pavel nikulshin - topsoe.com · pavel nikulshin modern approaches to designing highly effective...
TRANSCRIPT
Pavel Nikulshin
Modern approaches to designing highly
effective hydrotreating catalysts
PhD, Senior Researcher Samara State Technical University Chair of Chemical Technology of Oil and Gas Refining E-mail: [email protected]
Moscow, May 16, 2016
Introduction. Hydrotreating processes in oil refinery
Gasoline fractions
SRGO
VGO
Crude Oil after
Desalting Аtm Dist
Vac Dist
Deep
hydrotreating
Deep hydrotreating FCC
IBP-180 °С
180-360 °С
360-500 °С
180-360 °С
100-220 °С
Selective hydrotreating
Gasoline
Diesel fuel
…
Deep hydrotreating
> 500 °С Coking
Target tasks Undesirable reactions Gasoline
Remove sulfur to below 0.5 ppm (reforming feedstock) 10-40 ppm (FCC gasoline)
Aromatics & olefin hydrogenation
SRGO Remove sulfur to below 50-10 ppm condensed aromatics hydrogenation
Cracking
VGO Remove sulfur to below 350-500 ppm metals removal
Cracking
2
Worsening of oil crudes Stricter environmental
requirements to products Involvement of bio-raw materials Involvement of oil-slime to refining
Challenges in oil refining:
catalysts
Gasoline fractions
SRGO
VGO
Crude Oil after
Desalting Аtm Dist
Vac Dist
Deep
hydrotreating
Deep hydrotreating FCC
IBP-180 °С
180-360 °С
360-500 °С
180-360 °С
100-220 °С
Selective hydrotreating
Gasoline …
Deep hydrotreating
> 500 °С Coking
2
Diesel fuel
Introduction. Hydrotreating processes in oil refinery
mm μm nm Å
NiMoS phase CoMoS phase NiWS phase
Particle length 25-60 Å
S = 1.8 % wt. (18 000 ppm)
S = 0.001 % wt. (10 ppm)
H2 Feedstock
Catalysts
30–100 m3
Product H2S
P = 2-10 МPа, T = 280-420 ºC
3 Introduction. Industrial hydrotreating catalysts
> 100 brands of catalysts
NiMo/Al2O3; CoMo/Al2O3 NiW/Al2O3; NiW/ASA
The “Rim-edge” model M. Daage, R. R. Chianelli // J. Catal. 149 (2)
(1994) 414
“Co(Ni)MoS” phase model H. Topsøe et al. // J. Catal. 68 (1981) 433
J.V. Lauritsen et al. // J. Catal. 249 (2007) 220
H. Toulhoat and P. Raybaud // J. Catal. (2003)
Main developed concepts of catalysis by sulfides
The electronic model of promoting
S. Harris, R.R. Chianelli // J. Catal. 98 (1986) 17
S S S
S S S
S S S S S Co Ni Ni
4
Al2O3
5 Scientific challenges in sulfide catalysis
Turnover frequency [mol DBT × mol act. site-1 × s-1]
MS2 Dibenzothiophene
Biphenyl
H2S
Al2O3
5
TOFXMS,P,T = f(L,N,X,M, ni,..?)
Scientific challenges in sulfide catalysis
Turnover frequency [mol DBT × mol act. site-1 × s-1]
Fundamental questions: Intrinsic nature of active sites (electronic,
structural) “Structure – activity” relationships Evolution of active sites at reaction conditions (T,
p(H2), H2S, N-,O-containing compounds…) Support effects (electronic, new compositions,
Brønsted/Lewis…) Create new active sites (CoMoS-III, NiCoMoS,
NiMoWS, …)
N
L
X = Co, Ni…
M = Mo, W…
MS2 Dibenzothiophene
Biphenyl
H2S
6 Haldor Topsøe’s grants for PhD students of Samara State Technical University
Alexander Mozhaev 2011 winner
Deep HDS, HYD. Co2Mo10HPA based catalysts. NiCoMoS catalysts
Daria Ishutenko 2012 winner
Selective HDS of FCC gasoline. KCoMoS catalysts based on PMo12HPA
Pavel Nikulshin 2008 winner
Deep HDS of diesel XMo6HPAs as precursors for HDS catalysts. C-coated supports
Maria Kulikova 2015 winner
Deep HDS&HYD NiMoWS catalysts based on
SiMonW12-nHPA
Andrey Varakin 2014 winner
HDO reactions. Co-hydrotreating. Unsupported catalysts
Aleksey Pimerzin 2013 winner
Deep HDS, HYD, HDN. Spillover effects in sulfide catalysis
TOFXMS = f(L,N,X,M, ni,..?)
Topics 1. Development of new sulfide catalysts
1.1 New molecular precursors of active phases 1.2 Effect of composition and morphology of active phase species on
catalytic properties 2. Catalysts for deep hydrotreating of oil fractions
2.1 Trimetallic NiCoMoS catalysts with enhanced HDS & HYD activities 2.2 NiW/Al2O3 catalysts prepared with heteropolycompounds
3. Catalysts for selective hydrodesulfurization of FCC gasolines 3.1 Trimetallic KCoMoS catalysts with improved HDS/HYDO selectivity
4. Catalysts for co-hydrotreating of diesel and vegetable oil 4.1 Carbon-covered supports for sulfide catalysts
Topics 1. Development of new sulfide catalysts
1.1 New molecular precursors of active phases 1.2 Effect of composition and morphology of active phase species on
catalytic properties 2. Catalysts for deep hydrotreating of oil fractions
2.1 Trimetallic NiCoMoS catalysts with enhanced HDS & HYD activities 2.2 NiW/Al2O3 catalysts prepared with heteropolycompounds
3. Catalysts for selective hydrodesulfurization of FCC gasolines 3.1 Trimetallic KCoMoS catalysts with improved HDS/HYDO selectivity
4. Catalysts for co-hydrotreating of diesel and vegetable oil 4.1 Carbon-covered supports for sulfide catalysts
Co
Co9S8
MoS2Co
Co9S8
MoS2
(1) Impregnation with (NH4)6Mo7O24 and Ni(NO3)2
(2) Drying and calcination
(3) Sulfidation
7
Drawbacks: Cо atoms introduced in Al2O3 Co atoms exists in nonactive
Co9S8 species MoS2 not fully sulfided and
strongly bonded with Al2O3
Some problems in preparation of Co(Ni)Mo/Al2O3 catalysts
Catalysts improvement
Use of HPA in the impregnating
solution (Co2Mo10O34
6-, PMo12O40
3-)
Increase of active metals contents
Use of «Doping» elements (Rh, Pt,
Ru, P, F)
Use of new carriers (C, TiO2, zeolite,…)
Use of chelating agent in the
impregnating solution
(NTA, EDTA...)
Modification of the oxidic precursor by organic agents (TEG, TGA…)
How to improve HDS catalysts?
Use of unsupported sulfides and
nonsulfide catalysts
8
Catalysts improvement
Use of HPA in the impregnating
solution (Co2Mo10O34
6-, PMo12O40
3-)
Increase of active metals contents
Use of «Doping» elements (Rh, Pt,
Ru, P, F)
Use of new carriers (C, TiO2, zeolite,…)
Use of chelating agent in the
impregnating solution
(NTA, EDTA...)
Modification of the oxidic precursor by organic agents (TEG, TGA…)
How to improve HDS catalysts?
Use of unsupported sulfides and
nonsulfide catalysts
8
Blue octahedra: MoO6; green octahedra: octahedral heteroatom (Co); pink tetrahedra: central heteroatom in Keggin structure (P, Si).
Preparation of catalysts with heteropolyanions
887 877 Solution of HPA
Impregnation
of Al2O3
Impregnated carrier
Drying at 110 0C 6 h
Catalyst in oxide state
Sulfided catalyst
Sulfidation at 400 0C, H2S/H2
Al2O3 Al2O3Al2O3
Typical HPAs structures used for preparation of hydroprocessing catalysts
9
Catalytic properties: thiophene HDS
Thiophene hydrodesulfurization (HDS)
SS
2H2+
H2
Conditions: Pulse microcatalytic reactor
t = 300 – 4000C
P = 0.125 MPa
V(H2) = 20 сm3/min
Vthiophene = 0.2 μL;
m.= 0.25 mg
P.A. Nikulshin et al. // Appl. Catal. A 393 (2011) 146
0,000
0,020
0,040
0,060
0,080
0,100
0,120
Cr Mn Fe Co Ni Cu Zn Ga
400 0С380 0С
360 0С340 0С
320 0С300 0С
HDS,
0,0000,0200,0400,0600,0800,1000,1200,1400,160
Cr Mn Fe Co Ni Cu Zn Ga
HDS, 400 0С380 0С
360 0С340 0С
320 0С300 0С
XMo6/Al2O3
Ni3-XMo6/Al2O3
Mo/Al2O3 (400 0C)
Ni0.5-Mo/Al2O3 (400 0C)
10 Anderson type XMo6HPA
Selective HDS of FCC gasoline
Catalytic properties: HDS vs HYDO
Mo/Al2O3
SS
2H2+
H2
Conditions: Bench scale flow reactor Feedstock: n-hexene-1 (36 wt.%), thiophene (0.1 wt.% S),
n-heptane (solvent) t = 2200C P = 1.5 MPa LHSV = 5.0 h-1; H2/feedstock = 100 NL/L; mcat = 0.3 g
XMo6/Al2O3
CH2CH3CH3CH3
+2H2
0
5
10
15
20
25
Cr Mn Fe Co Ni Cu Zn Ga
Thiophene HDSHexene-1
Conversion, %
0.00
0.20
0.40
0.60
0.80
1.00
1.20
Cr Mn Fe Co Ni Cu Zn Ga
HDS/HYDO selectivity factor
)1ln()1ln( HDS/HYDO
HYD
HDS
xx
−−
=
Undesirable reaction HYDO
Target reaction HDS
Mo/Al2O3
11 Anderson type XMo6HPA
Physical-chemical properties of the catalysts
Catalyst Ni(Co)MoS
phase, at. %
Ni(Co)Sx phase, at. %
Ni(Co)2+ phase, at. %
(Co/Mo)slab
NiMo6/Al2O3 67 8 25 0.14
CoMo6/Al2O3 71 9 20 0.13
XPS Co2p spectrum of СоМо6/Al2O3 catalyst
Co2p3/2 (CoMoS)
Co2p1/2 (CoMoS)
Co2p3/2 (Co2+)Co2p1/2 (Co2+)
Co2p3/2 (Co9S8)
Co2p1/2 (Co9S8)
The decomposition of the Mo3d and Co2p XPS spectra were performed using approaches proposed by [] and with the use of CasaXPS Version 2.3.16 software. A.D. Gandubert et al // Oil & Gas Sci. & Tech. 62 (2007), No. 1, 79 K. Marchand et al // Oil & Gas Sci. & Tech. 64 (2009), No. 6, 719
Active phase of the catalysts is Co(Ni)MoS phase with deficiency of promoter atoms Role of HPA is in the formation of “framework” of an active phase, i.e. multilayer MoS2 slabs.
12 Anderson type XMo6HPA
MoS2
Sabatier’s principle in catalysis by supported TMS
=> Heteroatom X promotes optimization of the electron density on the anti-bonding d-orbital of Mo in the active mixed sulfide phase and, thereby, facilitates productivities of the active sites
13 Anderson type XMo6HPA
Thiophene HDS over XMo6/Al2O3 catalysts vs DFT calculated heat of thiophene adsorption
0.00
0.02
0.04
0.06
0.08
0.10
0.12
0.0 0.2 0.4 0.6 0.8 1.0
HDS,
Cu
Zn
Ni
Co
Fe
Cr
∑ ⋅+ sMo)mol(XSHmolC 44
eVΔH Tads,−
HDS activity vs T of TPR peak maximum of sulfided catalysts
0.0
5.0
10.0
15.0
20.0
300 310 320 330 340 350 360
Thi
ophe
ne H
DS
(%)
Temperature of maximum peak reduction (°С)
CoNi
Fe
CrCu
Zn
Mo
DFT calculations of the heat of adsorption of thiophene H. Orita et. al. // Appl. Catal. A
258 (1) (2003) 115
XMo-S
TPR curves (TCD signals) of sulfided XMo6/Al2O3 and Mo/Al2O3 catalysts
40
50
60
70
80
90
100
0.00 0.10 0.20 0.30 0.40 0.50 0.60Promoter/Mo
Thi
ophe
ne c
onve
rsio
n ( %
)
CoMo/Al2O3(industrial)
NiMo6-emuls
FeMo6-emuls
Co3/2-PMo12O40/Al2O3
CoMo6/Al2O3
Co2Mo10/Al2O3
Co7/2-PMo12O40/Al2O3
Co3-Co2Mo10/Al2O3
Co-CoMo6/Al2O3 ?
Shortcomings: There is no HPA structure with higher Co (Ni)/Mo ratio
than 5:1 Use only HPA as a precursor of catalysts leads to
formation of active phase with deficiency of CoMo sites
Advantages: Application of HPCs gives a possibility to introduce Mo
and a promoter (modifiers) into a catalyst simultaneously – from one molecule
CoMoS phase of type II formed from HPCs
14 Heteropolycompounds as precursors of hydrotreating catalysts
15
40
50
60
70
80
90
100
0.00 0.10 0.20 0.30 0.40 0.50 0.60Promoter/Mo
Thi
ophe
ne c
onve
rsio
n ( %
)
CoMo/Al2O3(industrial)
NiMo6-emuls
FeMo6-emuls
Co3/2-PMo12O40/Al2O3
CoMo6/Al2O3
Co2Mo10/Al2O3
Co7/2-PMo12O40/Al2O3
Co3-Co2Mo10/Al2O3
Co-CoMo6/Al2O3 ?
C. Lamonier et al. // Appl. Catal. B 70 (2007) 548–556 J. Mazurelle et al. // Catal. Today 130 (2008) 41–49 A. Mozhaev / PhD thesis, Moscow, 2012, 173 p. P. Nikulshin, C. Lamonier et al. // Comptes Rendus Chimie (2015)
Heteropolycompounds as precursors of hydrotreating catalysts: overcoming of shortcomings
Use of Co salt of HPAs for catalysts preparation
Heteropolycompounds as precursors of hydrotreating catalysts: overcoming of shortcomings
15
40
50
60
70
80
90
100
0.00 0.10 0.20 0.30 0.40 0.50 0.60Promoter/Mo
Thi
ophe
ne c
onve
rsio
n ( %
)
CoMo/Al2O3(industrial)
NiMo6-emuls
FeMo6-emuls
Co3/2-PMo12O40/Al2O3
CoMo6/Al2O3
Co2Mo10/Al2O3
Co7/2-PMo12O40/Al2O3
Co3-Co2Mo10/Al2O3
Co-CoMo6/Al2O3 ?
Use of Co salt of HPAs for catalysts preparation
C. Lamonier et al. // Appl. Catal. B 70 (2007) 548–556 J. Mazurelle et al. // Catal. Today 130 (2008) 41–49 A. Mozhaev / PhD thesis, Moscow, 2012, 173 p. P. Nikulshin, C. Lamonier et al. // Comptes Rendus Chimie (2015)
Difficulties in deep hydrodesulfurization of oil fractions
16
σ-bonding
π-bonding
Steric hindrance
Sulfur compound Relative HDS rate
Thiophene 2250
Benzothiophene 1330
Dibenzothiophene (DBT) 100
4-methyldibenzothiophene (4-MDBT) 9
4,6-dimethyldibenzothiophene (4,6-DMDBT) 7
C. Song / Catal. Today 86 (2003) 211
Reactivity of various organic sulfur compounds in HDS versus their ring sizes and positions of alkyl
substitutions on the ring
17
0
10
20
30
40
50
0.0 0.2 0.4 0.6 0.8 1.0
k HD
S×10
5(m
ol·h
-1·g
-1)
DBT HDS4,6-DMDBT HDS
(Co/Mo)edge
Co2+
Co2+
Co2+
P. Nikulshin et al. // J. Catalysis 312 (2014) 152 P. Nikulshin, C. Lamonier et al. / Comptes Rendus Chimie (2015)
Heteropolycompounds as precursors of hydrotreating catalysts: overcoming of shortcomings
17
0
10
20
30
40
50
0.0 0.2 0.4 0.6 0.8 1.0
k HD
S×10
5(m
ol·h
-1·g
-1)
DBT HDS4,6-DMDBT HDS
(Co/Mo)edge
Co2+
Co2+
Co2+
Promotion degree of the MoS2 edges (Co/Mo)edge became only 0.64
Co salt of Co2Mo10HPA does not provide required molecular contact of Co2+ with HPA on the alumina surface
New approach?
Heteropolycompounds as precursors of hydrotreating catalysts: overcoming of shortcomings
Catalysts improvement
Use of HPA in the impregnating
solution (Co2Mo10O34
6-, PMo12O40
3-)
Increase of active metals contents
Use of «Doping» elements (Rh, Pt,
Ru, P, F)
Use of new carriers (C, TiO2, zeolite,…)
Use of chelating agent in the
impregnating solution
(NTA, EDTA...)
Modification of the oxidic precursor by organic agents (TEG, TGA…)
How to improve HDS catalysts?
Use of unsupported sulfides and
nonsulfide catalysts
What results will be obtained if both HPA and chelating agent are used for catalyst preparation?
Topics 1. Development of new sulfide catalysts
1.1 New molecular precursors of active phases 1.2 Effect of composition and morphology of active phase species on
catalytic properties 2. Catalysts for deep hydrotreating of oil fractions
2.1 Trimetallic NiCoMoS catalysts with enhanced HDS & HYD activities 2.2 NiW/Al2O3 catalysts prepared with heteropolycompounds
3. Catalysts for selective hydrodesulfurization of FCC gasolines
4. Catalysts for co-hydrotreating of diesel and vegetable oil 4.1 Carbon-covered supports for sulfide catalysts
Catalyst
Presence in impregnating solution
Amount in the Catalysts (wt. %) Co/Mo
ratio
Textural characteristics
Со2+ NH4+ Chelating
agent Mo Co SSA (m2/g)
Vp (cm3/g)
APR (Å)
Co2Mo10HPA – + – 10.0 1.2 0.17 183 0.58 62
Co3-Co2Mo10HPA + – – 9.9 3.1 0.31 170 0.46 62
[Co(NTA)]3-Co2Mo10HPA + + NTA 10.0 3.2 0.32 168 0.46 62
[Co(EDTA)]3-Co2Mo10HPA + + EDTA 10.1 3.0 0.30 172 0.46 62
[Co(CA)]3-Co2Mo10HPA + – Citric acid 10.1 3.0 0.30 170 0.46 62
[Co(TA)]3-Co2Mo10HPA + – Tartaric acid 10.1 3.0 0.30 170 0.46 62
Simultaneous using Co2Mo10HPA and different types of chelating agents
Co complex with chelating agent
(NTA, EDTA, CA, TA)
Co2Mo10HPA (T=40 °C, aqueous sol.)
Al2O3 Sg= 240 m2/g, Vp= 0.7 cm3/g,
Dp= 12 nm
Drying 110 °C (5h)
[Co(Ligand)]-Co2Mo10HPA/Al2O3 catalysts
18
Composition of CoMoS species present at the surface of sulfided catalysts (from TEM and XPS)
Catalyst (Co/Mo)tot (Co/Mo)edge Co in CoMoS and multi-slabs CoMoS/ (wt. %)
Co2Mo10/Al2O3 0.2 0.4
Co3-Co2Mo10/Al2O3 0.5 0.6
Co3[NTA]-Co2Mo10/Al2O3 0.5 0.9
Co3[EDTA]-Co2Mo10/Al2O3 0.5 0.7
Co3[CA]-Co2Mo10/Al2O3 0.5 1.1
Co3[TA]-Co2Mo10/Al2O3 0.5 0.8
19
Al2O3
CoMoSC/CoMoSC
0.14
0.43
0.3
0.21
0.72
0.52
0 0.5 1 1.5
Simultaneous using Co2Mo10HPA with Co(Chel) complexes resulted in formation of CoMoS species fully covered with Co promoter atoms
Differences in morphological properties of sulfide species connects with the features of the formed supported oxidic precursors that was indicated by Raman P. Nikulshin et al. // J. Catalysis 312 (2014) 152
Al2O3
Correlation of reaction rate constants with Co content into CoMoS and multi-CoMoS/ species
Hydrodesulfurization of DBT and 4,6-DMDBT
Hydrotreating of thiophene with n-hexene
R² = 0.72R² = 0.95
0.0
2.0
4.0
6.0
8.0
10.0
12.0
14.0
16.0
18.0
20.0
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4
k HD
S×10
5(m
ol·h
-1·g
-1)
R² = 0.67R² = 1.00
0
200
400
600
800
1000
1200
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4
k HY
D×1
05(m
ol·h
-1·g
-1)
R² = 0.89
R² = 0.43
R² = 0.89 R² = 0.49
0.0
10.0
20.0
30.0
40.0
50.0
60.0
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4
k HD
S×10
5(m
ol·h
-1·g
-1)
DBT
4,6-DMDBT
Good correlation between rate constants of HDS and HYD of “light” molecules and CoMoS phase content and bad – for “heavy” molecules
+ +
20
CoMoSC
Thiophene HDS
Hexene-1 HYD
St. # ≥ 1
Al2O3
Hydrodesulfurization of DBT and 4,6-DMDBT
Hydrotreating of thiophene with n-hexene
R² = 0.72R² = 0.95
0.0
2.0
4.0
6.0
8.0
10.0
12.0
14.0
16.0
18.0
20.0
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4
k HD
S×10
5(m
ol·h
-1·g
-1)
R² = 0.67R² = 1.00
0
200
400
600
800
1000
1200
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4
k HY
D×1
05(m
ol·h
-1·g
-1)
R² = 0.89
R² = 0.43
R² = 0.89 R² = 0.49
0.0
10.0
20.0
30.0
40.0
50.0
60.0
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4
k HD
S×10
5(m
ol·h
-1·g
-1)
DBT
4,6-DMDBT
+ + +
20
Good correlation between rate constants of DBT and 4,5-DMDBT and multi-slab CoMoS phase content
CoMoSC/CoMoSC
Thiophene HDS
Hexene-1 HYD
St. # ≥ 1 St. # ≥ 2
Correlation of reaction rate constants with Co content into CoMoS and multi-CoMoS/ species
21
Catalyst Activity
SF Reference HDS HYD
CoMo/Al2O3-1 30.9 58.2 0.42 Qiherima et al. Chin. J. of Catal. 32
(2011) 240 CoMo/Al2O3-2 42.2 59.1 0.61
CoMo/γ-Al2O3-1 33.6 54.8 0.52 M. Li et al. Catal. Today 149 (2010)
35 Co/Mo-S/δ-γ-Al2O3 39.8 46.4 0.81 CoMo/SiO2 10.2 9.8 1.04 CoMo/Al2O3 (industrial) 11.0 11.0 1.00
D. Mey et al. J. of Catal. 227 (2004)
436 CoMo/Al2O3 62.0 98.0 0.25 J.-S. Choi et al.
Appl. Catal. A 267 (2004) 203
Sn-CoMo/Al2O3 11.16 24.5 0.42
CoMo/Al2O3 31.0 47.0 0.58 D.J. Pérez-Martínez et al. Appl. Catal. A
390 (2010) 59
K-CoMo/Al2O3 25.0 47.0 0.45 K-CoMo/Al2O3 10.0 26.0 0.35 B-CoMo/Al2O3 24.0 37.0 0.59
(Co/Mo)edge
Average length (nm)
HDS/HYDOselectivity factor
0.20.30.4
0.50.6
0.70.8
0.91.0
1.11.2 2.8
3.0
3.23.4
3.63.8
4.04.2
4.41.2
1.4
1.6
1.8
2.0
2.2
2.4
2.6
Comparison of HDS and HYD activities and selectivity factor of CoMo-supported catalysts
HDS CoMo edge site HYDO
CoMo corner site The HDS/HYDO selectivities linearly depend on the number of CoMo sites on the slab edges. P. Nikulshin et al. // J. Catalysis 312 (2014) 152
Towards control of selectivity factor HDS/HYDO in FCC gasoline HDT: composition and size effects
CA NTA
TA
[Co(Lig)]-Co2Mo10Al2O3 catalysts
TOF number in HDS of DBT and 4,6-DMDBT vs average length of CoMoS phase and (Co/Mo)edge ratio
22
0.20.30.40.50.6
0.70.8
0.91.0
1.11.2 2.8
3.03.2
3.43.6
3.84.0
4.24.4
5.0
10.0
15.0
20.0
25.0
(Co/Mo)edge
Average length (nm)
DBT
4,6-DMDBT
)(s10 TOF 14/ −×
During DBT HDS, the highest TOF/ value is achieved at a minimal (Co/Mo)edge ratio (0.3 – 0.4) when the Co atoms are located on the S-edge and when the active phase is short
P. Nikulshin et al. // J. Catalysis 312 (2014) 152
(Ni/W)edge
(Co/Mo)edge
Catalyst DBT 4,6-DMDBT Ref Co2Mo10/Al2O3 23.9 4.4 Present work Co3[EDTA]-Co2Mo10/Al2O3 18.8 4.9 Industrial catalyst CoMoS/Al2O3
0.4 - S.T. Oyama et al. Catal. Today 143
(2009) 94 Industrial catalyst CoMoS/Al2O3
0.4 0.1 M. Kouzu et al. Appl. Catal. A 276
(2004) 241 CoMo/Al2O3 10.8 1.4 Lee et al.
Catal. Today 86 (2003) 141
CoMo/C 9.5 1.1
CoMo-S/γ-Al2O3 - 0.8 Laurenti et al. J. Catalysis 297
(2013) 165 CoMoS-S/γT-Al2O3 - 1.3 CoMoS-S/δ-Al2O3 - 1.9 CoMoS-acac/γ-Al2O3 - 1.3 CoMoS-acac/γT-Al2O3 - 1.8 CoMoS-acac/δ-Al2O3 - 2.3
Activity of СоМо catalysts in DBT and 4,6-DMDBT HDS
S
S Mo Mo
S
S
S Mo
S Mo Co
Co Co Mo S
S
S S
Co Co Co S S S
Mixed CoMoS sites located on short slabs
are the most active
EDTA
Co2Mo10
[Co(Lig)]-Co2Mo10Al2O3 catalysts
CA
TA NTA
Dependence of S content in hydrogenated products of diesel HDT on effective Co content in CoMoS determined by XPS
P. Nikulshin et al. / Fuel 100 (2012) 24–33 A. Mozhaev / PhD thesis, Moscow, 2012, 173 p.
Bench-scale flow reactor Feedstock: SRGO&LCO (80/20) Catalyst : 10 cm3 in SiC P(H2) = 4.0 MPa Temperature = 340 0C LHSV = 2.0 h-1
HTO = 500 NL/L
Deep diesel hydrotreating over Co3[Chel]-Co2Mo10/Al2O3 catalysts
23
Nikulshin et. al. Patent of Russia
0
20
40
60
80
100
120
140
160
180
200
0.0 0.2 0.4 0.6 0.8 1.0
Prod
uct s
ulfu
r (w
tppm
)
Co3-Co2Mo10/Al2O3
Co3(CA)-Co2Mo10/Al2O3
Co3(TA)-Co2Mo10/Al2O3
Co3(EDTA)-Co2Mo10/Al2O3
Co3(NTA)-Co2Mo10/Al2O3
Euro-5
ULSD 8 ppm S
T = 355 0C ОСПС = 1.5 h-1
1.1 % wt. S
Co3[CA]-Co2Mo10/Al2O3
Topics 1. Development of new sulfide catalysts
1.1 New molecular precursors of active phases 1.2 Effect of composition and morphology of active phase species on
catalytic properties 2. Catalysts for deep hydrotreating of oil fractions
2.1 Trimetallic NiCoMoS catalysts with enhanced HDS & HYD activities 2.2 Spillover effect in catalysis by sulfides 2.3 NiW/Al2O3 catalysts prepared with heteropolycompounds
3. Catalysts for selective hydrodesulfurization of FCC gasolines 3.1 Trimetallic KCoMoS catalysts with improved HDS/HYDO selectivity
4. Catalysts for co-hydrotreating of diesel and vegetable oil 4.1 Carbon-covered supports for sulfide catalysts
Al2O3
Trimetallic NiCoMoS catalysts
[Co2Mo10O38H4]6-
HDS activity
NiCoMoS phase?
Citric Acid
Ni2+
The aim of this work was to investigate the co-promotion effect in NiCoMo/Al2O3 catalysts based on Co2Mo10-heteropolyacid and nickel citrate.
MoS2
24
Catalyst Atomic ratio Content in the catalyst (wt. %) Specific
surface area (m2/g)
Pore volume (cm3/g)
Average pore
diameter (Å) Mo Co Ni Carbon
Mo/Al2O3 - - 10.2 - - - 134 0.31 56 Co2Mo10/Al2O3 0.17 - 10.1 1.3 - - 115 0.25 56
Co1-Co2Mo10/Al2O3 0.25 - 9.9 2.0 - 0.6 105 0.21 56
Co3-Co2Mo10/Al2O3 0.35 - 10.0 3.3 - 1.5 90 0.18 56/38
Co6-Co2Mo10/Al2O3 0.45 - 10.0 5.0 - 2.6 75 0.14 56/38
Ni1-Co2Mo10/Al2O3 0.16 0.09 10.2 1.3 0.8 0.5 111 0.26 56 Ni3-Co2Mo10/Al2O3 0.14 0.21 9.9 1.3 2.0 1.6 92 0.18 56/38 Ni6-Co2Mo10/Al2O3 0.11 0.34 10.1 1.3 3.8 2.5 80 0.16 56/38
MoNiCoCo++ MoNiCo
Ni++
Composition of prepared Cox-Co2Mo10/Al2O3 and Nix-Co2Mo10/Al2O3 catalysts
Al2O3 Sg= 220 m2gг, Vp= 0.60 cm3/g,
Dp= 6.0 нм
Dried, 120 0C (5 h)
25
Co2Mo10HPA (T=400C, water
solution)
Cox-Co2Mo10/Al2O3 catalysts
Co complex with CA
Ni complex with CA
Nix-Co2Mo10/Al2O3 catalysts
Incipient pore-volume impregnation
A. Mozhaev, P. Nikulshin et al. // Catal Today (2015)
Dependence of effective amount of Со and Ni particles on Co(Ni)/(Co+Ni+Mo) promotion degree
26
0.0
0.5
1.0
1.5
2.0
0 0.1 0.2 0.3 0.4 0.5
Effe
ctiv
e am
ount
of C
o (w
t. %
)
CoMoS
Co2+
Co9S8
Cox-Co2Mo10/Al2O3
XPS Ni2p spectra recorded for Ni3-Co2Mo10/Al2O3 catalyst
130
135
140
145
150
155
160
165
170
175
890 885 880 875 870 865 860 855 850 845
Binding energy (eV)
CPS
×10
2
Ni2p3/2 (NiS)
Ni2p1/2 (Ni2+)
Ni2p1/2 (NiMoS)
Ni2p1/2 (NiS)
Ni2p3/2 (Ni2+)
Ni2p3/2 (NiMoS)
Catalyst Co percentage in
Ni percentage in
CoMoS Co9S8 Co2+ NiMoS NiS Ni2+ Mo/Al2O3 - - - - - - Co2Mo10/Al2O3 63 2 35 - - - Co1-Co2Mo10/Al2O3 55 9 36 - - - Co3-Co2Mo10/Al2O3 50 15 35 - - - Co6-Co2Mo10/Al2O3 31 31 38 - - - Ni1-Co2Mo10/Al2O3 62 3 35 47 28 25 Ni3-Co2Mo10/Al2O3 63 2 35 44 28 28 Ni6-Co2Mo10/Al2O3 62 2 36 25 40 35
0.0
0.5
1.0
1.5
2.0
0 0.1 0.2 0.3 0.4 0.5
Effe
ctiv
e am
ount
of C
o (N
i) (w
t. %
)
NiMoS
Ni2+
NiS
CoMoS
Co2+
Co9S8
MoNiCo(Ni) Co++
Nix-Co2Mo10/Al2O3
27 Rate constants in DBT HDS vs promotion degree and the effective amount of active phase species
0.0
2.0
4.0
6.0
8.0
10.0
12.0
14.0
0 0.1 0.2 0.3 0.4 0.5
k HD
S×1
0-4 (m
ol h
-1g-1
)
Nix-Co2Mo10/Al2O3
Cox-Co2Mo10/Al2O3
MoNiCo(Ni) Co++
0.0
2.0
4.0
6.0
8.0
10.0
12.0
14.0
0.0 0.5 1.0 1.5 2.0 2.5Effective amount of Co (Ni) in (Ni)CoMoS phase (wt. %)
Co3-Co2Mo10/Al2O3
Mo/Al2O3
k HD
S×1
0-4 (m
ol h
-1g-1
)
CoMoSNiMoS
Ni3-Co2Mo10/Al2O3
Ni6-Co2Mo10/Al2O3
Ni1-Co2Mo10/Al2O3
Co6-Co2Mo10/Al2O3
Co1-Co2Mo10/Al2O3
Co2Mo10/Al2O3
For both series of the catalysts, HDS activity passed through maximum with increasing Ni or Co. Maximal rate constants were reached at 0.33 of Co(Ni)/(Co+Ni+Mo).
At equal content of Co in CoMoS and sum of the Co and Ni in the NiCoMoS phase, the Nix-Co2Mo10S/Al2O3 catalysts were more active.
Conditions: t = 2750C; P= 3.0 MPa; LHSW= 27 h-1; HTO = 700 NL/L; mcat = 0.15 g.
What are the reasons of the changes in the activities of the promoted (Ni)CoMoS catalysts?
28
Catalysts Number of MoIV
edge site (1020 at. g-1) TOFedge TOFMo TOFCo TOFNi
Mo/Al2O3 1.26 - - 0.63 0.63 - - Co2Mo10/Al2O3 1.68 0.43 - 3.5 0.63 7.3 - Co1-Co2Mo10/Al2O3 1.48 0.68 - 5.1 0.63 6.9 Co3-Co2Mo10/Al2O3 1.66 1.09 - 7.1 - 6.4 - Co6-Co2Mo10/Al2O3 1.35 1.16 - 7.1 - 6.1 - Ni1-Co2Mo10/Al2O3 1.64 0.44 0.23 7.5 0.63 7.3 17.9 Ni3-Co2Mo10/Al2O3 1.66 0.44 0.57 9.8 - 7.3 11.6 Ni6-Co2Mo10/Al2O3 1.66 0.45 0.64 9.7 - 7.3 10.0
( )edgeMoCo ( )edgeMo
Ni
Content of active sites and TOF values (× 10-4 s-1) in HDS of DBT
TOF values in DBT HDS on prepared Cox-Co2Mo10/Al2O3 and Nix-Co2Mo10/Al2O3 catalysts
TOFedge × [MoIVedge] = TOFMo × [Mo] + TOFCo × [Co] + TOFNi × [Ni]
TOFedge × [MoIVedge] = TOFMo × [Mo] + TOFCo × [Co]
TOFedge × [MoIVedge] = TOFMo × [Mo]
For CoMoS2/Al2O3 catalysts:
For NiCoMoS2/Al2O3 catalysts:
For MoS2/Al2O3 catalysts:
MoS2
0.00.3
0.60.9
1.22.53.0
3.54.0
4.5
5
10
15
20
TOF × 104 (s-1)
Average length (nm)
( )edgeMoNiCo+
Mo/Al2O3
Cox-Co2Mo10/Al2O3
Nix-Co2Mo10/Al2O3
Topics 1. Development of new sulfide catalysts
1.1 New molecular precursors of active phases 1.2 Effect of composition and morphology of active phase species on
catalytic properties 2. Catalysts for deep hydrotreating of oil fractions
2.1 Trimetallic NiCoMoS catalysts with enhanced HDS & HYD activities 2.2 NiW/Al2O3 catalysts prepared with heteropolycompounds
3. Catalysts for selective hydrodesulfurization of FCC gasolines 3.1 Trimetallic KCoMoS catalysts with improved HDS/HYDO selectivity
4. Catalysts for co-hydrotreating of diesel and vegetable oil 4.1 Carbon-covered supports for sulfide catalysts
29 The use of H3PW12O40 and Ni(Citr) for preparation of NiWS/Al2O3 catalysts
MoS2
4.05.0
6.0
7.0
8.00.0
0.30.6
0.91.2
5
10
15
(Ni/W)edge
TOF × 104 (s-1)
Average length (nm)
λ = 0.33λ = 0.24λ = 0.11
λ = 0
λ = 0.45λ = 0.60
DBT HDSNaphthalene HYDQuinoline HDN
0.0
5.0
10.0
15.0
0.11 0.33
Ni-CA-PW0.11-NiPW0.33-NiW
WNiNi+=λ
k×10
4(m
ol·h
-1·g
-1)
NiWS
Rate constants of the DBT HDS over NiWS/Al2O3 catalysts
Ni3/2PW12O40
(NH4)6W12O39 and Ni(NO3)2
H3PW12O40 and Ni(Citr)
3D dependence of the TOF number in DBT HDS, naphthalene HYD and quinoline HDN over λ-Ni-CA-PW/Al2O3 catalysts on
the average length of the NiWS phase species and (Ni/W)edge
⇒ Simultaneous use of PW12HPA and Ni(Citr) led to formation of NiWS phase contained much more Ni than in the references
⇒ Both NiW reference catalysts had active sites with lower TOF than their counterparts from PW12HPA and Ni(Citr).
⇒ Better dispersion of NiWS species and beneficial role of coke formed from citric molecules during catalyst sulfidation P. Minaev, P. Nikulshin et al // Appl. Catal A (2015)
Testing of catalytic properties in VGO hydrotreating
Bench-scale flow reactor Catalyst: 15 cm3 in SiC P(H2) = 5.0 MPa, T = 360-390 0C LHSV = 0.5 – 1.5 h-1, HTO = 800 NL/L
30
Item VGO Distillation (°C) Density at 20 °C (g/cm3)
350 – 500 901
Content (wt. %) Sulfur 1.7 Nitrogen 0.089 Polycyclic aromatics 9.2
Characteristics of VGO
Catalyst Hydrotreating conditions Content in the hydrogenated products
T (ºС)
LHSV (h-1)
P (МPа)
HTO (NL/L) Sulfur
(ppm) Nitrogen
(ppm) PACs] (% wt)
NiWS/Al2O3 360 0.5 5.0 800 120 147 3.9 360 1.0 5.0 800 342 264 4.2 390 1.0 5.0 800 60 82 5.2
Conditions and results of VGO hydrotreating over NiWS/Al2O3 catalyst
Topics 1. Development of new sulfide catalysts
1.1 New molecular precursors of active phases 1.2 Effect of composition and morphology of active phase species on
catalytic properties 2. Catalysts for deep hydrotreating of oil fractions
2.1 Trimetallic NiCoMoS catalysts with enhanced HDS & HYD activities 2.3 NiW/Al2O3 catalysts prepared with heteropolycompounds
3. Catalysts for selective hydrodesulfurization of FCC gasolines 3.1 Trimetallic KCoMoS catalysts with improved HDS/HYDO selectivity
4. Catalysts for co-hydrotreating of diesel and vegetable oil 4.1 Carbon-covered supports for sulfide catalysts
Gasoline fractions
SRGO
VGO
Crude Oil after
Desalting Аtm Dist
Vac Dist
Deep
hydrotreating
Deep hydrotreating FCC
IBP-1800С
180-3600С
360-5000С 180-3600С
100-2200С
Selective hydrotreating
Gasoline
Diesel fuel
…
Deep hydrotreating
> 5000С Coking
Typical components
of regular gasoline
Hydrotreating processes in oil refinery
(Co/Mo)edge
Average length (nm)
HDS/HYDOselectivity factor
0.20.30.4
0.50.6
0.70.8
0.91.0
1.11.2 2.8
3.0
3.23.4
3.63.8
4.04.2
4.41.2
1.4
1.6
1.8
2.0
2.2
2.4
2.6
HDS CoMo edge site HYDO
CoMo corner site
CA NTA
TA
Towards control of selectivity factor HDS/HYDO in FCC gasoline HDT: background
[Co(Ligand)]-Co2Mo10Al2O3 catalysts
Preparation of KCoMoS/Al2O3 catalysts and their textural properties
31
PМо12HPA
Al2O3 Sg= 220 m2/g,
Vp= 0.747 сm3/g
Kх-(CA)-PMo12/Al2O3
in oxide form
Catalysts in sulfide form
Citric acid
КОН Co6(CA)-Kх-PMo12/Al2O3 in oxide form
СоCO3
Catalysts in sulfide form
Catalyst Metal content (% wt.) Textural characteristics
Mo Co K SБET (m2/g) Vp (сm3/g) R (Å)
PMo12/Al2O3 12 - - 169 0.30 67 К5%(CA)-PMo12/Al2O3 12 - 5 92 0.28 67 К10%(CA)-PMo12/Al2O3 12 - 10 73 0.27 67 К15%(CA)-PMo12/Al2O3 12 - 15 47 0.19 67
Co6(CA-PMo12/Al2O3 12 3.7 - 178 0.36 67 Co6(CA)-К5%-PMo12/Al2O3 12 3.7 5 111 0.35 67 Co6(CA)-К7.5%-PMo12/Al2O3 12 3.7 7.5 94 0.34 59 Co6(CA)-К10%-PMo12/Al2O3 12 3.7 10 58 0.23 59 Co6(CA)-К15%-PMo12/Al2O3 12 3.7 15 23 0.10 59
Physical-chemical properties of synthesized catalysts: NH3-TPD and Raman spectroscopy
9 84
800 900 1000 1100
936
885
936
855
Wavenumber (cm )-1
881
926
0 wt. %
5 wt. %
10 wt. %
15 wt. %
955
CoMoO4
νMo=Mo 940 and 818 cm-1
K2MoO4
νMo=Mo 875 and 820 cm-1
J.A. Bergwerff et al. // J. AM. CHEM. SOC. 126 (2004) 14548
Polymolybdate entities are formed
G. Mestl, T.K.K. Srinivasan // Catal. Rev.-Sci.Eng. 40(4) (1998) 451
Mo4(Citrate)2O114-
νMo=Mo 944, 901 and 860 cm-1
Mo(HxCitrate)3O11(4-x)-
νMo=Mo 933, 901 and 861 cm-1
Raman spectra of Co(CA)-Kx-PMo12/Al2O3 catalysts
NH3-TPD profiles of Co(CA)-Kx-PMo12/Al2O3 catalysts
32
Potassium decreases the amount of acidic sites on the catalyst surface.
Poymolybdate entities are saved on the oxidic catalysts within investigated potassium content (5-15 wt. %).
Physical-chemical properties of synthesized (K)Mo and (K)CoMo catalysts: XPS and TEM
Catalyst Relative particles amount (%)
(nm) CoMoS Co9S8 Co2+ MoS2 MoSxOy Mo6+
PMo12/Al2O3 - - - 70 10 20 3.4 1.6
К5%-PMo12/Al2O3 - - - 80 7 12 3.9 1.6
К10%-PMo12/Al2O3 - - - 82 8 10 - -
К15%-PMo12/Al2O3 - - - 86 7 7 5.8 2.4
Co(CA)-PMo12/Al2O3 57 13 30 70 16 14 3.8 1.5
Co(CA)-К5%-PMo12/Al2O3 63 12 25 74 14 12 4.6 1.8
Co(CA)-К7.5%-PMo12/Al2O3 66 10 24 74 12 14 - -
Co(CA)-К10%-PMo12/Al2O3 - - - - - - 5.4 2.1
Co(CA)-К15%-PMo12/Al2O3 74 5 21 82 10 10 6.3 2.4
L N
Potassium improves: the sulfidation degree of active metals with
more selective formation of CoMoS phase; the growth of average slab length
Potassium partially insert in sulfide slab with changing the nature of active sites and probably with formation of new type of active sites.
K+
K+
K+
10 nm
33
Hydrotreating of model gasoline
Kx-PMo12/Al2O3
Co(CA)-Kx-PMo12/Al2O3
34
Al2O3
Conditions: Bench scale flow reactor Feedstock: n-hexene-1 (36 wt.%), thiophene (0.1 wt.% S), n-heptane (solvent) t = 2200C P = 1.5 MPa LHSV = 5.0 h-1; H2/feedstock = 100 NL/L;
5.1=Nnm 3.8=L
Hydrotreating of model gasoline
Kx-PMo12/Al2O3
Co(CA)-Kx-PMo12/Al2O3
34
K+
K+ K+
K+
K+ K+
K+
Conditions: Bench scale flow reactor Feedstock: n-hexene-1 (36 wt.%), thiophene (0.1 wt.% S), n-heptane (solvent) t = 2200C P = 1.5 MPa LHSV = 5.0 h-1; H2/feedstock = 100 NL/L;
Al2O3
5.1=Nnm 3.8=L
Hydrotreating of model gasoline
Kx-PMo12/Al2O3
Co(CA)-Kx-PMo12/Al2O3
34
K+
Al2O3
K+ K+ K+
K+
K+
Conditions: Bench scale flow reactor Feedstock: n-hexene-1 (36 wt.%), thiophene (0.1 wt.% S), n-heptane (solvent) t = 2200C P = 1.5 MPa LHSV = 5.0 h-1; H2/feedstock = 100 NL/L;
4.2=Nnm 6.3=L
Hydrotreating of model gasoline
Kx-PMo12/Al2O3
Co(CA)-Kx-PMo12/Al2O3
34
K+
Al2O3
K+ K+ K+
K+
K+
4.2=Nnm 6.3=L
Promoting catalysts by potassium leads to the partial poisoning the active sites.
Potassium increases the sulfidation degree of metals, content of CoMoS phase and average slab length
K+
Al2O3
K+ K+ K+
K+
Hydrotreating of model gasoline
Kx-PMo12/Al2O3
Co(CA)-Kx-PMo12/Al2O3
Promoting catalysts with potassium leads to the partial poisoning of the active sites.
34
K+
Potassium increases the sulfidation degree of metals, content of CoMoS phase and average slab length
Al2O3
CH2CH2
H2S +
CH2CH2
H2S +
K+
Al2O3
K+ K+ K+
K+
Hydrotreating of model gasoline
Kx-PMo12/Al2O3
Co(CA)-Kx-PMo12/Al2O3
34
K+
Olefin HYD is more sensitive to potassium than HDS reaction.
Al2O3
CH2CH2
H2S +
CH2CH2
H2S +
D. Ishutenko, P. Nikulshin et al. // Catal Today (2015)
Promoting catalysts with potassium leads to the partial poisoning of the active sites.
Potassium increases the sulfidation degree of metals, content of CoMoS phase and average slab length
35
Nikulshin et. al. Patent of RF
Heavy FCC gasoline hydrotreating over KCoPMo12/Al2O3 catalysts
FCC gasoline
28 - 110°С
110 - FBP°С
Merox
Selective HDS
Blended product
RON = 91.2S cont. = 49.4 ppmOlefins = 19.8 wt. %
RON = 91.2S cont. = 12.0 ppmOlefins = 22.6 wt. %
RON = 91.7S cont. = 92.1 ppmOlefins = 13.5 wt. %
RON = 91.6S cont. = 14.0 ppmOlefins = 12.9 wt. %
Split
ter
RON = 91.0S cont. = 13.0 ppmOlefins = 19.6 wt. %
HYDO = 4.4 % HDS = 84.8 %
Saving octane number!
Topics 1. Development of new sulfide catalysts
1.1 New molecular precursors of active phases 1.2 Effect of composition and morphology of active phase species on
catalytic properties 2. Catalysts for deep hydrotreating of oil fractions
2.1 Trimetallic NiCoMoS catalysts with enhanced HDS & HYD activities 2. NiW/Al2O3 catalysts prepared with heteropolycompounds
3. Catalysts for selective hydrodesulfurization of FCC gasolines 3.1 Trimetallic KCoMoS catalysts with improved HDS/HYDO selectivity
4. Catalysts for co-hydrotreating of diesel and vegetable oil 4.1 Carbon-covered supports for sulfide catalysts
Publication evolution by Scopus database
0
50
100
150
200
2010 2025 2050 Fuels from oil Bio-fuels
4,0 mln.
L/year
EJ/year
Consumption of energy by transports (Shell)
Bio-oil
Amount
Oil refining industry
+Н2
Wood biomass
Triglycerides of fatty acids
Bio-diesel
Re-esterification СН3ОН
Green diesel
Co-processing of bio- and oil raw materials
Pyrolysis
36
New fuels
Production of biofuels
Guaiacol HDO
Catalytic properties: guaiacol HDO
XMo6/Al2O3
OHOMe
DME
CH3+or CH4
OHOH OH
HYD
OH
DDO
OHOH OH OH
HYD+
Conditions: Bench scale flow reactor Feedstock: guaiacol (3 wt.%), DMDS (0.6 wt.% S),
toluene (solvent) t = 250 0C; P = 3.0 MPa; LHSV = 50 h-1; H2/feedstock = 500 NL/L; mcat = 0.2 g
0.0
2.0
4.0
6.0
8.0
10.0
12.0
Cr Mn Fe Co Ni Cu Zn Ga
kHDO × 103, mol/(g·h)
%1001 InitHDO
StatHDO
HDO ×
−=
xxDea
)1ln(HDO HDOxWFk −−=
0
10
20
30
40
50
60
Cr Mn Fe Co Ni Cu Zn Ga
Dea, %
TOS = 15 h
Activity
Deactivation
37 Anderson type XMo6HPA
Support Content Textural properties
carbon, % wt.
acid sites (μmol NH3/g)
SBET, (m2/g)
Vp (cm3/g)
Rav (Å)
Al2O3 - 200 208 0.62 48 Al2O3-ZSM-5 - 233 240 0.67 48 Al2O3-BETA - 308 263 0.66 48 C6/Al2O3 5.6 142 184 0.49 48 Sibunit (C) 99.4 10 233 0.41 19
Ammonia TPD profiles for modified supports
38 Effect of support acidity of CoMo catalysts on their activity in guaiacol HDO
0
20
40
60
80
100
0 50 100 150 200 250 300 350Acidity,
μmol NH3/g
Dd, %
DdGua
DdHDO
C C6/Al2O3
Al2O3
Al2O3-ZSM-5
Al2O3-BETA
0 10 20 30 40 50 60 70 80
0 2 4 6 8 10
HD
O c
onve
rsio
n (%
)
Time-on-stream (h)
C Al 2 O 3 - ZSM - 5 Al 2 O 3 - BETA Al 2 O 3 C 6 /Al 2 O 3
CoMo catalysts supported on alumina modified carriers were prepared
Catalysts were tested in guaiacol HDO reaction
P. Nikulshin et al. Catal Ind 6 (2014) 338
Co(CA)-PMo12HPA catalysts Deactivation vs support acidity
Selectivity С18 /С
17
Dea
ctiv
atio
n de
gree
(%)
0.0
0.3
0.6
0.9
1.2
1.5
1.8
0.0
5.0
10.0
15.0
20.0
25.0
30.0
35.0
0 1.0 5.0 Carbon content in C/Al2О3 (% wt.)
30
40
50
60
70
80
90
100
0 1.0 5.0
280 0C 300 0C 320 0C
xHDO (%)
Carbon content in C/Al2О3 (% wt.)
Activity of Co-PMo/С/Al2O3 catalysts in oleic acid HDO 39
P. Nikulshin et al. Catal Today (2015)
Al2O3
Co-PMo/Сx/Al2O3 catalyst
+H2
+ H2S+ H2
– H2S
+H2
– H2O
+H2
+H2
+H2
+H2
+H2
+H2
+H2
HDO pathway
DEC pathway
– CO
– CO
– H2O
+H2
– H2O
C17H35
O
OH
C17H32
C17H34 CH2
C17H33
O
OH
C17H35
O
H
– H2O
+ H2S
C17H36
C17H34
– CO– H2O
C18H38
C17H35 CH2SH
C17H35 CH2OH
C17H33 CH2OH
– H2O
C17H33
O
H
– H2O
Oleic acid
+H2 – H2S
Heptadecene
Heptadecane
Stearic acid
Heptadecyne
OctadecaneOctadecene
Octadecenol
Octadecanol
Octadecanal Octadecanthiol
Octadecenal
РПС
РПС
ВОДО
РОД
АЗОТ
ВЗ(3)
ВЗ(6)
ВЗ(8)ВЗ(7)
ВЗ(9)
ВЗ(2)
ВЗ(5)
ВЗ(1)
ВЗ(4)
ВP(2)
КМ1(0-100)
М4(0-100) М2
(0-10)
М (0-10)
1ВЗ(12)
РРГ1(0-30 nl/h)
РРГ2(0-30 nl/h)
Ф
Ф
PV300SV300
PV300SV300
ALARM
ОК
TT
РДС
ВР(1)
Сброс
СНД
СВД
Х
Р
РТ
T
ИТ
EВЗ(10)
ВЗ(11)НЖ
М3 (0-160)
Ф
Сырье
Обезвоздушивание
Ф
FLO W RA TE 50 ML/MINFLO W RATE 50 ML/MIN
FL OW RATE 50 ML/ MINFL OW RATE 50 ML /MIN
БПИ
ОК
ОК
М5 (0-16)
ВИУ
H2S/
H2
РПСИРГ( )up to 5 nl/h
ИРГ(Н2 30 )up to nl/h
ИРГ( )up to nl/h10
ВТР
ВТР
(0,6-300,0 )g/h
БОГ
AIR
СДГ
ПК
Co-hydrotreating o SRGO with sunflower oil (SO) in bench-scale flow reactor
Conditions: t = 280 - 380 0C; P = 4.0 MPa; LHSV = 1.0 – 4.0 h-1; Н2/feed = 500 nL/L; Vcat = 15 сm3
Item SRGO (100 wt.)
SRGO (85 % wt.) + SO (15 % wt.)
Cetane number, p. 49 50 Total sulfur content, ppm 9209 8031 Density at 20 0С, kg/m3 0.837 0.849 Distillation: - IBP - 10% at temperature - 50% at temperature - 90% at temperature - 95% at temperature
186 217 278 344 365
190 217 284 364 372
Flash point, 0С 75 74 Pour point, 0С - 6.5 - 5.5 Iodine number, g I2/100 g 1.5 20.2
Mixture with 5, 10 and 15 % of sunflower oil with SRGO were used
Characteristics of used feedstock
40
)1(
101
HDS nCСk
nS
nS
−⋅−
=−−
τ
Catalyst ΔT for 50 ppm S
(0C) Co-РMo/Al2O3 +19 Ni-РMo/Al2O3 +3 Ni-РMo/C2/Al2O3 -
Necessary temperature increase (ΔT) to produce diesel with S = 50 ppm from
SRGO and SO 15 %
Dependence of S content in the hydrogenated products on time contact
41
Co-PMo12/Al2O3 catalyst
0 100 200 300 400 500 600 700 800
0.00 0.25 0.50 0.75 1.00 1.25
Sulfu
r con
tent
(ppm
)
1/LHSV (h)
SRGO (100%) SRGO (85%) + SO (15%)
0
50
100
150
200
0.0 5.0 10.0 15.0 20.0
Rem
aini
ng S
con
tent
, ppm
Sunflower content in mixture with SRGO (wt. %)
Co - PMo /Al 2 O 3 Ni - PMo /Al 2 O 3 Ni - PMo /C 2 /Al 2 O 3
Hydrogenated products from SRGO and SO
SRGO (85 % wt.) + SO (15 % wt.)
SRGO
Full conversion of triglycerides
600110016002100260031003600
Волновое число, см -1
а
б
в
-С-H st
=С-H st
-СH2 δ
С=О st С-О-С st
-СH3 δ-(СH2)n-
Wavenumber (cm-1)
Co-hydrotreating o SRGO with sunflower oil (SO) in bench-scale flow reactor
Co(Ni)-PMo/Sup catalysts in co-hydrotreating of SRGO with sunflower oil: accelerated deactivation
Catalyst Sulfur content (ppm)
Cetane number
Pour point (˚С)
Deactivation HDS (%)
Coke content (% wt.)
Deactivation HDS (%) SRGO + LCO+LCGO []
Co-РMo/Al2O3 170 55.0 -0.5 318 7.3 15-30 Ni-РMo/Al2O3 70 55.0 -0.5 263 6.1 - Ni-РMo/C2/Al2O3 50 55.0 -0.5 184 5.7 -
Time-on-stream (h)
T = 340 0C, P = 4.0 MPа,
LHSV = 2.0 h-1, HTO = 500 nL/L,
Feedstock: SRGO+SO
T = 340 0C, P = 4.0 MPа,
ОСПС = 2.0 h-1, HTO = 500 nL/L,
Feedstock: SRGO+SO
T = 340 0C, P = 4.0 MPа,
LHSV = 2.0 h-1, HTO = 500 nL/L,
Feedstock: SRGO
R2
R1 Co-РMo/Al2O3
Ni-РMo/Al2O3
Ni-РMo/C2/Al2O3
AD T = 380 0C, P = 1.0 MPа,
ОСПС = 2.0 h-1, HTO = 150 nL/L,
Feedstock: SRGO+SO
0
100
200
300
400
500
600
700
800
900
1000
40 60 80 100 120 140 160 180
Sulfu
r con
tent
(ppm
)
P.A. Nikulshin et al. // Appl. Catal. B 158–159 (2014) 161
42
Instead of conclusions
Hydroprocessing Active phase composition
Active phase morphology Promoter degree of Mo(W)S2 edges
(Co(Ni)/Mo(W))edge Content of active sites
Со(Ni)Mo(W) (% wt.)
Hydrogen activation and
spillover Average stacking
number of Mo(W)S2 Average length
L (nm)
Gasoline hydrotreating
CoMoS NiMoS ≥ 1 2 – 4 0.1 – 0.6 > 0.6 Necessary
FCC gasoline selective hydrotreating
KCoMoS ≥ 1 ≥ 5 0.9 – 1.0 0.6 – 0.9 Unnecessary
Diesel hydrotreating CoMoS, NiMoS,
NiCoMoS ≥ 1.6 2 – 3 0.3 – 0.5 > 1.2 Necessary
VGO hydrotreating NiMoS,
NiCoMoS, NiWS,
NiMoWS ≥ 1.6 3 - 4 0.3 – 0.7 > 1.5 Necessary
Co-hydrotreating of diesel and vegetable oil
NiMoS, NiWS,
NiMoWS ≥ 1.6 2 – 3 0.3 – 0.7 > 1.3 Necessary
43
NL
MoS2
Principals of molecular designing of hydrotreating catalysts
TOFXMS = f(Mor(N, L), (X/M)edge) × f(P, T) × f(Spillover)
PhD students A. Mozhaev (2012) D. Ishutenko (2013) V. Salnikov (2014) P. Minaev (2015)
Al. Pimerzin (2015) A. Varakin (2016)
Acknowledgments
Ministry of Science and Education of Russian Federation
Prof. and Drs. Prof. A. Pimerzin Prof. N. Tomina Dr. A. Layshenko Dr. V. Zvetkov
Samara State Technical University
M.V. Lomonosov Moscow State
University
Dr. K. Maslakov
N.D. Zelinsky Institute of Organic
Chemistry
Prof. V. Kogan Dr. V. Dorokhov
Russian Foundation for Basic Research
Thank you for your attention!