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Lecture

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CEE-Lectures on Industrial Chemistry

• Crystallization as an example of an industrial process (ex. of Ind. Inorg. Chemistry)

� Fundamentals (solubility (thermodynamics), kinetics, principle)� Process design (reactors, processes)� Applications, example: KCl

• Chem. Process Technologies: From raw materials to final products (ex. of Ind. Organic Chemistry

� Fossile resources as raw materials of the chem. industry & energy sources: From the resources to the base materials (general aspects)

� Resources � Base materials and selected intermediates• Oil � ETHENE and its “family tree”• Oil/nat. gas, coal � syngas � METHANOL and selected intermediates

� Fine chemicals manufacture

energy – raw material – product-network

Part of the resources as raw materials for chemical industry [%]

Rawmaterial

World (1980)today

FRG (1980)

FRG (1991)

Germany (2005)

Oil 56 55 76 82 77

Gas 25 27 9 8 10

Coal 11 10 9 2 3

Renewableresources

8 8 6 8 10

Part of coal as source for base chemicals:

• benzene (3 -17 % worldwide)

• condensed aromates/heteroaromates (95 %) – bit. coal tar

• C2H2, technical C (soot, graphite)

• …coke � steel industry, synthesis gas

From the resources to the base materials

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coal

natural gas

nuclear energyhydroelectricity

oil

1977

26,5 %

4,7 % 1,6 %20,3 %

46,9 %

2002

25,8 %

6,2 % 6,7 %

24,3 %

37,0 %

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Perspectives of world energy supply

World energy consumption(billion t bit. coal units)

Coal

Oil

Natural gas

HydropowerNuclear energy

Other renewable energies

How long do the resources last? (range of availability)

Source: BMWA-Dok. Nr. 519

Oilconventional

conventional + non-conventional

Natural gas

Hard coal

Brown coal

Uranium

Reserves:feedstocks that can be exploited with technical possibilities economi-cally (at present)

Resources:technically and/or economically not exploitable at present

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Composition of oil and natural gasOilC 85-90 wt.-% (paraffins, cycloalcanes, aromates)H 10-14O 0-2N 0.1-2S 0.1-7Metals (V, Ni, Na) traces

„wet gas“

„dry gas“

Further: „acidic gas“ (e.g. Lacq/F: 15.2 wt.-% H2S), „inert rich gas“ (e.g. Panhandle/USA: 14.3 wt.-% N2 and 0.7 wt.-% He)

Primary oil treatment1. Removal of salt (extraction)2. Atmospheric distillation (valve tray column � 60 m, capacity � 20000 t/day)

Products of atm. distillation

130°C

main column

(fractionator)

condenser

steam

steam

strippers

strippers

stripper

„straight-run-gasoline“

column

(Heavy) gas oil (...C25)225-350 °C

Atmospheric residue> 350 °C

Naphtha (C7-C10)75-175 °C

Light gasoline (C5-C7)20-75 °C

Liquid gas (C2-C4)≤ 20 °C

Kerosene (C11...)175-225 °C

Vacuum distillation(40-70 mbar, 400 °C,� lubricating oil, heavy fuel oil, vacuum residue)

Removal of salt Atmospheric distillation(first step in both a gasoline refinery and a petro-chemical refinery)

crude oil

condensatecollector

steam

water+ surfactants

extraction

furnace350°C

salt watersteam

reflux

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Cracking processes

Aim: decrease of chainlength by converting heavier to lighter fractions

Thermal processes Catalytic processes

Visbreaking Coking(delayed coking)

Catcacking Hydrocracking

Reactionconditions

Short-term thermal480-490°C

Longer-termthermal>490°C

Catalytic480-540°C

Catalytic crack. & hydrogenation300-450°C

Frequentfeedstocks

Atmosphericresidue

Vacuum residue Heavy oil fractions

Yields [%]GasesGasolineNaphtha/keroseneHigh boiling prod.coke

2513800

720271729

21472075

controllable, e.g.

185515120

72854110

Desired products High boilingproducts

Petrolium coke Middle distillates

Flow scheme of a complex oil refinery (gasoline)Distillation Refinery + Mix ing Pro ducts

Hydrotreating : 400°C, 20 MPa H2, CoO/MoO3 (γ-Al2O3) � removal of catalyst poisonsReforming : 490-540°C, 1-4 MPa H2, Pt (γ-Al2O3) � decrease H-content, isomerization, cycliz. � increase RONCracking (thermal/catalytic) : decrease chainlength (heavier to lighter fractions)

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Simplified scheme of a petrochemical refinery

Aim : production of low molecular organic base chemicals

(D-distillation)

Aromates

1530 14

Butenes8

Pentenes28

≥ C5: Pyrolysis benzine (source for BTX-aromates)

crude oil

atmospheric distillation

decrease H, isomerization, cyclization

700…900 °C

1600…2000 °C

CH4

ethenepropene

(CH4, C2H6, C3H8)

gases

Steam cracking(mid T pyrolysis)

High temperat. pyrolysis

Isolation ofaromates

aromates

non-aromates

benzenetoluenexyleneparaffines

C4-separation

Product distribution[wt.-%]

butadieneisobutenen-butenesbutanes

C5-separation

isoprenecyclo-pentadiene

acetylene

pyrolysis benzine

gases

Chemical treatment of coal – coal conversion products

(P – processing)

Devola-tilization

P

Carbide-Production

900...1400 °C

600...700 °C

Gasification

Hydrogenation P

O2/H2OCOAL

Bergius/Pier

Liqui-faction

Electrothermal reaction (CaO)

direct

indirect

H20

Processes

Aromates

Aliphates/Phenole

F-T-Synthesis

High T carbonization

Low T carbonization

Products

Gas BenzeneTarCoke

CO/H2CH4

GasGasoline, DieselKerosinediff. oil fractions

Ethine

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Oil versus coal

Organic base chemicals produced from oil and coal

High-temperature-pyrolysis

Steam-crackingOlefins

Ethine

Methanol

Aromates

OILReforming

Crack-processes

...

COAL

Motor fuels

Coke

Steam-reforming,Partial Oxidation

Hydrogenation

Plasma-pyrolysis

Carbide synthesis

Carbonization

GasificationSyngas

F-T-Synthesis

Methanol-Synthesis

Mobil-Process

(gasoline, diesel oil...)

Primary treatment of natural gas

Purisol - process,Sulfinol - process � „sweetening“Rectisol -process

cooling

liquid gas

Distillation- higher p- low T, ambient p

Boiling point-164 °C

-269 °C

-88.5 °C

-42 °C

+ 0.65 °C

+ 36.2 °C

(expansion of the compressed crude gas)

crude gasCondensate separator

Glycol dehydration

(triethylene glycol),absorption

and Claus-unit

Dehydration (zeolites)

CondensationD

CO2

sulphur

methane

ethane

propane

butane

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Natural gas purification: absorption-desorption principle

Solvent: triethylene glycol (for H2O removal)

crude gas

purified gas

exhaust gas

solvent (regenerated, unloaded)

solvent (loaded)

Counter-current process mode