SEPARATION AND PURIFICATION OPERATIONS

SYNTHESIS
Definition of the problem

Known

Products specifications and properties as well as storing phase and storage operation conditions

Reaction stage operation conditions and composition, phase and properties of the outlet streams or final
reaction mixtures at the reaction stage

And

Considering the portfolio of unit operations

The objective is

To find the more sustainable set of separation and purification operations to bring the products from the
reaction conditions to the storage ones, accomplishing their specifications. 1
SEPARATION AND
PURIFICATION SYNTHESIS
Initial mixture
or stream To propose possible separation sequences

To identify suitable separation

methods

NO To gather information about each

separation method

To select the most sustainable separation

method

Yes Does the stream

To analyze the sub-mixtures or sub-
have the product
specifications? stream
To include the
block in the
diagram

Adapted from Dimian AC, Bildea CS, Kiss A, Integrated Design and Simulation of Chemical Processes, Elsevier, Amsterdam, 2014. 2
PROPOSITION OF POSSIBLE
SPLITS
General heuristics for separation sequences

Transform heterogeneous mixtures or streams in homogeneous mixtures or streams in first place

Remove components that can impact negatively product specifications in first place

Remove troublesome impurities: corrosive, hazardous and toxic materials in the first place

Remove the component in highest concentration first

Dimian AC, Bildea CS, Kiss A, Integrated Design and Simulation of Chemical Processes, Elsevier, Amsterdam, 3
2014.
PROPOSITION OF POSSIBLE
SPLITS
General heuristics for select separation methods

Favor separation that match directly the desired products

Prefer separations that split the feed stream as equally as possible

As the ratio of distillate to bottoms moves away from unity, other separation methods
compete more favorably with distillation

All forms of distillation (simple, extractive, and azeotropic) can be eliminated as potential
methods for dilute separations.

Dimian AC, Bildea CS, Kiss A, Integrated Design and Simulation of Chemical Processes, Elsevier, Amsterdam, 4
2014.
IDENTIFICATION OF
SEPARATION METHODS
Identify if the initial stream is

Homogeneous Heterogeneous

Gas/liquid
Liquid phase

Liquid/Liquid
Gas pase

Gas/solid
Liquid gas
transition
Liquid/solid

Solid phase Liquid/gas/solid

Adapted from: Dimian AC, Bildea CS, Kiss A, Integrated Design and Simulation of Chemical Processes, Elsevier, Amsterdam, 2014.

5
IDENTIFICATION OF
SEPARATION METHODS

Driving force of the

Type of feed stream Feed phase Unit operation
separation: difference in
Solid - gas Fluidization Density
Liquid – solid Direct drying Boiling temperature

Liquid - solid Indirect drying Boiling temperature

Gas – liquid, gas –solid or solid - liquid Inertial separation Density

Solid – liquid or liquid - liquid Flotation Surface tension

Heterogeneous
Solid – liquid or solid - gas Filtration Phase

Solid –liquid, liquid – liquid or solid – liquid -

Centrifugation Density
liquid
Liquid – liquid, gas - liquid Decantation Density
Solid - liquid Sedimentation Density
Solid - gas Electrostatic precipitation Ionization potential

6
IDENTIFICATION OF
SEPARATION METHODS
Initial
homogeneous
mixture

Rank the components

by normal boiling
point and divide them
in

Gas Gas –Liquid transition Liquid

Tb≤ -20ºC -20 ºC≤ Tb≤ 50 ºC Tb≥50 ºC

Perform a flash and Liquid separation

Gas separation
divide the stream in methodology and
method and heuristics
gas an liquid streams heuristics

Dimian AC, Bildea CS, Kiss A, Integrated Design and Simulation of Chemical Processes, Elsevier, Amsterdam, 2014.
7
IDENTIFICATION OF
SEPARATION METHODS
Driving force of the separation:
Type of feed stream Feed phase Unit operation
difference
Cryogenic distillation Relative volatility
Physical absorption Solubility
Chemical absorption
Catalytic oxidation
Chemical family
Catalytic hydrogenation
Gas Chemical treatment
Membrane permeation Membrane selectivity
Adsorption Adsorption coefficient and kinetic diameter

Condensation Boiling temperature

Distillation Relative volatility
Evaporation Boiling temperature,
Homogeneous Stripping Boiling temperature
Extractive distillation Chemical family
Azeotropic distillation Chemical family
Crystallization Fusion point, Solubility
Liquid – Liquid extraction Solubility
Liquid Absorption Solubility
Adsorption Adsorption coefficient
Adsorption using molecular sieves Kinetic diameter
Membranes separation:
Permeability
Ultra and microfiltration, reverse osmosis, pervaporation
8
Chemical treatment Chemical family
 IDENTIFICATION OF
SEPARATION METHODS
General heuristics for gas separations

There are four major gas separations: condensation, absorption, adsorption, membrane separation

Favor condensation for removing high boilers from non-condensable when cooling water can be used
as thermal agent

Favor catalytic conversion when impurities can be converted in product

Favor adsorption for small-scale desiccation operations

Favor adsorption for complete removal of water vapor

Favor glycol absorption for large scale desiccation operations when dew point reductions are about

Dimian AC, Bildea CS, Kiss A, Integrated Design and Simulation of Chemical Processes, Elsevier, Amsterdam, 2014.
9
IDENTIFICATION OF
SEPARATION METHODS
Classify the gas
separation
operation as

Enrichment
Purification
Refination (Sharp)
Increase in concentration of one
or more species in one of the Removal of impurities to
product streams and the Splitting in products with achieve high concentration of
depletion of the same species in high recovery of target the product (≥99%).
the other product stream. products. Ratio product to Impurity removal from
feed concentration ≥10 2000ppm to less than
Neither high purity nor high
recovery of any components is 100ppm
achieved.

Dimian AC, Bildea CS, Kiss A, Integrated Design and Simulation of Chemical Processes, Elsevier, Amsterdam, 2014.

10
IDENTIFICATION OF
SEPARATION METHODS

Separation method Enrichment Refination Purification

Condensation Applicable Non applicable Non applicable
Cryogenic distillation Applicable Applicable Non applicable
Absorption Applicable Applicable Non applicable

Chemical scrubbing Non applicable Applicable Applicable

Molecular sieve Applicable Applicable Applicable
adsorption
Equilibrium limited Applicable Applicable Applicable
adsorption
Membranes Applicable Applicable Non applicable

Chemical treatment Non applicable Non applicable Applicable

Dimian AC, Bildea CS, Kiss A, Integrated Design and Simulation of Chemical Processes, Elsevier, Amsterdam, 2014.
11
IDENTIFICATION OF
SEPARATION METHODS
General heuristics for liquid separations

When distillation is feasible, prefer it in the first attempt.

Remove first the light ends

Perform difficult separations latter

Isolate zeotropic and azeotropic mixtures

Examine separation of azeotropic mixtures last

Remove components in order of decreasing percentage of the feed

Dimian AC, Bildea CS, Kiss A, Integrated Design and Simulation of Chemical Processes, Elsevier, Amsterdam, 2014.
12
IDENTIFICATION OF
SEPARATION METHODS

Classify the liquid

separation as

Dilute Bulk Temperature

Azeotropic
sensible
Total distillate or Total distillate or
bottoms of a bottoms of a An azeotropic
potential distillation potential distillation mixture has to be The mixture is
operation is less separated affected negatively
operation is less
than 5% of the feed. by temperature
than 5% of the feed.

Dimian AC, Bildea CS, Kiss A, Integrated Design and Simulation of Chemical Processes, Elsevier, Amsterdam, 2014.

13
IDENTIFICATION OF
SEPARATION METHODS

Separation method Dilute Bulk Azeotropic Temperature

sensitive
Simple distillation Applicable Applicable Non applicable Vaccum
Complex Distillation Non applicable Applicable Non applicable Non applicable

Stripping Applicable Applicable Non applicable Applicable

Extractive distillation Non applicable Applicable Applicable Non applicable

Azeotropic distillation Applicable Applicable Applicable Non applicable

LL Extraction Applicable Applicable Applicable Applicable

Adsorption Applicable Applicable Applicable Applicable

Molecular sieving Applicable Applicable Applicable Applicable

Membrane permeation Applicable Applicable Applicable Applicable

Melt crystallization Non applicable Applicable Non applicable Applicable

Dimian AC, Bildea CS, Kiss A, Integrated Design and Simulation of Chemical Processes, Elsevier, Amsterdam, 2014.
14
SELECTION OF A SEPARATION
ALTERNATIVES
Sustainability analysis
How to select the most sustainable separation alternative

Identification of Assessment of Integration of

alternatives alternatives assessments
• Identification of • Selection of • Calculation of
separation indicators weights of
alternatives indicators
• Calculation of
• Gathering of indicators • Calculation of SCI
information: short for each separation
methods for design alternative
the separation
alternatives • Results analysis
15
GMS Data Sheet
Specification Value

Mono and diesters (min, wt%) 70

Total glycerol (max, wt%) 16-33

Free glycerol (max, wt%) 7
Polyglycerols (max, wt%) 4+1
Sulphated ash (max, wt%) 0.5
6
Acid value ( max, mg KOH/g)

Water (max, wt%) 2

Iodine value (max, gI2/g) 0.5
Arsenic (max, mg/kg) 3
Mercury (max, mg/kg) 1
Lead (max, mg/kg) 2
Cadmium (max, mg/kg) 1

The specifications on the table were taken from EFEMA, EFEMA Index of Food Emulsifiers, 2019, for Mono- and diglycerides of fatty acids, page 52,
Available in http://www.emulsifiers.org/Images/EFEMA%20emulsifier%20index%20-%20March%202019.pdf
16
April 15th, 2019
REACTION STAGE

Nitrogen
Methanol

Methyl ester glycerolysis

T= 135 ºC
P= 1 atm No
Molar ratio glycerol: methyl
stearate = 2: 1
Catalyst= sodium methoxide
MG+DG
Concentration of catalyst= Min 70% Yes
1%wt based on reaction MG min 30%
mixture
Mixing speed=XX rpm
MG+DG close to 0 % wt
Nitrogen atmosphere

17
STORAGE OPERATIONS
DESIGN

GMS storing Yes

T= room Note 1
P= atmospheric

NO

Methanol Yes
storing Note 2
T= room
P= atmospheric

NO

18
SEPARATION AND
PURIFICATION SYNTHESIS

Mixture Mixture Mixture Separation Driving Alternatives to be

description class sequence force evaluated

19
SEPARATION AND
PURIFICATION SYNTHESIS

Mixture Mixture Mixture Separation Driving Alternatives to be

description class sequence force evaluated
MG+DG Het (G-L-L) 1. Nitrogen Relative Distillation
TG and volatility Stripping
G Methanol
Sodium methoxide
1%
1
Soaps
2. Sodium Solubility
Water methoxide
Metals
Nitrogen 3. Glycerol Density
Methanol

20
SEPARATION AND
PURIFICATION SYNTHESIS 6

Nitrogen
2 Condensation
Decantation
Ti= 135 ºC
T=30ºC
Tf=30ºC
P= 1 atm
P= 1 atm 5
Nitrogen
Methanol Methanol

7
Methyl ester glycerolysis
T= 135 ºC
P= 1 atm No 3
Molar ratio glycerol: methyl
stearate = 2: 1
Catalyst= sodium methoxide
MG+DG
Concentration of catalyst= Min 70% Yes XXXXXXXXXXXXXX
1%wt based on reaction MG min 30%
mixture 1
Mixing speed=XX rpm
MG+DG close to 0 % wt
Nitrogen atmosphere
4

21