ChemicalProcessDesign

Subject4.ChemicalProductDesign

JavierR.ViguriFuente
CHEMICALENGINEERINGANDINORGANIC
CHEMISTRYDEPARTMENT
UNIVERSITYOFCANTABRIA
javier.viguri@unican.es

License:
CreaLveCommonsBYNCSA3.0
INDEX
1.- Introduction
2.- What are chemical products ?
3.- Product and technology development framework

3.1.- General methodology

3.2.- Typical Steps in Product Development

4.- Product design for basic chemicals

4.1.- Property estimation methods

4.2.- Optimization to locate molecular structure
4.3.- Examples of basic chemicals design

5.- Product design for industrial chemicals

6.- Product design for configured consumer products
7.- Further reading and references
1.- Introduction

Process Design vs. Product Design: Chemical Engineering Design

Successful product and process design are based on a uniform set of

engineering design strategies.

The initial design analysis of a product design problem identifies constraints

on physical and chemical properties, (e.g., the product must be an
azeotrope, or must be emulsified in water, or must retain its flexibility even
after years of UV exposure).
These constraints are used to generate design candidates that may have
different compositions and possibly different forms.
The composition, form, and physical properties of each of these product
candidates determines the required processing operations for its
production, (e.g., the product must be coated, the liquid components must
be mixed with emulsifier at high speed, or various additives must be
blended into product).
Economic, environmental, health, and safety analyses must be performed on
the product and process to provide metrics for evaluating between
alternatives and ultimately deciding if the design is viable.
3
1.- Introduction

Process Design vs. Product Design: Chemical Engineering Design

Process Design Product Design

1.- Batch vs. Continuous 1.- Customer Need (Market Pull-
Technology Push)

2.- Input/Output structure 2.- Idea generation

3.- Reaction and Recycle 3.- Selection

4.- Separation system / Heat 4.- Manufacture
Process

recovery

Adapted from Cussler, 2011.

Cussler, E., 2011, Education for the New Chemical Industry. XXXII National Meeting of AMIDIQ. Mexico,
May 4,2011
4
1.- Introduction
The Changing Chemical Engineer

Chemical engineers, on account of their training, are extremely

versatile individuals and now find themselves engaged in all
kinds of activities well beyond traditional chemical engineering.
Chemical engineers now find themselves engaged all kinds of
activities such a primary metal manufacture, food, consumer
goods, electronics, medical devices, pharmaceuticals, water,
finance, etc.
Societal megatrends such as human health, water, food, etc.
will demand new technologies of ChemEs unlike their
predecessors (not too distant past!!).
Products are no longer just another truck or rail car of a solvent
or plastic but can be a consumer good, a system, a
manufactured article, etc.
this requires a different skill set of
chemical engineers.
 2.- What are chemical products ?

Natural Manufacturing Basic Chemical

Basic Chemical Products: resources Process Products

Primary Chemicals: Commodity or Bulk chemicals

Sulfuric acid, ethylene, propylene, phosphoric acid, ammonia.

Secondary chemicals: Fine chemicals and Specialty chemicals
Cosmetic components, drugs.

Industrial Products Basic Manufacturing Industrial

Chemicals Process Products

Films, fibers, paper, creams, pastes

Configured Consumer Product: Basic Manufacturing Configured

Industrial Process Consumer
Products Products

Dialysis devices (devices that effect chemical change), post-it notes, ink-
jet cartridges, transparencies, detergents, diapers, pharmaceuticals.
 2.- What are chemical products ?
Basic Chemical Products: Involve well-defined molecules and mixtures of molecules. Not sold
directly to the consumer. Technological inventions normally associated with new materials and less
often with new process/manufacturing and product technologies.

Primary Chemicals: Commodity or Bulk chemicals:

- Manufactured in large-scale processes (>1000 t/year) in continuous operation.
- Product that is sold without differentiation by all suppliers (quality and composition are identical);
characterized by thermophysical and transport properties.
- Sold into a global market: products differentiated only by price (low selling prices + high sales V).
- Focus of the design is on the process to produce them from various raw materials

Secondary chemicals: Fine chemicals and Specialty chemicals:

- Manufactured in small quantities (<100 t/year) in batch processing.
- Low sales volume with high selling prices (6 /kg cosmetic component 2000 /100 mg tPA drug)
- Focus of the design on identify the chemicals or mixture of chemicals that have the desired
properties to satisfy consumer needs.

Fine chemicals: Defined by their chemical structure and content

Specialty chemicals: Identified by their performance. Trade marked names and their
chemical composition is often proprietary

Industrial Products: Properties in satisfying customer needs are dominant (microstructure,

particle-size distribution, functional, sensorial and physical properties). Few industrial chemicals are
purchased by the consumer. Are ingredients and building blocks of configured consumer products

Configured Consumer Products: Normally sold to the consumer. Characterized by properties

similar to those of Industrial chemicals; in same cases their three-dimensional configurations are
crucial to satisfying customer needs.
2.- What are chemical products ?
 2.- What are chemical products ?

Changes in Chemical Products
Education Beyond Commodities

Commodities Molecules Microstructures

Key Cost Speed Function, attribute

Unit Operations
Basis (Integration- Chemistry Microstructure
Intensification)
Discovery
Feedstock & Science
Risk (Market-
Energy (Interrelation)
Technology)

Adapted from Cussler, 2011.

Cussler, E., 2011, Education for the New Chemical Industry. XXXII National Meeting of AMIDIQ. Mexico, May
4,2011
2.- What are chemical products ?

Changes in the industry

During the 20th century, the chemical industry was dominated by

manufacture of bulk commodity chemicals

Petroleum industry, Petro-chemicals

Past two decades demonstrate paradigm shift characterized by

two primary changes:

1. Only very large and very efficient companies can succeed in the commodities
market
Restructuring, reorganization,

2. Design and manufacture of specialty, high value-added chemicals

Pharmaceuticals
Cosmetics
Coatings for the electronics industry
 2.- What are chemical products ?

History of innovation in chemical product design

Market pull: marketplace demands a better product
Necessity is the mother of invention
Market need observed
Technology developed by
Experimentation with variants of current product
Rubber
Looking into novel use of existing materials
Ether as anesthetic
Creation of new synthetic materials
CFCs

Technology push: new invention looking for a use in society

Condensation polymerization (Carothers*)
Nylon fibers to replace silk stockings (DuPont)
(*) Carothers was a group leader at the DuPont Experimental Station laboratory, where most polymer research was done.
In addition to first developing nylon, also helped lay the groundwork for Neoprene.

Accidental discovery/Market pull

Penicillin
3.- Product and technology development framework

3.1. General Methodology to PRODUCT DESIGN

Market pull Technology push

Identify need
Customers needs
Properties required
Competitive products
Generate suggestions
Test suitable technology
Synthesize/collect samples
Measure properties
Identify technology
Capabilities
Properties
Generate suggestions
Alternative markets
Test samples in market

Refrigerants Nylon, Post-it

3.1. General Methodology to product design

Manufacturing

Product Business
Development Development

Technology
Development

Technology Technology Technology Technology

Development Scoping Assessment Transfer

Product
Development Concept Feasibility Development Manufacturing

Product
Introduction
3.1. General Methodology to product design

Concept Feasibility Development Product

Manufacturing Introduction
3.2.- Typical Steps in Product Development

I.- Identification of needs

II.- Determine key parameters which are
necessary for success
III.- Develop ideas which are potential solutions
IV.- Select best candidates for development
V.- Laboratory work/pilot work
VI.- Small/full scale testing
VII.- Product launch
VIII.- SUCCESS!!
 I.- Identification of Needs
Needs begin with statements of we need a
better x or wouldnt it be great if we could
do this or your product is great EXCEPT Y

Typically are customer driven

Sometimes the problem is not the real issue

In other cases, the need comes from societal

trends and anticipating them before they
happen
II.- Parameters necessary for success
Imperative to define ALL parameters/product
properties for success
What is absolutely necessary?
What can be compromised to a degree?
It is an optimization problem

Needs to include ALL other issues such as

intellectual property, safety and health,
manufacturing capability, etc. These can not
be ignored or it may be fatal later on
 II.- Parameters necessary for success
Product Attributes
Composition Size Shape Flowability
Taste Viscosity Yield Strength Sheen
Particle Size Distribution Color Texture Elasticity
Reliability Gloss Silkyness Compaction

One needs to think very carefully how you will

measure the product attribute!
In some cases, the only test may be a product use
test.
You may not understand fully why a product works.
Important to recognize that failure on any one metric
is likely to kill the product development !!
Some product attributes can be compromised BUT
one needs to understand how much they can be
compromised
 II.- Parameters necessary for success
Hypromellose (HPMC) is
a widely used rate-
controlling polymer in
oral controlled-release
(CR) drug delivery
applications.

The product attributes

for a Direct
Compression grade
HPMC for CR
applications require
balancing several,
sometimes conflicting,
performance
dimensions.
 III.- Idea Development
Many different sources of ideas
Subject matter experts beware!
Literature
Patent literature will help to define the
limitations on the solution space
Brainstorming all off the wall ideas are
good
Process at this point is VERY divergent no
ideas should be dismissed
 IV.- Selection of Alternatives
Convergent part of the process
Need to selection realistic alternatives
Metrics might be ease of implementation, speed
to market, manufacturing capability, etc.
Need to seriously ask at this point does this idea
violate the fundamental laws of science and
engineering?
Economics what is the expected manufacturing
cost? Can a profit be made? Are there
competitors/alternatives?
Science is not democratic everybody doesnt get
the same vote on alternatives
 V.- Lab Work/Prototype Development
This is the nuts and bolts of what we as ChemEs
do
Begin to wrestle with is this possible?
Issues such as equipment and chemical selection
become key
How will the process scale?
Issus such as EH&S start to be increasingly
important
Understand what product attribute will be the most
difficult to achieve
 VI.- Small Scale/Full Scale Testing
Manufacture of developmental quantities
where, how? Specialized equipment required?
Are there significant manufacturing issues?
Packaging selection
Shipment to customers
What does the supply chain look like?
Are there still E&HS issues, especially in
manufacturing?
How will the product be marketed? Is there a
channel to market?
Production economics should now be in hand
4.- Product design for basic chemicals

Natural resources Manufacturing Basic Chemical Products

Process (well defined molecules and
mixtures of molecules)

Design problem formulated by manipulation of molecular structure

using optimization methods to achieve the desired properties.

Step 1: Properties estimation

Step 2: Optimization to locate molecular structure

* Use of Methods of properties estimation and molecular simulation.

Polymers, Refrigerants, Solvents, Proteins for pharma.

* New process technologies for products.

Heat and mass exchanger technologies in NH3 production.

* Traditional steps in the process design.

4.1.- Property estimation methods

A) Databanks

* v-l: Properties of gases and liquids (Poling et al., 2001).

ASPEN PROPERTIES

* Polymers: Properties of polymers (van Krevelen, 1990)

* Electrolytes /Solids: Less predictive and less accurate

B) Regression of experimental data

Pv, , C = F (T)

C) Estimation of properties in function of molecular structure

* Group- and Bond- Contribution methods, using Tb

* Microsimulation: Molecular Dynamics (MD) and Monte Carlo
simulations
4.1.- Property estimation methods
Especially important when laboratory and pilot-plant data are not available.
Estimation of constants and parameters for pure species: Vc, T, l, hvap

- NRTL, UNIQUAC, UNIFAC
Activity Coefficients

- Designer provide the molecular structure of the chemical species
- Divides up a molecule into a number of functional groups; single atom (Cl-), fragment
that often stays together (-CH3). Assumes that same properties of a molecule can be
estimated as sums of contributions from each group. Linear (Tb, Tf) and Non-linear (Tc,
Pc, Vc) relations of these properties with group contributions.
(Poling at al., 2001; Joback and Reid, 1987)
Polymer property estimation (van Krevelen, 1990)
- Semiempirical group-contribution method and data for each group in a
polymer repeating unit
- Data are provided to estimate Tg, l, W, refractive index.

For a specific property p[n], there are two forms, where

N

Ai ni
d
N
ni: number of groups of type 1 in the polymer repeating unit. Ai ni
p[ n] = iN=1
i =1
p[n] = N
N: number of types of groups in the repeating unit

B n i i
Ai: contribution associated with group I
Bi: molecular weight of group I i i
B n
i =1 i =1
d: exponent of each property to be estimated
4.2.- Optimization to locate molecular structure

Molecular structure design relies on
accurate property estimation

methods

Atoms and Groups in the molecular structure are adjusted to Minimize

the sum of squares of the differences between the property estimates
and the specified values for property j in an array of P target
properties.

The function is subject to specified bounds where ni is the number of

groups of type i in molecule j, and N is the number of types of
molecular groups in molecule j.

p p Lj p j (n) pUj
min[ p j (n) p spec
j ]2
n
j =1
ni ( niL , niU ), i = 1,...N
4.3.- Examples of basic chemicals design

POLYMERS DESIGN
Problem: Polymer film o protect an electronic device.
Product-Quality specifications (Constraints): , Tg, W
Objective Function: Minimize the sum of squares of the differences between the estimates
and the specified , Tg, W properties.
Solution: [(CH2)3, (CHCl)6]

* REFRIGERANT DESIGN
Problem: Refrigerant that absorb heat at low T in evaporator an reject heat at T from the
condenser without ozone depletion potential.
Product-Quality specifications (Constraints): Pv (T), hvap
Objective Function: Minimize the sum of squares of the differences between the estimates
and the specified Pv (T), hvap properties.
Solutions: [SF2] and [CH3CHF2]

* SOLVENT DESIGN
Problem: Dissolve dried ink in a lithographic printing process with small latent heat of
vaporization
short drying time, low utility cost of vaporization, non flammable.
Product-Quality specifications (Constraints): D, P, H, Kow, Tb, Tm
Objective Function: minimize heat vaporization to reduce drying time and cost of heating
utilities
Solutions: Methyl ethyl cetone, Diethylketone, Ethylene glycol monomethyl ether
5.- Product design for industrial chemicals

Basic Chemical Products Manufacturing Industrial Chemical Products

Process (Thermophysical & Transport
properties +properties to satisfy
customer needs)

New process technologies for products.

Isopipe process for the fusion of thin glass substrates.

Simulation methods less used than in Basic Chemicals. More

experimental approaches.

Microstructures characterize industrial chemicals and creates value

Pastes and creams, Anti-fouling agents, Industrial catalysts,

Microspheres for controlled release of pesticides.
5.- Product design for industrial chemicals

MIXTURES
Chemical products: mainly mixtures not pure compounds.

Problem Statement: Given a set of chemicals and a specific

set of property constraints, determine a mixture of the
chemicals that meets these properties

Small quantities easier to manage, less expensive, but difficult to

predict properties after mixing.

Mixtures properties have non-linear relationships to individual

components properties.

Examples: Solvent mixtures, polymer formulations, oil

blends in refinery, specialty chemicals (Pesticides, drugs,
drilling fluids), beauty bar.
6.- Product design for configured consumer products

Basic Chemical Products Manufacturing Configured Consumer Products

Industrial Products Process (Properties to satisfy customer needs
+ Sold directly to the consumer)

Use of product technologies which includes:

- Microstructures that often characterize industrial chemicals

- Secondary or supporting devices and the like that are an

integral part of the final product construction

* Involved new technologies from other disciplines.

Halogen light bulbs, Hemodialysis devices, Soap bars, Ice

cream, Cheese substitutes.
 Application of Chemical Engineering
Science a diaper
Technical Demands on Diaper

- Safe for use on a child. No safety issues

- Not leak
- Stay closed
- Reasonably child-proof
- Comfortable
- Easy to use

-Sufficiently absorbent even under repeated insults

- No leaks due to load of baby/child/adult
- Gender differences
- Disposal/long term environmental issue

Quick absorption in Superabsorbent particles

Slow desorption
Flexibility and Resistance

Transport Problem + Materials + Mechanical Problem

7.- Further Reading and References
Cussler, E., Moggridge, 2001, Chemical Product Design. Cambridge University Press.

Cussler, E., 2011, Education for the New Chemical Industry. XXXII National Meeting of AMIDIQ.
Mexico, May 4,2011

Joback K.G., Reid R.C., 1987, Estimation of Pure-Component Properties from Group
Contributions, Chemical Engineering Communications, 57, 233-243.

Ng, K., Gani, R., Dam-Johansen, K., (eds.), 2007, Chemical Product Design: Toward a
Perspective through Case Studies, Elsevier.

Nimitz, J., Skaggs, S., 1992 , Estimating tropospheric lifetimes and ozone-depletion potentials of
one-and two-carbon hydrofluorocarbons and hydrochlorofluorocarbons. Environmental Science
and Technology, 26 (4), 639-744.

Poling, B., Prausnitz, J., Connell, J., 2001, Properties of Gases and Liquids, 5th ed., McGraw-Hill,
NY.

Roberts, R., 2010, Serendipia: Descubrimientos accidentales en la ciencia. Alianza Ed.

Seider, W., Seader, J., Lewin, D., Widagdo, S., 2010, Product and Process Design Principles.
Synthesis, Analysis and Evaluation. Third Ed. John Wiley & Sons.

van Krevelen, D.W., 1990, Properties of polymers. Elsevier, Amsterdam.

Wei, J., 2007, Product Engineering-Molecular Structure and Property, Oxford University Press.