CEE-Lectures on Industrial Chemistry

Lecture
1. • 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 energy – raw material – product-network
2.
Fossile resources as raw materials of the chem. industry & energy sources:
From the resources to the base materials (general aspects)
3.
Resources  Base materials and selected intermediates
• Oil  ETHENE and its “family tree”
• Oil/nat. gas, coal  syngas  METHANOL and selected intermediates
4.
Fine chemicals manufacture

Structure of the chemical industry

Source: Moulijn, J.A., Makkee, M., van Diepen, A.: Chemical Process Technology, Wiley 2001

1
 Classification of chemicals
• In chemical industry, one usually distincts between commodities (bulk
chemicals), fine chemicals and specialties
• Bulk and fine chemicals are identified acc. to specifications (what they are);
specialties are identified acc. to performance (what they can do)

Volume Commodities
e.g. Methanol
Ammonia
Acetic acid…
Fine chemicals Specialties

Character

Classification of chemicals on the basis of volume

and character
e.g. advanced intermediates e.g. adhesives Diagnostics
Bulk drugs Disinfectants Pharmaceuticals
Bulk pesticides Dyestuffs Perfumes
Bulk vitamins Photoogr. chemicals Specialty polymers…
Flavour & fragrance chemicals…
Source: A. Cybulski et al.: Fine chemicals manufacture – technology and engineering. Elsevier, 2001

Fine chemicals: General

Fine chemicals (FC): products of high & well-defined purity, manufactured in
relatively small amounts and sold at relatively high price
- reasonable limits: 10.000 t/a and 10 $/kg
- fine chemicals: products of large variety  number exceeds 10.000
- size of global fine chemicals market (1993): 42.000 Mio. $; average annual growth
between 1989 and 1995: ~4.5%*
- 2 trends visible:
(1) custom synthesis: dedicated prod. for a single client; world-wide a 6.000 Mio. $/a business
(2) specialization in production of chemicals grouped in chemical trees characterized by same
chemical roots (compounds) or the same/similar method of manufacturing

Other
Food additives
Dyes & Pigments
Fragrances &
Flavours
Drug industry

Agrochemicals

Division of fine chemicals production by outlet

*Source: Cybulski, A.et al.: Fine chemicals manufacture – technology and engineering. Elsevier, 2001

2
Characteristics of bulk vs. fine chemicals manufacture
Bulk Fine

Volume (kt/a) > 10 < 10

Price ($/kg) < 10 > 10

Added value Low High

Lifecycle Long Relatively short

Processing Continuous Batch-wise

Plants Dedicated Multi-purpose & -product (MPP‘s)

Flexibility Low High
Raw materials quote Relatively high Relatively low
(raw material costs could
represent >80% of total costs)
Labour costs/kg product Low High

Capital investment/kg High Even higher

product (fixed costs could be reduced by pro-
cess simplification..e.g. less steps)
Producers Many Limited number

Waste per kg product Relatively low High

Source: Cybulski, A.et al.: Fine chemicals manufacture – technology and engineering. Elsevier, 2001

Multi-Purpose and Multi-Product-Plants (MPP‘s)

Heart of the plant
Typically consist of:
• Stirred stainless-steel & glass-lined batch reactors with reflux condensers
• Feed systems for gaseous, liquid and solid reactants
• Feed systems for blanketing with inert gases
• Equipment for separation and purification, e.g.

Filters, centrifuges (most fine chemicals are solids!)

fluidized-bed driers, tray driers, rotary driers

Distillation equipment
• Facilities for recovery of solvents
• Storage facilities
• Effluent treatment facilities

Sewage treatment

Liquids and solids incinerators

Off-gas treatment
• Utilities

3
 Batch reactor systems (1)

Heat exchange area limited

(esp. with glass-lined
reactors); internal coil
hinders stirring, cleaning and
inline sensors

When large heat

(1) exchange area needed,
• external heat exchanger:
part of liquid circulated; no
agitator required, liquid
circulation provides mixing
(2) (1).
• when reaction at boiling
point, reflux condenser
can be used (2).

Typical practically used batch reactor systems

Batch reactor systems (2) (special reactors)

• 1 reactant is gaseous (g-l reactions):

Mechanically stirred tank reactor, where gas is supplied
through a sparger plate  semi-batch reactor (1 reactant (g)
continuous, 1 reactant (l) loaded)

Bubble-column reactors

Spray columns
• g-l-s-systems: common when solid catalyst is present

Fixed bed reactors

Reactors with moving catalyst particles
• Suspension reactors (stirred tank, bubble-column, jet-loop
(venturi) reactor) (for fine catalyst particles <200µm)
• (3-phase fluidized-bed reactor (for larger catalyst particles <3mm))

4
Example: Aspirin® production (Bayer trademark)

Synthesis routes to
acetylsalicylic acid

• Salicin isolated from willow

bark (historical/natural route)
• current industrial route via
phenol (Kolbe-Schmitt-
Kolbe-
Schmitt-
reaction: carboxylation)
reaction

Salicylic acid Acetylsalicylic acid

Main reaction: exothermic reaction

of salicylic acid with acetic
anhydride

Acetylsalicylic acid: ester of

salicylic acid (provides the
hydroxyl group) and acetic acid

Production of acetylsalicylic acid (ASA)

- so called dedicated plant (no MPP)
- production volume: ~ 35.000 t/a
(not clearly a fine chem. process)

ASS crystals

(reaction:
(storage) esterification) (crystallization) (downstream processing)

• Glass-lined or stainless-steel batch reactor; solvent: HAc, (CCl4, hydrocarbons)

• Reaction period: 2-3 h; T must be kept below 90°C (∆RH < 0)
• After reaction, liquid product mixture is pumped to a crystallizer, where it is cooled to 0°C
• Suspension is transferred to a filter for mother liquor removal; crystals are washed with solvent,
afterwards slurried and washed again; dried
• HAc as by-product is recovered; solvent and unconverted anhydride are recycled to the reactor