Riogen - Catalysis for Chemicals & Energy

Reaction

Catalyst

Remarks

Adsorption

Separation technology

Polysiloxanes with various substitution groups

Packed catalyst columns

Adsorption

Water treatment

Zeolites

Activated carbon

Adsorption

Air treatment

Zeolites

Activated carbon

Alkylation

Benzene----> Toluene

Toluene----> Xylenes or styrene

AlCl₃

Zeolite-X

Zeolite-Y

ZSM-5

Ag/Al2O3

MCM-42

MCM-49

Pt/H-ZSM-5

La-Zeolite-X

SBA-15

H-MCM-22

CeO2-MgO

Hydroformylation

CO+C_n⁼ +H2----->C_n+1 aldehyde

Rh/Al2O3

Rh/SiO2

Rh/SiO2-Al2O3

Pd/SiO2

Rh-Pd/SiO2

Rh-Co/SiO2

Au/Co3O4

Co/Al2O3

Co/SiO2

Hydrotreating – HDS

R-SH+H2----> R+ R⁼ + H2S

Sulfided CoMo/Al2O3

Sulfided NiMo/Al2O3

Industrial catalyst

Hydrotreating – HDN

R-NH2+H2----> R+ R⁼ + NH3

Sulfided NiMo/Al2O3, Pd/Al2O3

Epoxidation

CH2=CH2----> (CH₂-CH₂)O

CH₂=CH-CH₃----->

(CH₂-CH-CH₃)O

Ag, Ag/Au supported on

zeolites, carbonates (CaCO3, MgCO3, SrCO3, BaCO3), CaF, CaTiO2, tribasic calcium phosphate, calcium molybdate, magnesium molybdate, strancium molybdate

Catl. Lett.: 2002, 80, 93

Selective hydrogenation

1,3-butadiene

α,β-unsaturated aldehydes

Crotonaldehyde---->

Crotyl alcohol

3-methyl crotonaldehyde---->

3-methyl crotyl alcohol

Lindlar catalyst

Pd/CaCO3 with Pb/Bi  or Amine/Sulfur

Al2O3 supported catalysts of

Fe, Co(10%), Ni, Cu(10%), or Pd(5%)

Al2O3 supported catalysts of Cu, Ni, Fe

Ru, Re, Os supported on ZnO

Pt (promoted by Fe or Sn)/SiO2   with Pt:Sn 4:1

Cu or Cu(sulfidation) /Al2O3

Cu/SiO2

Cu-Pd (3:1)

Pt/TiO2

Pharma, Perfumes, Flavors

Batch reactors

Selective oxidation

Propylene glycol----> acids

aldehydes, ketones

Glycerol oxidation

Pt, Pd (promoted by Bi or Pb)

Supported on C or Al2O3

Also: Cd, Co, Cu, Se, Ce, Te, Sn, Au, Ru serve as promoters

Pt, Pd, Au, or Ag supported on C, graphite, pumice

Also: PdAg/Pumice

CO oxidation

Water gas shift reaction

DeSox

Complete oxidation of CH4

Selective partial oxidation of propene

Olefin hydrogenation

NO reduction with hydrocarbons

All these reactions utilize:

Au/CeO

Au/TiO2

Au/TiC

(Ceria, oxides, carbides titania serve as goos supports)

Enantio selective reaction

Adams Pt catalyst

Pt/Cinchona

2.5%Pt/SiO2

Pt/Al2O3

DeSOx

Decomposition of SO2

SO2+2H2S-----> 2H2O+3S

Au/TiO2

Fischer Tropsch (FT) process

CO+H2--> Hydrocarbons

                   C-C compounds

In general:

nCO+nH2----> (-CH2-)n + nH2O

Fe and Co based catalysts with Ru, Cu, Ni and K2O promotion

(Sasol reaction)

Fe/ZrO2

Fe/K/ZrO2

Co/SiO2 (FT Catalyst)

Fe-H-ZSM-5

0.5%La promoted using La2O3

On 15%Co/Activated carbon

Co/Al2O3

Ru/Co/ZrO2-Al2O3

CoRe/Al2O3

Low Temp FT uses Co

High Temp FT uses Fe

Promotes alcohol formation

Methanol synthesis

CO/CO2/H2-----> CH3OH

CO+2H2------> CH3OH

Cu/ZnO/Al2O3

Cu-Zn

Cu/SiO2-Zr

Cu/ZrO2

Cu/ZnO

Pd/SiO2

Pd/ZrO2

Pd/TiO2

Ca-Pd/SiO2

Cs-Cu/ZnO/Al2O3

Rh/SiO2

Rh/Al2O3

Rh/ZrO2 or TiO2 or CeO2 or MnO or La2O3

Rh/SiO2 promoted by Mn/Fe/Li or Nb

EtOH product

(C-C product formation)

Hydrocarbons (HC) formation

EtOH formation

C2 oxygenates

Hydrogenation

Alkene-----> alkane

Acids-----> alcohols

Esters-----> alcohols

Oils and fats

Ru/C, Pd/C

Ru/C, Pd/C, Pt/C

Cu/SiO2, copper chromite, Ba promoted copper chromite

Supported Ni

Dehydrogenation

Alkane dehydrogenation

Supported ZSM-5

Ga/ZSM-5

Pt/Mg(Ga)(Al)O

Pt/Fe/ZSM-5

Pt/Mg(In)(Al)O

V2O5/MCM-41

V/Al2O3

CrOx/SiO2

Pd/Al2O3

Supported Cr catalysts

Oxidation

Partial oxidation of alkanes

Fe/SiO2

PdV/TiO2

Ti-Beta

V/MCM-41

Pt/Al2O3

Rh/Al2O3

Mn-Zeolite-5, 55, 58

Ti-Silicates

Pt/Mg(Ga)(Al)O

V2O5

V2O5/TiO2

Ammonia synthesis

Os

Ur

Fe promoted with K₂O, CaO, SiO₂, and Al₂O₃

Ru/C

Co/C

Ba-Fe-Co/C

Ru/MgO

CO₂ hydrogenation

CO2+H2-----> CO, HCOOH, HCHO, CH3OH

CO2+CH4-----> 2CO+2H2

Cu-Zn-chromite

H-zeoliteY

ZrO2 – good support for high temperature hydrogenation

Pt(Sn)/SiO2

Fe(K, Cu)/Al2O3

Dry reformation

CH4 Partial oxidation

CH4-----> CH3OH or

                  HCO species

Oligomerization

Dimerization

Partial oxidation

Dry reforming of CH4

Ru/TiO2

Ru/SiO2

Ru/Al2O3

Pt/CeZrO2/Al2O3

Ni or Ni-Au/MgO-Al2O3

Ni/Al2O3-aluminium nitride

Ni/SiO2

Ni/Mg(Al)O

Ni/MCM-41

Re/Al2O3

Mg-Al LDH

Ru/SiO2

Ru/Al2O3

Ru/C

Pt/Al2O3

Ni/Al2O3

PtNi/Al2O3

Rh/Al2O3

Rh/La2O3

NiCu/SiO2

Methanol to Hydrocarbons (MTG)

CH3OH-----> C2-C9  

                       hydrocarbons

H-ZSM-5

Cu/SiO2

Raney-Ni

Cu+-zeolite-X

Dimethyl carbonate

Steam reforming

CH4 + H2O-----> CO+3H2

Ni on Al2O3 or MgO promoted with Au, Ag, Sn, Cu, M, Fe, Ru and other transition metals

Cu/ZnO

Water gas shift (WGS) reaction

CO+H2-----> CO2+H2

CuO-ZnO-Al2O3

Fe2O3-Cr2O3-MgO

Au/CeO2 or TiO2

Cu/CeO2

Hydrogen production

(Steam reforming followed by WGS process)

CH4+H2O----->CO+3H2

ΔH= + 206 kJ/mol (298K)

Favored at high T and low P

Then do WGS:

CO+H2O-----> CO2+H2

ΔH= - 41 kJ/mol (298K)

Supported Ni catalyst

(Noble metals as activators)

High T shift:

Fe2O3/Cr2O3 at 670K

Low T shift:

Cu/ZnO at 470K

Ni/MgO

Ni/YSZ

Sn/Ni/YSZ

Ni/MgO/alkali

Pd/CeO2/Al2O3

Ni/MgO

Ni/TiO2

Pt/TiO2

Pt/ZrO2

Ag-Ni/Al2O3

Co-Ni/ZrO2

700 - 1250K / 30 bar

TOF = 0.5 s^-1 at 723K

(with 10% CH4 conversion)

Coking should be controlled

Steam dissociation

CO2 reforming

Methanol to Aromatics

Impregnated Zeolites

Ni/ZSM-5

Cu/ZSM-5

Zn/ZSM-5

Ga/ZSM-5

Ir/ZSM-5

Ru/ZSM-5

Pd/ZSM-5

Ag/ZSM-5