Li ∗, Dazhou
Zhang, Xiangxue Zhu, Fucun Chen, Shenglin Liu, Sujuan Xie, Longya
Xu. Journal of molecular catalysis. Vol 372. 2013.

54