GerardsNotesOnPortOfRotterdamPhysicalFlowTable

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[edit] Gerard's notes on PortOfRotterdamPhysicalFlowTable

[edit] Introduction

Go to this page to see my notes on specific processes implemented: GerardsNotesOnPortOfRotterdamPhysicalFlowTable

Guido's notes on the PoR diagram: User:Gkuijpers

By the way I (Guido) have also updated some stuff below.

Reminder to myself: we did a project on the C4 and C5 network in Rotterdam with Ellis Steenkamp -- digup the report.

Does anyone have a plan what to do about these comments / suggestions / mistakes? The one task I (ChrisDavis) could really use help with is that of gathering more data about the PoR. Perhaps get Maarten, Robert to help out? For the rest, I'll update the wiki and we'll continue to look for problems. This will be done this week. ChrisDavis 18:35, 20 April 2010 (UTC)

[edit] General note / workflow on the PortOfRotterdamPhysicalFlowTable

I have browsed some of the instances, but it appears that the (generic) industrial process representation for many an instance is incomplete and incorrect

  • for example Shell_Chemie_Moerdijk/production_of_Ethyl_Benzene
    • input is 500000 ton benzene
    • output is 400000 ton ethylbenzene
  • input ethylene is missing
  • material efficiency would be very low if these numbers were correct
    • reaction: H2C=CH2 + C6H6 --> C6H5-C2H5
    • the overall industrial efficiency of this reaction is in excess of 95% if not 99%

Suggest I first check the overall completeness of the industrial complex in the model and its structure, and later look at individual numbers around the industrial processes. 

  * What is missing here is an input of ethylene. http://en.wikipedia.org/wiki/Ethylbenzene

Ethylene has been added, but the scale still needs to be fixed. ChrisDavis 16:08, 25 May 2010 (CEST)

[edit] Names & abbreviations

  • BDO = 1,4-Butanediol
  • Isoprene = 1,4-butadiene
  • MEK = Methyl Ethyl Ketone
  • MIBK = Methyl Iso Butyl Keton
  • MTBE = Methyl-Tertiary-Butyl-Ether
  • PO = Propylene-oxide
  • SAN = Styrene AcryloNitrile polymer
  • TBA = Tertiary Butyl Alcohol * http://en.wikipedia.org/wiki/Tert-Butanol

[edit] Lyondell Chemical Botlek/production of TBA

TBA is manufactured in the TBA-PO process: 

inputs: 
iso-butane            2.35 ton
propylene             0.9
oxygen                1.0
outputs:
TBA                   2.45 (co product)
Propylene-oxide (PO) 1.00 (reference prod)
Fuels                4.0 MJ (Not desired, but accepted)

Utilities: 9.5 ton steam, 400 kWh electricity, cooling water 380 m3

Data from Chauvel&Lefebvre 1989 pt.II pg. 19

Generic process: TBA-PO_process ChrisDavis 10:36, 26 April 2010 (CEST)

[edit] Lyondell Chemical Botlek/production of Tertbutyl Hydroperoxide

This process is a PART OF the TBA-PO process. Apparantly, Lyondell has set it up to extract the intermediate product. The TBA-PO process' first step is to oxidize iso-butane to tert-butyl-hydroperoxide 

  * http://en.wikipedia.org/wiki/Tert-Butyl_hydroperoxide
  * the dutch wiki is beter: http://nl.wikipedia.org/wiki/Tert-butylhydroperoxide

TBHP wordt gevormd door de omzetting van tert-butanol met waterstofperoxide, of door de reactie tussen isobutaan en zuurstof. Het ruwe TBHP wordt gezuiverd door middel van destillatie en verkocht als een 70% à 80%-oplossing in water.

[edit] Lyondell Chemical Botlek/production of Propylene Oxide

This process is the second step in the TBA-PO process. The inputs are of course wrong. It does take tert-butyl-hydroperoxide, but no mass is created :-)

[edit] Lyondell Chemical Botlek/production of MTBE

It is listed this process uses MethanolIsobutylene as input. This is a mistake. MethanolIsobutylene is a trivial name for MTBE(see above).

The input-output for the MTBE process is: inputs: isobutylene and Methanol output: MTBE

The conversion efficiency of this process is almost 100%

Lyondell also employs another route to MTBE when TBA prices are low inputs: TBA and methanol outputs: MTBE and water 

  * http://en.wikipedia.org/wiki/Methyl_tert-butyl_ether

TODO this needs to be set up as another OperationalConfiguration. ChrisDavis 16:11, 25 May 2010 (CEST)

[edit] Lyondell Bayer Maasvlakte/production of Propylene Oxide

This is an interesting one.

  • this plant is built using Lyondell technology
  • Bayer took a 50% share in the project, but Lyondell remains the operator
  • Lyondell Maasvlakte is one of the two locations of Lyondell in Rijnmond
  • the third location is the headquarters of Lyondell in Rotterdam
  • the process manufactures PO, but NOT from TBA or something.
  • this is the (formerly ARCO, now LYONDELL) styrene-monomer / propylene-oxide technology or SMPO
  • the process takes in ethylbenzene and propylene
  • it produces styrene and propylene oxide
  • the PO-11 as it is known at Lyondell has a capacity for 285000 ton PO en 640000 ton of SM per year
  • on-stream in 2003
  • so the input of tertbutyl hydroperoxide is not right.

[edit] Lyondell Botlek BDO

This is the newest plant of Lyondell on this site, it produces 1,4-Butanediol or BDO. The capacity is 130000 tons. Completion in 2002 (?). There is no page for this facility yet.

Lyondell uses their propylene oxide as input --> convert to allyl alcohol (see below), which is then hydroformylated and hydrogenated to 1,4 BDO. This is a reaction with 1:1 synthesis gas (CO:H2) and hydrogen or 1:2 syngas.

Chauvel & Lefebvre, pt II page 320: PO --> allyl alcohol + CO/H2 --> 1-butene 1,4-diol + H2 --> 1,4 BDO 

  * This process is NOT named in the list of TechnologiesInPOR

[edit] Lyondell Chemical Botlek/production of Methyl Propanediol

This is a mistake -- 2-methyl 1,3 propanediol is a co-product of the BDO plant

[edit] Lyondell Chemical Botlek/production of Allyl Alcohol

This process is a part of the BDO process. Again, part of the intermediate product is used for other purposes than conversion to BDO. 

  * there is no input named

  * http://en.wikipedia.org/wiki/Allyl_alcohol

[edit] Internet source on Lyondell activities Rotterdam

http://ec.europa.eu/environment/emas/pdf/es_library/24_14nl_lyondell04_nl.pdf

Gives an overview of the activities of Lyondell Botlek.

[edit] Missing Lyondell Facility : Propyleen Glycol Ethers

[edit] Shell Chemie Pernis/production of C5 - Olefins

  • I do not know which process this is. Probably some isolation from an intermediate product from the catcracker in the refinery?
  • Or a process located in Moerdijk, as part of the SteamCracker complex.
    • The latter is the common way to obtain C5 olefins

[edit] Shell Chemie Pernis/production of Iso Propanol

Isopropanol or Isopropyl alcohol is made in Europe and the Botlek by hydrating propylene. C3H6 + H2O --> (CH3)2CHOH

This implies in the infobox one input is missing, water, and the mass balance is not right. The amount of IPA is greater than the propylene input. Alternatively, there maybe some co-production of 1-propanol -- (CH3)(CH2)CH2OH

[edit] Shell Chemie Pernis/production of Methyl Iso Butyl Keton

en.wikipedia has a decent description on this one (exception!) http://en.wikipedia.org/wiki/Methyl_isobutyl_ketone This confirms that for MIBK the mainn input is indeed acetone. Waste product output water is missing, however, as is a small input of hydrogen. From 80000 ton acetone to 45000 ton MIBK seems a bit much - molecular weight of acetone is 58.1, that of MIBK 100.2, so for every two moles of acetone (116.2 gram) you would ideally obtain 100.2 gram of MIB, or some 15% loss of mass).

[edit] Shell Chemie Pernis/production of MTBE

There is a mistake here. Currently, this process appears tho make MTBE out of a vacuum :-).

  • In an oil refinery, MTBE is often produced in situ, saving on separation costs, applying process integration:
    • In a number of streams, e.g. from the catcracker, there are unsaturated C4's present, including isobutylene.
    • if you treat these streams with methanol in the presence of a suitable catalyst, you will get the same stream as a product, but now the iso-butylene is converted to MTBE.
  • problem to represent this process - the isobutylene does not get separated, and the MTBE ends-up in the gasoline pool.
    • this process is part of a (complex) refinery
    • refineries come in three varieties: simple (hydroskimming), semi-complex and complex.
  • so either
    • input is C4-cut (refinery) and methanol
    • output is improved C4-cut with MTBE content (higher RON, research octane number)
  • or input is C4-olefins and methanol
    • output is MTBE
    • co-product possibly saturated C4's
    • in this case, the C4 olefins are isomerized to isobutylene and reacted with methanol

[edit] Shell Chemie Pernis/production of Polyether Polyols

  • The mass balance for this process appears to be allright.
    • Polyether polyols is a generic name for the oligomers of glycols (ethylene glycol, propylene glycol, butanediol);
    • glycol is a synonym or trivial name for a diol, a double alcohol
    • you can create them from the oxides -- ethylene oxide --> ethylene glycol; propylene oxide --> propylen glycol; PO + hydroformylation --> BDO
    • under the right conditions, they will react with themselves: 2 ethylene glycol -- ethylene ether diol HOCH2-CH2-O-CH2-CH2OH + H2O
    • 2 propylene glycol -- propylene ether diol HOCH(CH3)-CH2-O-CH(CH3)-CH2OH + H2O
  • what may be seen is that with mixtures, any oligomeric ether / diol can be created
    • this is used to tune their properties (e.g. in your polyether matress) and in polyurethane foam, of which polyehter polyols are a constituent

[edit] Shell Chemie Pernis/production of SAN Polymer Polyols

There is something wrong here.

  • Styrene Acrylonitrile (SAN) - Styrene and acrylonitrile monomers can be copolymerized to form a random, amorphous copolymer that has improved weatherability, stress crack resistance, and barrier properties. The copolymer is called styrene acrylonitrile or SAN. The SAN copolymer generally contains 70 to 80% styrene and 20 to 30% acrylonitrile. This combination provides higher strength, rigidity, and chemical resistance than polystyrene, but it is not quite as clear as crystal polystyrene and its appearance tends to yellow more quickly.

[edit] Shell Chemie Pernis/production of n-Butene

  • there is a mistake in the mass balance / streams: no data listed
  • n-Butene is probably a synonym for 1-Butene.
  • again, this is either part of the refinery, but more probably part of the SteamCracker complex in Moerdijk
  • C4 olefins can be isolated from catcracker (refinery) but more obvious from SteamCracker
  • isomerisation, isolation and recycle to get only 1-butene from a mix of butenes
  • 1-butene is important in polyethylene manufacture LLDPE is made polymerizing ethylene, grafting 1-butene (4-8 wt.%) in the chain to modify the LLDPE characteristics
    • i.e. input is mixed C4 olefins
    • output is 1-butene and saturated C4 hydrocarbons
  • Recap:
    • 1-Butene in Pernis for rubber production
    • 2-Butene in Moerdijk for Petrol production
    • n-Butene is not a usefull description

[edit] Shell Chemie Pernis/production of Acetone

This process has no inputs -- acetone out of a vacuum :-)

  • Need to check, but this most probably is made out of cumene (see above): Acetone is produced directly or indirectly from propylene. Most commonly, in the cumene process, benzene is alkylated with propene and the resulting cumene (isopropylbenzene) is oxidized to give phenol and acetone
    • C6H5CH(CH3)2 + O2 → C6H5OH + (CH3)2CO
    • so inputs are cumene and oxygen
    • outputs are phenol and aceton
  • In Germany, the older Wacker process - direct oxidation of propylene is also employed, but this is not state-of-the-art anymore I believe

[edit] Shell Chemie Pernis/production of MEK

This process has no inputs -- MEK out of a vacuum :-)

  • MEK is similar to acetone, with one extra C: CH3C(O)CH2CH3.
  • it is made from oxidizing 2-butanol, which in itself is made by hydration of 2-butene CH3CH(OH)CH2CH3 → CH3C(O)CH2CH3 + H2
  • thus, this may be a process of 2-steps again

[edit] Shell Chemie Pernis/production of C4 - Olefins

This process yet has no inputs nor outputs.

  • see my remarks above == this is either a process in the refinery, or part of the SteamCracker complex in Moerdijk
  • this process is not listed in the TechnologiesInPOR

[edit] Shell Chemie Pernis/production of Isoprene

This process yet has no inputs nor outputs.

  • isoprene is the trivial name of 1,4-butadiene, the basic constituent of artificial rubber
  • if I recall correctly, it is made out of dehydrogenation (removing hydrogen) from 1- or 2-butene (check)
  • inputs / outputs follow from earlier work

[edit] Shell Chemie Pernis/production of Propylene

This process has no input. The capacity appears to be OK.

  • this is the propane / propylene splitter that Shell operates in joint venture with I believe Nerefco (BP/Texaco)
  • the input is C3 from both these companies' catcracker distillation sections
  • this separation is one of the most difficult, requires a very tall distillation column with a lot of trays. Also operates at very low temperatures (-90 degrees Celsius)

[edit] Shell Chemie Pernis/production of Isobutane

This process yet has no inputs nor outputs.

  • this is probably one of the processes in the refinery, to isolate isobutane from C3/C4 (LPG) as a valuable feedstock
  • isobutane --> isobutylene upon dehydrogenation
  • need to check earlier work for details

[edit] Shell Chemie Pernis/production of Glycol Ethers

See remarks above on Polyether Polyols

  • this is probably a precursor to or part of that facility
  • these units contain subunits to be flexible in the exact oligomeric polyol or glycol ether to produce
  • http://en.wikipedia.org/wiki/Glycol_ethers
  • Shell Chemicals says it will invest "tens of millions of guilders" to build a 100,000-m.t./year propylene oxide (PO)-based glycol ether plant at Pernis, the Netherlands. Work on the plant is under way and it should be onstream by the end of 2001.
  • http://www.icis.com/Articles/2002/04/30/170937/going-global.html: The plant is 100000 tons per year and it produces a number of products. The new plant began on-specification production at the end of November 2001 and manufactures Methyl Proxitol, MethyldiProxitol and Ethyl Proxitol. It is sited alongside an existing multi-purpose plant in Pernis that will continue operating and will focus on producing 65 000 tonne/year of ethylene oxide (EO) glycol ethers and brake fluids.
  • the 165000 output seems to be wrong.

[edit] Fixed - Lyondell Chemical Botlek/production of Propylene Glycol

This process uses PO as input PO + H2O --> PG

[edit] Fixed - Shell Chemie Pernis/production of Cumene

This process produces Cumene out of Benzene and Propylene C6H6 + C3H6 --> C6H5-C(CH3)2

The propylene input is missing.

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