TECNOLOGÍA QUÍMICA
INDUSTRIAL
ETILENO
Yris González
Videos Etileno
▪ https://www.youtube.com/watch?v=iJhdPorGNEs
Polimeri Europa
Vinyl Chloride (VCM) Polyvinyl Chloride
Ethylene Polyethylenes
Ethylene Oxide (EO) Monoethylene Glycol (MEG)
Propylene Polypropylenes
Allyl Chloride Epichlorohydrin (ECH)
Olefins
Propylene Oxide (PO) Polyether Polyols
Butadiene Butadiene Rubber
Styrene Butadiene Rubber
Oil / Gas
Thermoplastic Rubber
Feedstocks
To Cracker
C5 Olefins Isoprene Isoprene Rubber
Styrene (SM) Polystyrenes
Acetone
Benzene Cumene Phenol Diphenylol Propane Epoxy Resins
Aromatics
Diphenyl methane Di-Isocyanate (MDI)
Polyurethanes
Toluene Toluene Di-Isocyanate (TDI)
Xylenes Para-Xylene Terephthalic Acid (PTA) Polyethylene Terephthalate
Derivados Etileno
Ethyl Benzene
7%
LLDPE/LDPE
34%
Oxide/Glycols
13%
EDC/VCM HDPE
14% 24%
Polyethylene
58%
Other
8%
BASF 2000
Steam
Cracking
Reacciones Quimicas
heat
Simple :
C C C C + H2
(C2H6 800 °C
Ethane) 0.1 second
Mecanismo C2H6 CH3 + CH3
:
C2H6+ CH3 CH4 + C2H5
C 2H 5 C 2H 4 + H
C 2H 6 + H C2H4 +H2 … etc … etc …
Radical Libre…
Vapor como Inerte
7
Reacciones Quimicas
Pero : CH4 + H2O CO + 3H2
CO + H2O CO2 + H2
CH3 , C2H5 C + H2
Coke !
8
Termodinámica
Reacción en equilibrio
Endotérmica
Favorece altas temperaturas
Baja Presión parcial
Dilución con vapor es importante
Cinética
▪ Cinética de Primer Orden
▪ Se favorece con el aumento de la
presión parcial
▪ Sin embargo esto también favorece
las reacciones colaterales.
▪ Por lo tanto la combinación de
variables como temperatura, presión
parcial, y tiempo de residencia, son
una alternativa.
Condiciones Optimas/ Reacción
Esquema Simplificado del Craqueo
Reactor de Craqueo
Reactor de Craqueo
A naphtha steam cracker (900 kt/a) at Shell Moerdijk, the Netherlands
Shell 2003
Hydrogen
Utilities Mixed
Butanes
Gasoline
Material Movements
Acid Gas
Steam Compressor and Propylene
Drier Chilling
Primary NAPD Propane
Fractionator Converter
Quench Ethylene
Feeds
Mixed
Products Ethane
Acetylene
Converter
Ethane
Methane
Quench
Fuel Oil
Cracking
Naphtha Furnaces
Conventional Naphtha-based Steam Cracking Process
IPPC/BREF 2001
Craqueo de Nafta
▪ The product mixture resulting from cracking of gaseous feedstocks is firstly cooled in the
transfer-line exchanger with subsequent cooling by direct quench withwater.
▪ Secondly, the product stream is compressed by multistage compression, typically in four
to six stages with intermediate cooling. Before the last compressor stages, acid gas
components (mainly hydrogen sulfide and carbon dioxide) are removed.
▪ After the last compressor stage, water removal takes place by chilling and drying over
zeolites.
▪ Subsequent fractionation of the cracking products is based on cryogenic distillation
(temperature <273 K) and conventional distillation under pressure (15–35 bar).
Cryogenic distillation is very energy intensive due to the need for a refrigeration system.
▪ The separation by distillation of ethene/ethane and propene/propane mixtures is
difficult: the separation of the former mixture requires 80–150 trays, while in the latter
case over 160 trays are needed . The trays are often placed in two towers in series
Conclusión
▪ Cuales son las reacciones químicas del proceso?
▪ Identifique su termodinámica y cinética?
▪ Defina las condiciones Optimas del Reactor.
▪ Explique el tipo de reactor.
▪ Identifique los procesos de separación de los productos.
▪ Indique las características principales de estos procesos.
▪ Cuales son las nuevas tendencias del proceso
Advanced naphtha steam cracking
▪ Advanced furnace materials (e.g. low coking
coating)
▪ Vacuum Swing Adsorption, mechanical vapor
recompression
▪ Advanced distillation columns, membrane and
combined refrigeration systems
▪ Conclusion: up to 20% energy savings are possible
in the pyrolysis section and up to 15% energy
savings are possible in the compression and
separation sections.
Some Backup Sheets
Why Do Catalytic Olefin Technologies Save Energy?
Energy saving!
Energy
Ren 2003
Process energy required in a pyrolysis furnace
Activation Energy In the case of conventional steam cracking
without catalysts
Process energy required in a reactor
In the case of catalytic olefin technologies
Activation Energy
with catalysts
Thermodynamic Olefins and byproducts
energy
requirement
Ethane, naphtha or other feedstocks
Progress of Cracking Process
Innovative Olefin Technologies
Propane
Ethane Catalytic Hydro-
Gas Stream Oxidative Byproduct upgrading Catalytic Pyrolysis
Oxidative De- cracking of pyrolysis of
Technologies dehydrogenatio (C4-9) Process (CPP)
hydrogenation naphtha Naphtha
n
Crude oil, refinery
Ethane and
Ethane and Propane and C4-C9 (from steam heavy oils,
Feed other gas Naphtha Naphtha
oxygen oxygen cracking, refinery, residues,
feedstock
etc.) atmospheric gas
oil, vacuum gas oil
Ethylene/propyl
Olefins Ethylene Ethylene Propylene Ethylene Propylene Ethylene/propylene
ene
Shockwave, Both a stem
Alloy Catalyst Reactors with
combustion reformer and
Reactor Reactor with Fluidized bed hydrogen co Fixed or fluidized Riser and transfer
gas; shift an (oxy-
hydrogen co feed but less bed line reactor
syngas; reactor); or,
feed steam
plasma; etc. cyclic fixed-bed
Zinc and
Zeolite (or
calcium Acidic zeolite
Mordenite various metal N/a Zeolite
Catalys N/a aluminate (Lewis sites)
zeolite oxides)
t based
Temp. 625-700 900-1100 550-600 650-680 785-825 580-650 650-750
oC
Blachownia:
Shockwave: Uhde: ca. 8-10
Process KRICT: ca. 19 ca. 16-20
ca. 8-10 Dow: ca. 10-12 GJ/t CPP: ca. 35 GJ/t
energy GJ/t ethylene GJ/t ethylene N/a
GJ/t GJ/t propylene; ca. ethylene and ca.
(SEC)i and ca. 10 GJ/t and
ethylene/HV ethylene/HVCs 8-10 GJ/t 12 GJ/t HVCs
HVCs ca. 10-13
Cs HVCs
Uhde: GJ/t HVCs
Dow: final
Shockwave: propylene final KRICT: ethylene Blachownia: UOP: total CPP: ethylene 21%,
ethylene ca.
Yield highest yield ca. 78% 38%, propylene Ethylene yield propylene yield propylene 18%, C4
53% if
(wt. %)j ethylene if weighted 17-20%, 36-40% and from steam cracking 11%, aromatics
weighted
yield ca. against aromatics 30% HVCs yield is 30% and HVCs 15% and
against ethane
90% propane and and HVCs 73% 70% yield 85% HVCs yield 60%
and oxygen
oxygen
Current
Commercially Commercially Commercially Lab and near
status Lab Lab Pilot plant
available available available commercialization
Deshidrogenación de Alquenos
ETILENO Y SUS DERIVADOS
VEA SU ARBOL PETROQUIMICO
Vinyl Chloride (VCM) Polyvinyl Chloride
Ethylene Polyethylenes
Ethylene Oxide (EO) Monoethylene Glycol (MEG)
Propylene Polypropylenes
Allyl Chloride Epichlorohydrin (ECH)
Olefins
Propylene Oxide (PO) Polyether Polyols
Butadiene Butadiene Rubber
Styrene Butadiene Rubber
Oil / Gas
Thermoplastic Rubber
Feedstocks
To Cracker
C5 Olefins Isoprene Isoprene Rubber
Styrene (SM) Polystyrenes
Acetone
Benzene Cumene Phenol Diphenylol Propane Epoxy Resins
Aromatics
Diphenyl methane Di-Isocyanate (MDI)
Polyurethanes
Toluene Toluene Di-Isocyanate (TDI)
Xylenes Para-Xylene Terephthalic Acid (PTA) Polyethylene Terephthalate
Exposición Próxima Clase
▪ Seleccionar su producto petroquímico.
▪ Preparar una presentación de 10 min.
▪ Uno del grupo hará la exposición.
▪ Resto del grupo puede complementar.
