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The Chemistry of Sulfur in Fluid Catalytic Cracking

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The Chemistry of Sulfur in Fluid Catalytic Cracking Catalytic Reduction of Sulfur in Fluid Catalytic Cracking Rick Wormsbecher Collaborators Grace Davison Laboratoire Catalyse et Spectrochimie, CNRS, Université de Caen Ruizhong Hu Michael Ziebarth Fabian Can Wu-Cheng Cheng Francoise Maugé Robert H. Harding Arnaud Travert Xinjin Zhao Terry Roberie Ranjit Kumar Thomas Albro Robert Gatte Outline • Review of fluid catalytic cracking. • Sulfur balance and sulfur cracking chemistry. • Catalytic reduction of sulfur by Zn aluminate/alumina. Fluid Catalytic Cracking • Refinery process that “cracks” high molecular weight hydrocarbons to lower molecular weight. • Refinery process that provides ~50 % of all transportation fuels indirectly. • Provides ~35 % of total gasoline pool directly from FCC produced naphtha. • ~80 % of the sulfur in gasolines comes from the FCC naphtha. Sulfur in Gasoline • Sulfur compounds reversibly poison the auto emission catalysts, increasing NOx and hydrocarbon emission. SOx emissions as well. • World-wide regulations to limit the sulfur content of transportation fuels. – 10 - 30 ppm gasoline. • Sulfur can be removed by hydrogenation chemistry. – Expensive. – Lowers fuel quality. Fluid Catalytic Cracking Unit Products Riser Flue Gas Reactor (~500 ºC) Regenerator (~725 ºC) Reaction is endothermic. 400 tons Catalyst circulates from catalyst Riser to Regenerator. inventory 50, 000 Air Feedstock barrels/day Carbon Distribution H2 ~0.05 % Flare C1 ~1.0 % Flare Petrochem Feed C2-C4 ~14-18 % Naphtha MW ~330 g/mole C5-C11 ~50 % C12-C22 ~15-25 % LCO C22+ ~5-15 % HCO Coke ~3-10 % Regen Catalyst Consumption • 0.25 – 0.75 #’s/barrel • About 300,000 tons catalyst/year world wide, for about 300 refiners. • Consumption depends on feedstock quality, mainly irreversible poisoning by vanadium FCC Catalysts • 10 - 50 % Y type zeolite, usually USY • 0 - 13 % Rare earth on zeolite • 0 - 80 % active silica/alumina matrix • 0 - 50 % binder and kaolin • Single component or blends • Additives for olefins, SOx, NOx, CO • SULFUR REDUCTION TECHNOLOGY Solid acid catalysis Zeolite Y structure Cracking is Catalyzed by Solid Acid/Hydrocarbon Interactions • Initiation: Hydride abstraction by a Lewis site or carbocation ion formation by a Brønsted site. • Propagation: Through primarily β-scission. • Product selectivities governed by stability of product and the precursor carbocation. • Isomerization, alkylation occur readily Formation of carbocation transition states H H CH2 + HZ R CH3 R Z H H R R' + L R CH3 HL H H H + HZ R R Beta scission β H RCZ CH2 CH CH2 CH2 R' H H RCH2 CH2 CH2 CH2 R' H Z R' C Z CH2 CH CH2 CH2 R H Charge isomerization H H Z CH2 CH2 R' CH3 CH2 R H Z Hydride Transfer (simplified) H H H -C -C -C - + H - Cfeed Cfeed + saturate H + H + Z Z Hydride abstraction High Brønsted site density favors hydride transfer. Catalysts can be tailored with high or low site density. Feedstocks • “Average” feed ~ 1.0 wt. % Sulfur • “Average” feed MW ~ 300 gr/mole • ~ one in ten feed molecules contain S • S content ranges from 0 - 4.5 % Sulfur Balance in a FCC Unit Fuel Gas, H2S 40% F Gasoline 5% Feed Sulfur (~0.3%) Saturated Sulfur C Light Cycle Oil 15 % Thiophenes Benzothiophenes C Bottoms 35 % Multi-ring Benzothiophenes Coke, SOx 5 % Sulfur Species in FCC Gasoline (by GCAED) S SH S R Sig. 2 in C:\HPCHEM\1\DATA\D51024A\012R0501.DS Benzothiophene 2.8e5 R R 2.7e5 2.6e5 Methylthiophenol 2.5e5 Methylthiophene 2.4e5 Thiophene Me-THT 2.3e5 C2-Thiophene 2.2e5 Benzenethiol 2.1e5 THT C2-THT C2-thiophenol 2.0e5 C3-thiophenes 1.9e5 1.8e5 1.7e5 20 40 60 80 100 Time (min.) Reaction Pathways of Sulfur Species in FCC Sulfur Species in Feedstock Sulfur Species in FCC Gasoline Multi-Ring Aromatic Thiophenes Alkylbenzothiophenes Alkylthiophenes ? Alkyl Sulfides, Mercaptans (Including cyclic sulfides) H2S + DiOlefin or Olefin Reaction Chemistry of S Compounds (Which Feedstock Sulfur Species End Up in Gasoline?) • Spike a low sulfur (0.3wt% S) base feedstock with model S compounds (0.7% wt% S). • Look for yield changes in Microactivity Testing • Compounds tested: Thiols (octanethiol) Sulfides (di-n-butylsulfide) Alkylthiophenes (n-hexylthiophene, n-decylthiophene) Alkylbenzothiophenes (3- and 5-methylbenzothiophene) Alkyldibenzothiophene (1,10-dimethyldibenzothiophene) Delta Yields of Gasoline Range Sulfur Base Feedstock Spiked with Model S Compounds (0.7% S) 1200 Octanethiol DecylThiophene 3-MethylBenzothiophene 1000 5-MethylBenzothiophene 800 600 Sulfur, ppm Sulfur, 400 200 0 Gasoline Sulfur C2-Thiophene C3-,C4-Thiophene Benzo-Thiophene and Lighter + Thiophenols Delta Yields of Gasoline Range Sulfur Base Feedstock (2.8% S) Spiked with Dimethyldibenzothiophene (0.45% S) 1,10 DiMethyl-DiBenzothiophene 120 100 80 60 40 Sulfur, ppm Sulfur, 20 0 C2- C3-, C4- Thio-phenols Benzo Thiophene Thiophenes thiophene and Lighter Recombination of H2S and diolefin DCR Testing: Polysulfide and diolefin addition to a low sulfur feedstock (1% S) Di-Olefin + Base 2% Di-Olefin Polysulfide Polysulfide Mercaptans, ppm 5.1 7.3 47.4 30.7 C0-C4 Thiophenes, ppm 44.4 50.7 68.0 145.9 BenzoThiophene, ppm 13.3 11.2 11.5 9.9 Reaction Pathways of Sulfur Species in FCC Sulfur Species in Feedstock Sulfur Species in FCC Gasoline Multi-Ring Aromatic Thiophenes Small amount to benzothiophene Alkylbenzothiophenes Benzothiophene by dealkylation Small amount to thiophenols Alkylthiophenes Thiophenes by dealkylation Small amount to benzothiophene Alkyl Sulfides, Mercaptans Thiophenes by cyclization, aromatization (Including cyclic sulfides) H2S + DiOlefin Thiophenes Hydride Transfer Controls Rate of Thiophenic Cracking Hydride-Transfer from feed R R H2S + Hydrocarbon S S Very stable and Less stable and Not-so Lewis basic sulfur More Lewis basic sulfur A Catalytic Approach • Zn Aluminate on γ-alumina. • Solid Lewis Acid. • Used as an additive (~10 - 75%) with FCC catalyst. • Reduces sulfur in gasoline by 20-45% without affecting other yields. • Most of reduction occurs in light (C3-) thiophenes. Why Zn? Zn(AlO2)2 on γ-Al2O3 • Nominal 17 % Zn(AlO2)2 83 % γ-Al2O3 • ~150 m2/gr surface area • Nominal monolayer of zinc (10 % Zn) on pseudo-boehmite • Converted to aluminate at 500 °C • Both Zn(AlO2)2 and γ-Al2O3 spinel structures Lewis Acidity •Zn(AlO2)2 and γ-Al2O3 have only Lewis acidity. •Zn(AlO2)2 increases the Lewis acidity of the γ-Al2O3. • Use pyridine DRIFTS for acid type determination. Probe Lewis and Bronsted Acid Sites by Pyridine-IR analysis 90 80 N 70 ⇑ 60 H 50 40 ZSM-5 30 Kubelka-Munk 20 10 γ -Al2O3 0 -10 -20 1650 1600 1550 1500 N 1450 Wavenumbers (cm-1) ⇓ M N ⇓ M Alumina Lewis acid sites Strong Weak Al Al Zn aluminate/alumina vs. alumina 34 32 30 Lewis Acid 28 26 24 Strong 22 Weak 20 18 16 Alumina Only Kubelka-Munk 14 12 10 8 10%Zn/Alumina 6 4 2 1650 1600 1550 1500 1450 Wavenumbers (cm-1) Simple Additive Approach (No Optimization of Hydride Transfer & sulfur activity) 950 900 FCC base catalyst only 850 ( Zn additive) 10% 800 15 % reduction 750 20% cut gasoline sulfur 700 650 600 64 65 66 67 68 69 70 71 72 73 Conversion, wt% REUSY and Zn aluminate/alumina MAT at 525 °C. Feedstock contains 1% S. REUSY- 95% GO-40 5% GSR-1 Std.Conv. Wt% 70 70 C/O 3.78 3.80 H2 0.05 0.05 C1+C2 1.74 1.73 LPG 16.49 16.21 C5+Gaso 48.67 48.73 LCO 20.27 20.39 640+Btms 9.75 9.60 REUSY + 5 % Zn Coke W% Feed 2.90 3.09 aluminate mercaptans 0.57 0.15 thiophene 55.62 40.35 C1-thiophene 140.22 91.52 tetrahydrothiophene 31.85 10.91 C2-thiophene 151.97 102.06 C3-thiophene + thiophenol 72.91 67.06 C4-thiophene + C1, C2 thiophenol 55.10 57.09 benzothiophene 387.61 365.13 tot w/benzo 895.86 734.28 ex benzo 508.25 369.15 %total S conv 18.0 % ex benzo 27.4 Working hypothesis S S k1 k3 R-R + H2S R k2 R k1 Hydride Transfer Catalyst site density k3 Zn/Alumina Fixed Bed Layered Studies feed Zn Zn Aluminate Aluminate mixed on bottom on top Samples feed Samples Samples intermeadiates products Sulfur Yields vs Zn Aluminate Location FCC cat w/10% Zn Aluminate Feedstock Contains 1.7% S 300 250 200 150 sulfur/ppm 100 50 0 Thiophene C1- Thiophene Tetrahydrothiophene C2- Thiophene C3- Thiophene + C4- Thiophene + C1, Thiophenol C2 Thiophenol FCC Zn Aluminate ABOVE Zn Aluminate MIXED Zn Aluminate BELOW Experimental : operando study at U. of Caen • Reactors : – Classical catalytic reactor – IR reactor cell : Gas inlet Air Kalrez cooling O-ring IR IR Surface beam KBr CaF2 analysis Teflon window holder Sample Heater (wafer) Gas outlet : IR, GC and MS Gas analysis simultaneously : adsorbed species products of a reaction Summary of pure compound operando studies on Zn/alumina and neat alumina • No reaction with thiophene. • Tetrahydrothiophene readily decomposes. • Evidence that paired Lewis/Brønsted sites are the active sites. More work. Reaction of tetrahydrothiophene over Zn/alumina at 723 ºK IR gas spectra during the reaction IR Chemigram THT 1,3-Butadiene THT 55 50 AbsAbs 0.04 45 40 35 30 minmin 25 20 Intensity 15 1,3-Butadiene 10 5 10 20 30 40 50 1800 1600 1400 Wavenumbers (cm-1) Time (minutes) ¾ Consumption of THT ; Work done at U. of Caen ¾ Formation of 1,3-butadiene. Mass spec analysis during reaction with tetrahydrothiophene Ionic current C4H8S C4H6 H2S t (min) Maximize Sulfur Reduction Approach (Optimize Hydride Transfer & sulfur activity) 245 225 205 Control 185 Increase site density + Zn/alumina in blend 165 145 125 cut gasoline sulfur gasoline cut 105 85 Further increase site density + Zn/alumina in blend 65 60 62 64 66 68 70 72 74 76 78 Conversion, wt% Deactivation of sulfur reduction activity 35% 30% 25% 20% 15% % Cut Gasoline Sulfur Reduction 10% 01234567 Days 50% Zn/alulmina in blend Deactivation Mechanism GSR 1.1 Day 7 GSR 1.1 day 2 GSR 1.1 Day 3 50 GSR 1.1 Day 4 GSR 1.1 Day 5 GSR 1.1 Day 6 45 GSR 1.1 Day 1 40 35 Kubelka-Munk 30 25 20 15 1650 1640 1630 1620 1610 1600 Wavenumbers (cm-1) 1.
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