CHE 3163 Sustainable Processing 1

Waste Identification and Minimisation in Reactors

Reading: Brennan Chapter 4 (pp. 55-80)

Subject matter today
Explore sources of waste and their minimization in reaction systems

Hierarchy of Process design - Onion diagram

how to identify and minimise wastes

Checklist for reaction systems and reactors

Chemistry of process route

Environmental effectiveness

Co-product and by-product utilisation

Impurities in feed

Mixing of reactants gaseous, liquid and solid

How do these relate to sustainable processing?

Hierarchy of Process design - Onion diagram

a logical sequence of developing a process

design and associated flowsheet

A main reactor
B Separation
C heat recovery and cooling
D final effluent treatment

Why important
- subsequent separation processes
- decide on the need for recycle process streams
- identify effluents their composition, undesirable products, by-products
- product quality
Checklist for reaction systems and reactors

Chemical reactions occurring

basic chemistry of intended reaction or reaction sequence

reversible or irreversible
exothermic or endothermic
catalytic or non-catalytic
reaction conditions - temperature, pressure and concentration
unintended side reactions? Selectivity?
conversion of reactant to desired product

Reactor
Phases under which the reaction proceeds (gas, liquid, solid,
multiphase)
batch or continuous
provisions for heating and/or cooling
CSTR or plug flow reactor
reactor configuration eg stirred vessel, furnace, platinum gauze,
electrochemical cell, packed bed
Checklist for reaction systems and reactors
Examples of reactor types in different processes

Furnace
steam reforming of natural gas for hydrogen production
steam cracking of ethane to produce ethylene

Packed bed reactor

sulphuric acid production (vanadium pentoxide catalyst)
isomerisation reactor in petroleum refining (alternative catalysts)

Electrolytic cell
For chlorine and caustic soda production
For conversion of alumina to aluminium in aluminium smelting

Stirred tank
For polymerization of vinyl chloride in PVC production
Alkylation reactions in petroleum refining

Platinum gauze reactors

oxidation of ammonia and methane in hydrogen cyanide production
oxidation of ammonia in nitric acid production
Chemistry of process

developing synthesis pathways which use alternative feedstocks or

more selective chemistry to generate less waste

finding alternative reaction conditions, for example lower

temperatures and pressures, which promote increased selectivity

finding new solvents, for example water might be used to replace an

organic solvent

finding improved catalysts

developing alternative chemical products which are inherently safer

or less toxic
Chemistry of process

Environmental effectiveness

E-factor = Ratio of kg waste (or by-products) to kg desired product

Industry Annual tonnage E factor

Oil refining 106- 108 ~ 0.1

Bulk chemicals 104- 106 <1 - 5
Fine chemicals 102- 104 5 - 50
Pharmaceuticals 101- 103 25 -100

Reference for E factor in clean chemistry

R.A.Sheldon Consider the Environmental Quotient Chemtech March 1994 pp 38-47.
Chemistry of process

Environmental quotient

The E-factor is incomplete no differentiation between harmful and

benign wastes
Therefore Sheldon proposed Environmental Quotient EQ = E * Q where Q is
environmental impact (concept only)
crude estimate, LCA is the real substitute (coming soon!)
Chemistry of process

Atom utilisation
a measure of how effectively chemical atoms participate in a reaction to
achieve the desired product.
atom utilisation can be calculated by dividing the molecular weight of the
desired product by the sum of molecular weights of all substances produced
in the stoichiometric equation

Example: ethylene oxide. The overall reaction for the obsolete chlorohydrin
route for manufacturing ethylene oxide may be shown as
C2H4 + Cl2 + Ca(OH)2 C2H4O + CaCl2 + H2O
Molecular weight 44 111 18
Atom utilisation = 44 / (44+111+18) = 0.25 = 25%

Compare to the modern direct route of ethylene to ethylene oxide:

C2H4 + O2 C2H4O
Here Atom Utilisation is 100%
Conversion and selectivity

Conversion & selectivity are common measures of reactor

performance. They have major impacts on downstream
separation and recycle.

Measures of reactor performance

Conversion = mass ratio of reactant consumed in a reactor to reactant fed to
the reactor

Selectivity = Moles desired product produced * stoichiometric factor

Moles reactant consumed
where
Stoichiometric factor = stoichiometric moles of reactant required per mole of
product

Low selectivity implies unwanted side reactions are occurring, in parallel or series:
Parallel: Reactant Desired product
Reactant Waste

Series: Reactant Desired product Waste

Co-product and by-product utilisation

could be useful
could be an environmental waste
could be turned into a useful product may or may not generate additional
waste in the process CO2 from chemical or power plants

Example 1. Manufacture of phosphoric acid by the acidulation of

phosphate rock
Ca3(PO4)2 + 3H2SO4-----> 2H3PO4 +3CaSO4 (Phosphoric acid + gypsum)

Example 2. Soda ash (Sodium carbonate, Na2CO3) is manufactured by the

ammonia soda process
Na2CO3 used for glass making (with silica and lime), food additives

originally Leblanc process was used

better option is to use Solvay process
Co-product and by-product utilisation

Leblanc process

sodium chloride boiled in sulfuric acid to yield sodium sulfate and hydrogen
chloride gas, according to the chemical equation
2 NaCl + H2SO4 Na2SO4 + 2 HCl Major pollutant

The sodium sulfate was blended with crushed limestone (calcium carbonate) and
coal, and the mixture was burnt, producing calcium sulfide

Na2SO4 + CaCO3 + 2 C Na2CO3 + 2 CO2 + CaS

The sodium carbonate was extracted from the ashes with water, and then collected
by allowing the water to evaporate
Co-product and by-product utilisation
Solvay process

Used in a large hollow tower

At the bottom, calcium carbonate (limestone) was heated to release carbon
dioxide: CaCO3 CaO + CO2

At the top a concentrated solution of sodium chloride and ammonia

Carbon dioxide bubbled up through it, sodium bicarbonate precipitated:
NaCl + NH3 + CO2 + H2O NaHCO3 + NH4Cl

The sodium bicarbonate then converted to sodium carbonate by heating,

produces water and carbon dioxide as well:
2 NaHCO3 Na2CO3 + CO2 + H2O

ammonia regenerated from the ammonium chloride byproduct treating with

the lime (calcium hydroxide) left over from carbon dioxide generation
CaO + H2O Ca(OH)2
Ca(OH)2 + 2 NH4Cl CaCl2 + 2 NH3 + 2 H2O

Overall Stoiciometry: 2NaCl + CaCO3 Na2CO3 + CaCl2

What are the advantages of Solvay process over Leblanc process and how
does it relate to sustainability?
Impurities in feed
Feed impurities contribute to waste in several ways:

can be unreacted and find their way into products as impurities

can react with reactants to produce a new waste species
can poison a catalyst in a reactor lower conversions and secondary
reactions
Ideally remove impurities as early as possible in feedstock processing

Mixing of reactants

Why important? homogeneity of process conditions

Want homogeneity in concentration and temperature (why?)

Mixing of gaseous reactants, liquids, even distribution of fluids

How to mix?
-CSTR (impeller, baffled vessel)
-Static mixer
Static mixer (picture courtesy of Sulzer)

Impeller / baffled wall mixer

(CSTR)
Minimising secondary reactions

Why?

ways of minimising secondary reactions cooling in waste heat boilers or heat

exchangers, product removal, direct contact cooling (quench)

Examples - Ethylene production

in the petrochemical industry by steam cracking
CxHy + H2O + heat C2H4 + byproducts + H2 + H2O
note: steam is NOT a reactant, just helps lower Partial Pressure of
hydrocarbon to minimise coking (formation of carbon deposits in tubes)
gaseous or light liquid hydrocarbons heated to 750950 C
numerous free radical reactions
immediate quench to stop these reactions
converts large hydrocarbons into smaller ones and introduces unsaturation
(double and triple bonded hydrocarbons)
separate Ethylene from the resulting complex mixture by repeated
compression and distillation
generate steam during quenching fed back for cracking
Recycle of unreacted feed from reactor effluent stream

Why?

economic benefit via improved process efficiency

waste reduction

a balance between the benefits and waste reduction and recycling

Reversible reactions

problem arises when reaction is reversible, one reactant is a pollutant

water shift reaction (CO + H2O CO2 + H2)

conversion limited by equilibrium

select appropriate/optimum process conditions
may need additional reaction stages

again a balance between the benefits and waste reduction and recycling
 Catalysis and catalyst life: Impact on waste
Catalysts important to improve conversion and selectivity.
Also reduce T, P of reaction, reducing energy consumption

However, catalysts degrade through:

-Poisoning due to impurities in reactor feed
-For heterogenous catalysts (porous solids) the pores can become blocked

Degradation can lead to:

-Deterioration of reactor performance (lower conversion, yield and/or selectivity)
-Increased pressure drop due to fines (for solid catalysts)
-May require in-situ regeneration, or disposal of catalyst
 Catalysis and catalyst life: example
An example is given of the effect of catalyst life on product quality. Hydrogen is a
byproduct of the catalytic reformer unit in a petroleum refinery.

Reactor purpose: Convert naphtha to aromatics to increase octane number.

Catalyst: Platinum supported on silica or silica alumina base

Reactions:
Dehydrogenation (removal of hydrogen from cycloalkanes to make aromatics)
Dehydroisomerisation (turning n-alkanes into iso-alkenes)
Dehydrocyclization (turning alkanes into aromatic hydrocarbons)

Middle of run End of run

H2 86.0 77.0
C1 6.5 13.5
C2 3.0 5.0
C3 2.5 3.0
iC4 0.8 0.6
nC4 0.7 0.6
iC5 0.3 0.3
nC5 0.2 0.1
 Agent materials
Used to enable reactions to proceed efficiently, but can be toxic or cause waste
production. For E.g.
Solvents
-Reaction enablers
-Reaction stoppers (e.g. to stop runaway reaction when cooling is lost)
Agent materials can contaminate products and make purification difficult.

Examples include Hg in Chloralkali production (some ends up in product, toxic)

Reaction stopper for PVC manufacture. Stops reaction but ruins product!
Matrix of waste sources in reactors and processes

CHEMICAL PROCESS
WASTE SOURCE WASTE MINIMISATION Cl2 H2SO 4 C2 H4 HCN HCHO
(formaldehyde)
STRATEGY Hg cell

Feed impurities **** **** ***** ****

Feed purification **** ***** ***** ****

Incomplete feed ***** ***** **** ****** *****

conversion
Feedstock recycling ***** ******

Secondary reactions **** ***** ****** ******

Reversible reaction *****

Catalyst degrades ***** ****** *******

Agent materials *****

Static mixer-gas feed **** ***** ***** ******

Waste heat boiler ***** ***** ****** ******

Direct quench ******