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.