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Heterogeneous catalysis CPT Chapter 9 Ullmann : Ethylbenzene, styrene, phenol, ethylene oxide, ethylene glycol, propylene oxide, maleic and fumaric acids, ... Farrauto and Bartholomew: Fundamentals of Industrial Catalytic Processes, Chapter 7
Acetic acid: homogeneous catalysis VAM: vinyl acetate monomer X PVOH: poly vinyl alcohol EPR, EBR: ethene propene rubber, ethene-butadiene rubber PU: polyurethane EO, EG: ethene oxide, ethene glycol X SM/PO: styrene, propene oxide X PG: poly-glycol PS, EPS: polystyrene, expanded PS BPA, PC: bisphenol A, polycarbonates X
Xylenol: 1,3-dimethyl phenol PPE: poly phenylether, PTBP: para-t-butyl phenol Acrylic acid SAP: superabsorbent polymers NPG: neopentyl glycol m-MMA: methylmethacrylate X INA: iso-nonane alcohol MBS: MMA-Styrene-butadiene PA: phthalic anhydride X
Ethylene Oxide Terephthalic Acid Acrylonitrile Adipic Acid and Caprolactam Propylene Oxide Vinyl Acetate
Petroleum geochemistry
Biochemical processes
Industrial Catalysis
Description Aromatic Alkylation Dehydrogenation Oxidation Paraffin/Isomerization Paraffin Dehydrogenation Resid Hydrocracking
Space-Time-Yield gmol/second cm3 6.8 x 10-7 6.9 x 10-7 2.1 x 10-7 7.0 x 10-6 9.7 x 10-7 1.2 x 10-7
Styrene
Styrene: 30 Mt/y, consumes more than 50% of benzene Found in: CD cases, yoghurt containers, insulation, ... Expanded PS foam (EPS) Acrylonitrile-butadiene-styrene (ABS) Styrene-butadiene rubber (SBR) Styrene-acrylonitrile (SAN) Production: 1. Alkylation of benzene with ethene using acid catalyst.
Catalyst: Lewis acids: AlCl3 (Friedel-Crafts) no more new plants Zeolites: ZSM-5 or MCM-22
Styrene
2. Dehydrogenation of ethylbenzene 85%
Catalyst: K promoted Fe2O3 Alternative: Oxidation route: coproduct of propylene oxide Oxidize EB to peroxide and react with propylene (Seraya, Singapore)
Alkylation to Ethylbenzene
Side reactions: 1. Further alkylations 2. Oligomerization of ethene 3. Isomerization Recycle DEB and transalkylation DEB + B -> EB Alkylation: low T, high p Transalkylation: independent of T, p Excess benzene for selectivity to EB: B/E = 2-16
Characteristics: Homogeneous catalysis, ethylchloride: promotor, Dry benzene (avoid corrosion) Process: 1. Liquid phase alkylator (B/E~2-3), 2. Transalkylator: Unreacted B and recycled DEB; 3. NaOH to neutralize Cl-; 4. Cat recovery is challenging (settlers)
Zeolites-shape selectivity
Pore size of zeolites as compared to dimensions of some molecules EthylBenzene (EB) fits in ZSM-5, poly-EB (PEB) doesnt
Zeolites SiO2 framework. Some Si are substituted by Al -> acid sites Crystalline, stable and porous material
Heterogeneous catalytic (ZSM-5), gas phase process B/ E~8-15 (to reduce coking) expensive B separation No benzene drying T=350 to 450C, p=10-30 bar DEB goes to (small) transalkylator Exothermic cooling by quench
EB dehydrogenation to Styrene
Reaction: similar to steam cracking
Thermo: high T, low p, high steam dilution (coking) 12-17 mol/mol Unlike SC, catalytic process to avoid side reactions Cat: Fe2O3 (K, Cr2O3) Conditions: 600-650 C pEB = 0.1 bar Selectivity: 90% Conversion: 50-70%
Difficult separation: Low T to avoid polymerization Vacuum distilation (special column) Polymerization inhibitor
Ethylene oxide
Production: Selective catalytic oxidation of ethylene, smallest epoxide Third largest consumer of ethylene (13%), 15 Mt/y (99) behind PE and PVC
Use: intermediate for glycol, polyesters (PET) and ethanolamines Two processes for epoxides: 1. Chlorohydrin process (old) 2. Selective oxidation
1. Chlorohydrin process:
Path 1: desired Path 2 & 3: total combustion lower yield Ag only catalyst with high selectivity (>90%) for selective oxidation of ethylene
Ethylene oxide-catalyst
Silver deposited on porous support ("-Al2O3). Support is inert and has low surface area No hydroxyl groups: avoid isomerization to acetaldehyde Finely devided Ag particles (0.1-1 m) 0.05 wt% promotors (Cs, Rb) Promotor (Cl- ) added to feed
Ethylene oxide-process
Selective oxidation: T and selectivity control crucial Below explosion region: 7% oxygen, 20-40 % ethene Multi-tubular reactor many small diameter tubes (2-5 cm) Inerts to control T Ethylene conversion/pass: 8-11 % - recycle Absorb EO (1-2 mol% in exit stream) in water (stripper) Side stream to CO2 absorption to prevent build-up
Air: more purge, higher conversion, less selective Oxygen: CO2 absorption required
Ethylene glycol
60% of EO is converted to ethylene glycol (hydrolysis)
HO O
+ H2O
OH
Process: Non-catalytic, 200C Excess H2O (20-fold) for selectivity Use: anti-freeze (50%) polyesters (PET) (40%)
Propylene oxide
O H3C
Production: 6 Mt/y (06) Singapore: Seraya Processes: 1.! Chlorohydrin (50%) 2.! Indirect oxidation with peroxides No successful direct selective oxidation
CaCl2 : waste! (DOW) Selectivity: 90-95 % Side reactions: Chlorinated products (dichloropropane)
1. EB oxidation: 12-14% conversion; 2. propylene epoxidation. Unreacted propylene is recycled; 3. Dehydration of "-phenylethanol over Al2O3
Acrylonitrile
H2C
Production: 5.5 Mt/y (98) Use: Acrylic fibers (50%), ABS, SAN (30%), adiponitrile for nylon (10%) CN
Early processes from C2: EO + HCN ! HOCH2CH2CN ! H2C=CHCN CH!CH + HCN ! H2C=CHCN Modern process from C3 : ammoxidation of propene (SOHIO)
Acrylonitrile-Sohio process
1960: Standard Oil of Ohio (later BP) 90 % of world capacity Mechanism: complex! Oxidative dehydrogenation Mars-van Krevelen NH addition Also total oxidation Very exothermic
Acrylonitrile catalyst
High-resolution STEM image of a promising acrylonitrile and acrolein catalyst, MoVNbTeO. (Buttrey et al., JPCC 2008)
Acrylonitrile-Sohio process
Very exothermic: -760 kJ/mol (also some total oxidation) Fluidized bed, 420 to 450C and added steam for T control Excess of air, stoichiometric NH3 and propene. 80% conversion, 70-80% selectivity. No recycle Byproduct: HCN and CH3CN (acetonitrile)
Acrylic acid
O
H2C
OH
Production: 2.9 Mt/y (99), large growth Use: coatings (paint), textiles, fibers, adhesives, superadsorbents,...
Byproduct (NH4HSO4)
New process: 3. Selective catalytic oxidation of propene CH2=CHCH3 + O2-> CH2=CHCHO (acrolein) + H2O CH2=CHCHO + " O2-> CH2=CHCOOH Bi/Mo Mo/V
Acrylic acid-process
First step: propene oxidation with air (steam) to acrolein and some acrylic acid Multi-tubular reactor, 350C, 2 bar Second step: acrolein oxidation to acrylic acid ~280C Overall conversion: 90%, selectivity: 75-80% (based on propene)
Methyl methacrylate
H3C O
H2C
Processes: 1. Acetone cyanohydrin (ACH) route (80%) Base catalyzed, 40 C High selectivity 2 steps: 1. Concentrated H2SO4 80 to 140 C 2. + Methanol
Methyl methacrylate
Cyanohydrins: chemistry
Second step and separation a: hydrolysis of CN group, 80-140C, 98% H2SO4 d: esterification with CH3OH e: phase separator: organic (MMA) and H2O/CH3OH/NH4HSO4 h: wash to recover CH3OH and methacrylic acid (byprod) 1.6 kg H2SO4 consumption/kg MMA
1.
2.
Sumitomo (cf. acrylic acid from propene) a: oxidation reactors. a1: Bi/Mo oxide 420C, S ~95 % a2: hetero poly acid b: quencher; c-e: unreacted methacrolein recycled f-h: methacrylic acid separation i: methacrylic acid esterification with methanol j-k: methanol recycle
Methyl methacrylate-economics
MMA: ACH process vs. i-butene oxidation
Maleic Anhydride
O
Production : 1.4 Mt/y (99) Use: polyesters (50-60%), paints Processes: 1. Selective oxidation of benzene (20% in 2000)
H 2O
Multi tubular reactor salt bath cooler T control Catalyst: V2O5, Mars-van Krevelen mechanism Conditions: 400C, 2-5 bar, short residence time (~0.1 s) Low selectivity (~65%), conversion ~90% Partial condensation (c) and Wash with water (d,e) leads to maleic acid
Catalyst: promoted V2O5 both V4+ and V5+ Mars-Van Krevelen mechanism: butane reacts with latice oxygen from catalyst, not from air Reactor (Dupont): riser: butane oxidation regenerator: cat reoxidation, fluidized bed Selectivity: 70-80%, Conversion: 40% No O2-hydrocarbon mixtures Catalyst concern: attrition
Phenol
OH
Production: 7.3 Mt/y (03) Second largest benzene consumer (20%) Use: bis-phenol A (polycarbonates) (37%), phenolic resins, (caprolactam (nylon 6))
Processes: Direct selective oxidation under development Indirect: 1. Benzenesulfonic acid (oldest, no longer used) 2. Oxychlorination to chlorobenzene still used 3. Toluene oxidation to benzoic acid 4. Cyclohexane oxidation to cyclohexanol 5. Benzene + propene -> cumene (Hock process) Cumene + O2 -> phenol and acetone 95% of world capacity
2. Oxidation
1.! Oxidation of cumene to cumene hydroperoxide (CHP) 2.! Cleave CHP in acid medium (H2SO4) Both reactions exothermic, byproducts
Phenol-Hock process
Autocatalytic oxidation of cumene in bubble towers (R1, R2) X1- X3: condensers to recycle cumene VC: vacuum distillation to increase CHP concentration Cleavage in series of heat exchangers (R3-R5) Neutralize product (Na-phenolate)
Phenol-new process
Bis-phenol A
CH3 HO CH3 OH
Production : 2.7 Mt/y (03) Use: polycarbonates, high quality plastics and epoxy resins
Economics: Cash cost same Higher finance costs, because phosgene plant is more expensive (safety!)
Vinyl acetate
O
H3C
CH2
80%
Mechanism: C2H4 + 2* # H* + C2H3* CH3COOH + 3* # CH3COO** + H* " O2 + * # O* C2H3* + CH3COO** # VA +3* 2H* + O* # H2O + 3* Catalyst: Au modified Pd
Vinyl acetate-process
Heterogeneous catalytic process, Pd/Au Recycle gas stream (ethylene) is saturated with AA and mixed with oxygen (<8% - flammability), Multitubular reactor Conversion: E: 8-10%; AA: 15-35%, O2: 90% l, e, m remove 40-50% of the water (m: phase separation) f: recycle washing; h, i, j: purge and manage CO2 in recycle
Vinyl Chloride
H2C Cl
Process: Step 1. Ethylene + Cl2 -> Ethylenedichloride (EDC) a. Direct Chlorination. Liq phase. cat: e.g. FeCl3
b. Oxychlorination. Heterogeneous cat: CuCl2 Mars-van Krevelen mechanism, very exothermic C2H4 + 0.5 O2 + 2 HCl -> CH2Cl CH2Cl + H2O !Hr=-240 kJ/mol
Vinyl Chloride
Oxychlorination catalytic cycle
Vinyl Chloride
Step 2. EDC dehydrochlorination via thermal cracking T: 500-600 C, p: 25-30 bar (compare steam cracking) 50-60% conversion, S~98% PFR, 1000 m long
Balance on HCl
Vinyl Chloride-Oxychlorination
Multi tubular reactor: exothermic reaction Catalyst: CuCl2 on Al2O3 support Quench in d and cooling in heat exchanger e Wash with NaOH (h) Bottom of (i) to Oxy-DC for further purification
EDC cracking furnace (a); quench (b, c) Separation (d, e). NaOH to remove residual HCl Mechanism:
1) ClCH2 CH2Cl ! ClCH2 C!H2 + Cl ! 2) Cl ! + ClCH2 CH2Cl ! ClCH2 C!HCl + HCl 3) ClCH2 C!HCl ! CH2 = CHCl + Cl ! Cl ! + ClCH2 CH2Cl ! ClCH2 C!HCl + HCl etc.
Course overview
1. Raw materials/ Fuels/ Base chemicals/ Intermediates/ speciality chemicals/ consumer products / bulk chemicals Raw material vs. Energy source have idea about oil reserves, usage in petrochemical industry, alternatives, green house problem Refining Different processes: distillation, FCC, HDS, HC, CR, alkylation, flexicoking,... Objectives, main reactions, cat, reactor, process scheme (not too detailed), process conditions (from thermo) Idea of different cuts (naphtha, gasoline, gas oil, vacuum gasoil, kerosene) Octane/cetane number Refinery types (have an idea of the different components why they are there) and future challenges
Syngas production and use Steam reforming: process, cat, conditions, reactor/furnace, main reactions, thermo, deactivation, different steps in process, autocatalytic, partial oxidation, shift reactions,... Coal gasification: main reactions Ammonia, methanol: use, production, reactions, thermo, kinetics, catalyst, process conditions, maximum rate curve, reactor concepts, process, kinetics and selectivity (methanol) Fischer-Tropsch: objective, reaction(s), Schulz-Flory, reactor design
Steam Cracking Process, feed and product, process conditionsrequirements Thermo/kinetics, severity/conversion (influence on product distribution) Process, Furnace (sections, heat flux...), reactor Coke formation and solutions Separation (block diagram not exact T/ps concept) Cooling circuit - principle Idea of alternative processes (dehydro, MTO) Polymerization Chain-growth (Rad. and coord. mechanism), step-growth Derive MWD for step-growth, radical and coordination poly and relation to process conditions Different processes: what are the differences, challenges in process design, cat/initiator, idea of process conditions, types of PE
Heterogeneous catalysis EB and Styrene : thermo, processes (concept recycle), process conditions (E/B,..), catalyst development Selective catalytic oxidation EO: process routes (SCO and chlorohydrin), cat, process (tubular reactor (why?), excess ethylene recycle) PO: the chlorohydrin and co-production processes, reactions, process steps AN: ammoxidation: reactions, cat, idea of process (reactor type)-byproducts Acrylic acid: SCO propene (chemistry, cat, reactor) MMA: reactants, chemistry (ACH and i-butene oxidation, economics) MA, PA: process, mechanism, reactor choice, catalyst, selectivity issues Phenol:
Heterogeneous catalysis Phenol: Hock process. Chemistry, process steps have idea about mechanism. Selective oxidation route, polycarbonates Vinyl acetate: reactions, catalyst, separation Vinylchloride: full chlorine utilization by direct chlorination with Cl2 and oxychlorination with HCl