Metrohm Applikon

Applications for Process Analytics

Titration

Photometry

Process
Electrochemistry

Spectroscopy

Handbook 2017

Selections of sold applications to customers installed

over the past 40+ years
 About this Handbook

02 This Metrohm Process Analytics Handbook for Sold

Ap­­pli­­­­­­­cations is meant to be a handy compendium to help
Fully automated, online customizable analyzers facilitate
process monitoring across a wide array of applications.
guide you through our work at Metrohm Applikon over Drawing on our core competencies in titration, spectros-
40+ years of process analysis control. Many major and copy, and electrochemistry, we leverage our applications
critical analysis parameters in various industries are com- knowledge to create reliable solutions for process analy-
piled here according to specific process areas, helping sis that optimize efficiency, decrease chemical consump-
you to find the proper solution to any challenge. tion and create a safer work environment.
Metrohm knows your industry, and we are an active
partner in your process control with our vast experience We back our systems with a team of experienced support
from thousands of installations around the globe. personnel to offer you the full value chain of process
ana­­lytics:
Additionally, attention is called to our Process Appli­ca­
tion Notes (PANs) at the beginning of each industry • Process Control
chapter, be­­low the introduction. PANs are a short over- • Process Optimization
view about a specific process, problem (and its repercus- • An increased yield
sions), and the Metrohm Process Analytics solution. These • Reduced operational cost
are freely downloadable from www.metrohm.com.
With our expertise and experience we do not just offer
Process Solutions from Metrohm Process Analytics process analyzers, but an integrated solution to the end
Metrohm Process Analytics is the brand name represent- user. This helps optimizing process efficiency while reduc-
ing the well-known Metrohm Applikon wet chemistry ing operation cost. Real time analysis as an integrated
pro­­cess ana­lyzers as well as the Metrohm NIRSystems part of process control and automation will help you in­­
ins­­truments for process analysis. Our process analyzers crease yields and improve production quality.
take the famous Metrohm laboratory solutions a step
further, offering ana­lytical systems for titration, spectros-
copy, electroche­mis­try, ion chromatography, photometry, For your information, this document has been made
as well as ion selective measure­­ments. interactive for easier usage on electronic devices.

New in 2016: Process Ion Chromatograph

Metrohm Process Analytics has now added ion chroma- A wide range of analytical columns, detectors, and addi-
tography to our wide selection of analytical techniques tional equipment is available from Metrohm to adapt
offered for online, inline, and atline process control. Take your application to almost any process requirement.
note that few applications will be found here as a result.
• Application areas from harsh electroplating baths to
The Process Ion Chromatograph from Metrohm Process trace impurities in boiler water
Analytics is a complete and flexible system for online • Calibration and validation at the press of a button
monitoring of ionic compounds in aqueous media from • Pressureless ultrapure water feed from ELGA® for
ng/L to % concentrations. With one injection, analyze reliable trace analysis
multiple components with automated, intelligent inline
sample preparation and injection techniques. For more information, visit:
www.metrohm.com/en/products/process-
analyzers/process-ion-chromatograph/
Table of Contents

Chemical Industry: Chlor-Alkali Production 6–7 03

Brine Production: 7
Brine Purification: 7
Chlorine Production:  7
Ion Exchange Cell Membrane Electrolyzer: 7
Secondary Purification Resin Treatment: 7
Waste Water: 7
Other Applications for the Chlor-Alkali Industry: 7

Chemical Industry: Soda Ash Production 8

Soda Ash Production: 8
Brine Preparation: 8
Waste Water: 8

Chemical Industry: Polymer Production 9–11

Applications for PVC: 10
NIRS Applications for the Polymer Industry: 10
Physical Characteristics (Thickness, Density, Viscosity): 10
Monitoring Curing Rate: 10
Hydroxyl Number: 11
Moisture/Water Content: 11
Comparison / Distinguishing: 11
Monitoring Blend/Reaction Characteristics: 11
Additives: 11

Chemical Industry 12–15

Applications for Cumene Process: Phenols + Toluene: 13
Applications for Cumene Process Waste: 13
Applications for Polyamide/Caprolactam Production: 13
Applications for Caprolactam Process Waste: 13
Applications for the HPPO Process: 14
Applications for HPPO Process Waste: 14
Applications for Fertilizer Production:  14
Applications for Fertilizer Emission Control:  15
Other Applications for the Chemical Industry: 15
Waste Water: 15
NIRS Applications for the Chemical Industry: 15
Surfactants: 15
Moisture Analysis: 15
Reaction Monitoring: 15
Mixtures: 15
Solvent purity and recovery: 15

Petrochemical Industry 16–18

Biodiesel Production: 17
Kerosene Production: 17
Other Downstream Processes: 17
Waste Water: 17
Other Applications for the Petrochemical Industry: 17
NIRS Applications for the Petrochemical Industry: 18
04 Semiconductor / Electronics Industry 19–21
Aluminum Foil Etching: 20
Glass Etching: 20
Solar Etching: 20
Wafer Etching: 20
Photolithography: 21
Plating Baths: 21
Waste Water: 21
Other Applications for the Semiconductor / Electronics Industry: 22

Mining Industry 23–25

Copper Mining & Purification: 24
Electrowinning Processes: 24
Gold Mining & Purification: 24
Leaching Processes: 24
Nickel Mining & Purification: 24
Platinum Refineries: 25
Zinc Mining & Purification: 25
Waste Water: 25
Other Applications for the Mining Industry: 25

Steel / Metal Industry 26–28

Pickling Process: 27
Waste Water: 27
Aluminum Milling: 27
Other Applications for the Steel / Metal Industry: 28

Galvanic / Metal Surface Industry 29–31

Waste Water: 31
Other Applications for the Galvanic / Metal Surface Industry: 31

Pulp and Paper Industry 32–33

Bleaching Process: 33
Waste Water: 33
Other Applications for the Pulp and Paper Industry: 33
NIRS Applications for the Pulp and Paper Industry: 33
Kappa Number: 33
Moisture Content: 33
Resin Levels: 33

Energy / Power Industry 34–36

Boiler Feed: 36
Cooling Water: 36
Waste Water: 36
Other Applications for the Energy / Power Industry: 36
Automotive and Aerospace Industry 37–38 05
Electroplating Surface Treatment: 38
Etching Baths: 38
Zinc-Phosphatizing: 38
Waste Water: 38
Other Applications for the Automotive and Aerospace Industry: 38

Textile Industry 39–40

Acrylic Fiber Production: 40
Cellulose Fiber Production: 40
Spin Bath Process: 40
Other Applications for the Textile Industry: 40
NIRS Applications for the Textile Industry: 40
Fiber Blends: 40
Finishing: 40
Fire Resistance: 40
Heatset Monitoring: 40

Pharmaceutical / Biochemical Sector 41–43

Waste Water: 42
Other Applications for the Pharmaceutical / Biochemical Sector: 42
NIRS Applications for the Pharmaceutical Industry: 42–43
Active Ingredients (API) / Content Uniformity: 43
API – Antacids: 43
API – Cough Syrup: 43
API – Foot Powder: 43
API – Transdermal Patches: 43
Drying: 43

Food and Beverage Industry 44–45

Beverages: 45
Potato Products: 45
Waste Water: 45
Other Applications for the Food and Beverage Industry: 45

Industrial Waste Water 46–47

Environmental Sector 48–49

Potable (Drinking) Water: 49
River and Surface Waters: 49
Air Pollution: 49

Overview of Process Analyzers 50–51

06

Chemical Industry: Chlor-Alkali Production

Production Processes Brine Purity

The chlor-alkali production process mainly relies upon the In the membrane electrolysis production of chlor-alkali,
electrolysis of NaCl brine to produce caustic soda (sodium the purity of the brine is very important. The presence of
hydroxide, NaOH) and chlorine (Cl2), which are then used impurities such as calcium and magnesium can shorten
in countless other industries. the performance and lifetime of the membranes or can
damage the electrodes. Partial membrane blockage from
Three main techniques are in use for the production of precipitation reactions will lead to high electrical opera-
chlor-alkali from salt: the membrane technology which tional costs and the high cost associated with replacing
accounted for 59.2% of production in Europe in 2014, membranes.
followed by the mercury process (24.7%) and the dia-
phragm process (13.7%). All new plants are based on the
membrane technique, which does not include mercury
and asbestos like the other processes. The shift towards
membrane technology is in line with Euro Chlor’s voluntary
agreement to phase out the installed mercury capacity by
2020.

Chlor-Alkali
 Process Application Notes for the Chlor-Alkali Industry 07
• Chlor-alkali industry: Hardness in Brine.
AN-PAN-1005

Sold and Installed Applications

Brine Production: Secondary Purification Resin Treatment:

• Alkalinity in Brine (Brine Production) • Hydroxide [OH-] + Carbonate [CO32-] in Brine (Brine
• Bromide [Br-] in Brine (Brine production) Purification, Resin Treatment)
• Calcium [Ca2+] in Brine (NaCl Production)
• Chloride [Cl-] in Brine (Brine production) Waste Water:
• Chloride [Cl-] in effluent waste to river (Effluent
Brine Purification: WWTP to river)
• Caustic [OH-] + Carbonate [CO32-] in Brine (Pretreat­ • Hypochlorite [ClO-] + Sulfite [SO3-] (Mercury Cell
ment Raw Brine) Effluent)
• Hydroxide [OH-], Carbonate [CO32-], + Calcium [Ca2+] • Sulfate [SO42-], Chlorine [Cl2], + pH in waste water
in Brine (Brine Purification) (Effluent WWTP)
• Hydroxide [OH-], Carbonate [CO32-], + Hypochlorite
[ClO-] in Brine Other Applications for the Chlor-Alkali Industry:
• Magnesium [Mg2+] in Brine (Brine Purification) • Ammonia [NH3], Total Alkalinity, Carbonate [CO32-],
• Sodium Hydroxide [NaOH] in Brine (Brine Pre-Treatment) + Chloride [Cl-] in Brine
• Sodium Hydroxide [NaOH], Chlorine [Cl2], + • Carbonate [CO32-] in Overcarbonated Brine
Carbonate [CO32-] in Brine (Brine Purification)

Chlorine Production:
• Chloride [Cl-] in 50% Sodium Hydroxide [NaOH]
(Chlorine production)
• Chlorine [Cl2], Hydroxide [OH-], Carbonate [CO32-],
Chloride [Cl-], + pH in Brine (Chlorine plant)
• Potassium iodate [KIO3] in Brine (Chlorine production)

Ion Exchange Cell Membrane Electrolyzer:

• Calcium [Ca2+] + Magnesium [Mg2+] in Brine (Inlet
Membrane Electrolyzer, Brine Treatment)
• Calcium [Ca2+], Magnesium [Mg2+], + Chloride [Cl-] in
Brine with % Hydrochloric Acid [HCl]
(Inlet Membrane Electrolyzer)
• Calcium [Ca2+], Magnesium [Mg2+], Sodium Hydroxide
[NaOH], + Sodium Carbonate [Na2CO3] in Brine
(Inlet Resin Treatment)
• Chlorate [ClO3-] in Brine (Inlet Membrane Electrolyzer)
• Chlorine [Cl2] in Brine (Outlet Membrane Electrolyzer)

Chlor-Alkali
08

Chemical Industry: Soda Ash Production

Solvay Process Sold and Installed Applications

Soda ash (sodium carbonate, Na2CO3) is used as the pre-
cursor of many goods, in industries such as Pulp & Paper, Soda Ash production:
glass, detergents, and chemical manufacturing. There are • Calcium [Ca2+] + Magnesium [Mg2+] in Sodium
three major soda ash producers in the world: ANSAC of bicarbonate [NaHCO3] (Soda Ash production)
the United States, multiple producers in China, and • Calcium Oxide [CaO] in soda lime (Soda Ash production)
Solvay S.A. (now INOVYN) of Belgium. The major pro­­ • Carbon dioxide [CO2] in soda (Soda Ash production)
duc­tion process for soda ash is the Solvay process, which • Carbonate [CO32-] in the Gas Scrubber Carbonization
uses brine and limestone (calcium carbonate) as precur- Column (Soda Ash production)
sors. In 2014, world soda ash production created 52 • Hydroxide [OH-] in soda (Soda Ash production)
bil­­lion kilograms, which accounts for more than 7 kg per
each human on earth that year. Out of this amount, Brine Preparation:
about 72% has been created synthetically with the Sol­­ • Ammonia [NH3] / Ammonium [NH4+] in brine
vay process, while the remaining 28% has been mi­­ned (Preparation Ammonia Saturated Brine)
from natural sources. The Solvay process is responsible • Calcium [Ca2+] + Magnesium [Mg2+] in Brine (Soda Ash
for most soda ash production outside of the US, which production)
uses its own natural mineral deposits.
Waste Water:
Process Application Notes for the Soda • Chloride [Cl-] in effluent (WWTP)
Ash Industry • Ammonia [NH3] / Ammonium [NH4+] in waste water
(WWTP)
• Analysis of Ammonia in the Preparation
of Ammonia-Saturated Brine. Other relevant PANs can be found in the Chlor-Alkali
AN-PAN-1025 Industry section.

Soda Ash
 09

Chemical Industry: Polymer Production

Polymer and plastics in everyday life Final product

Polymers and plastics are a mainstay of modern life due Polymers are the result of complex reactions and pro-
to their versatility and physical properties: they can be cesses involving various raw materials and additives. The
formed into nearly any shape, with different degrees of final product must therefore be thoroughly inspected to
flexibility and other variable parameters. Polymers can ensure that it meets the specifications. Our instruments
also be made into fibers which are spun, woven, and and applications enable you to determine a variety of
made into synthetic fabrics with adjustable properties substances and parameters, including additives, copoly-
which can vary from flame resistance to bullet protec- mer levels, water content, halogens, and residual mono-
tion. Even rubber, such as the type used in automobile mers or impurities.
tires, is composed mainly of synthetic polymers.
Standards for quality control
Reaction monitoring and quality control The importance of polymer feedstock quality is reflected
Polymer production is a demanding process in which by the large number of standards relating to them.
high-purity raw materials undergo complex reactions and Metrohm instruments comply with numerous chemical
are turned into polymers, fibers, resins, rubbers, and standards, which can be found within the Polymer and
gums. The polymerization reaction is the critical point in plastics branch sites here:
the production process, and poor-quality raw materials www.metrohm.com/en/industries/
will inevitably yield poor-quality polymers. To make sure
that the products meet the specifications, the materials Process Application Notes for the
and processes have to be monitored along the entire Polymer Industry
production chain. You therefore need methods that
• Inline monitoring of free isocyanate (%NCO)
operate where the reaction takes place and that yield
content in polyurethane.
immediate results.
AN-PAN-1041

Polymers
10 Sold and Installed Applications

PVC Production NIRS Applications for the Polymer Industry:

Polyvinyl chloride (PVC) is a plastic polymer which is seen Near-Infrared Spectroscopy (NIRS) is a technique used to
all over in everyday life – in pipes, bank cards, sports quickly and accurately determine many properties in
equip­­ment, and even furniture. It is generally rigid, but process. No chemicals are needed and results are
can be made into more flexible forms with the addition obtained very quickly. NIR spectroscopy can be used in
of plasticizers such as phthalates. The precursor to PVC is many different areas within the polymer and plastic
the vinyl chloride monomer (VCM) which is reacted with manufacturing process, for any polymer type (liquids or
itself to create the PVC polymer. VCM is created by an­­ solids). Common applications include the determination
other process, which begins by chlorinating ethylene. of the acid value, amine value, hydroxyl number, mois-
Manufacturing PVC is in fact the largest use of chlorine ture (typically higher than 100 ppm), adhesive content,
for industrial purposes. The process is followed by oxy- antioxidant and UV inhibitor content, cure, melt index,
chlorination with hydrochloric acid, creating the interme- HDPE/LDPE, melamine content, plastic identification, po­­
diate – ethylene dichloride (EDC). EDC is then cracked by ly­­mer analysis, end point determination, alcohol detec-
heating in a furnace, which splits the compound into tion/analysis and residual solvent detection. NIRS analysis
vinyl chloride (VCM) and hydrochloric acid (which can be also allows for the determination of physical properties
reused). The VCM must be cooled quickly (quenched) such as molecular weight, degree of branching, tacticity,
before it degrades further, requiring large quantities of melting point, particle size verification, density, and
water, which is also reused throughout the plant after viscosity.
cleaning. VCM is purified by distillation in large towers,
then stored before making PVC. This list is intended as a starting point but is not
comprehensive. Many determinations listed below
The polymerization process happens inside of an auto- could also be applied to other chemicals and pro­
clave in an emulsion or suspension with water. At this ducts.
point, the process can be adjusted to produce different
grades of PVC which are made into different products. Physical Characteristics (Thickness, Density,
Once the reaction in the autoclave is stopped, any unre- Viscosity):
acted VCM is stripped, purified and reused. A centrifuge • Monitoring Viscosity During a Phenolformaldehyde
removes excess water from the PVC slurry, which is then Resin Reaction (NIRS)
fed into a hot air dryer and a sieve to complete the • Monitoring a Coating Material on Polystyrene Pellets
process. (NIRS)

Applications for PVC: Monitoring Curing Rate:

• Acidity in Vinyl Chloride (VC/EDC/PVC Production) • Monitoring Degree of Cure (Monomer Content) on
• Calcium [Ca2+] + Hydrochloric Acid [HCl] in PVC Polymer Film (NIRS)
Production (Electrolysis) • Monitoring Cure Rate of an Adhesive (NIRS)
• Free Chlorine [Cl2] in Incineration Furnace Waste • Monitoring the Degree of Cure of Resin-Coated
Treatment (PVC Production, WWTP) Fiberglass (NIRS)
• Free Chlorine [Cl2] in PVC (PVC Production)
• Water [H2O] content in 1,2-dichloroethane [C2H4Cl2]
(EDC/VCM production)

Polymers
Hydroxyl Number:
• Monitoring Hydroxyl Number and Acid Value in
11
Various Polymer Products (NIRS)
• Monitoring the Hydroxyl Number in Powdered Resins
(NIRS)
• Quantitatively Determining the Hydroxyl Number in
Various Solid and Liquid Polyols (NIRS)
• Monitoring Hydroxyl Level of Polymer in an Ethanol/
Water Solution (NIRS)

Moisture/Water Content:
• Monitoring Moisture in Nylon (NIRS)
• Monitoring the Level of Water in Blends (NIRS)
• Determining the Relative Amounts of Water in an
Acrylic Resin Throughout a Three Step Drying Process
(NIRS)
• Monitoring the Concentration of a Polymer
Intermediate and Moisture in a Feed Reactor (NIRS)
• Monitoring a Melamine Reaction and Determining
Moisture in a Melamine Mix (NIRS) • Monitoring the Levels of Vinyl-Acetate and Three
Antioxidants in a LDPE-Based Polymer Pellet (NIRS)
Comparison / Distinguishing: • Monitoring Calcium Carbonate, Calcium Stearate,
• Qualitative Comparison of Polystyrene Pellets (NIRS) and Talc in Chlorinated Polyethylene (NIRS)
• Distinguishing Among Various PVC Samples (NIRS)
Additives:
Monitoring Blend/Reaction Characteristics: • Monitoring the Level of an Additive in PVC Sidings
• Monitoring a Polyurethane Reaction (NIRS) (NIRS)
• Monitoring Blend Composition in Butadiene/Styrene/ • Monitoring the Presence of an Additive in
Acrylonitrile Polymer Resins (NIRS) Polypropylene RCP Base Resin (NIRS)
• Monitoring Butadiene, Polycarbonate, and Butyl • Quantifying an Additive in Polypropylene Pellets
Acrylate in Polymer Pellets (NIRS) (NIRS)

Polymers
12

Chemical Industry

The Chemical industry as a whole is responsible for creat- and phenol, caprolactam production for Nylon-6, the
ing and supplying the world with precursors and reagents HPPO process which converts hydrogen peroxide to pro-
for every possible use. Various grades of chemical quality pylene oxide, and also the chemical fertilizer manufactur-
are needed depending on their end use: pharmaceuticals ing process. Other sold and installed applications for
need higher purity chemical reagents than metal leach- various chemical industry processes can be found at the
ing solutions in the mining industry, for example. It end of the chapter.
would be impractical to list every manufacturing process
in this handbook, so for more information it is advisable Standards for quality control
to search for the most updated global market informa- The importance of chemical products is reflected by the
tion online. large number of standards relating to them. Metrohm
instruments comply with numerous chemical and solvent
Process analyzers from Metrohm Applikon have been standards, which can be found below:
installed at numerous chemical plants worldwide for a www.metrohm.com/en/industries/chemical/
variety of applications in many areas. The following are a chemical-industry-basic-chemicals/chemical-
selection of some of the more prominent chemical ma­­ standards/
nufacturing processes to which we have sold many appli­
cations: the cumene process which produces acetone
www.metrohm.com/en/industries/chemical/
c h e m i c a l - i n d u s t r y - s o l ve n t s /c h e m i c a l -
solvent-standards/

Chemicals
Process Application Notes for the Chemical Industry 13
• HPPO process for Propylene oxide (PO): Analysis of peroxide.
AN-PAN-1007
• Cumene process: Analysis of Sulfuric Acid in Acetone and Phenol.
AN-PAN-1008
• Caprolactam Production: Determination of Permanganate Absorption Number.
AN-PAN-1011

Sold and Installed Applications

Cumene process for Phenol & Acetone production Applications for Cumene Process Waste:
In this process, two products (acetone and phenol) are • Total Cyanide [TCN] in waste water (WWTP –
created from a cumene precursor (itself created by the Toluene/Cumene production)
reaction of benzene and propene). Both phenol and • Phenol in waste water (WWTP)
acetone are widely used in many industries – phenol
mostly as a precursor to creating plastics and resins, and Caprolactam industry
acetone mainly as a solvent and also the precursor to Caprolactam is the precursor chemical to create Nylon-6,
plexiglass (Poly(methyl methacrylate)). If the two prod- which is ubiquitous in our lives. Nylon can be made into
ucts are allowed to react together, they form a third fabric, plastic machine parts, and even cookware (like
compound, bisphenol, which is used as a starting point spatulas) due to heat resistance up to its melting point of
in formation of polycarbonate plastics. Polycarbonate 256 °C. Multiple methods have been developed to syn-
plastics are known to be lightweight and transparent, thesize caprolactam, though the majority is now created
but also exhibit high impact strength and heat resistance. via a cyclohexanone precursor with bases and acids.
These plastics are used in many industries – from auto- Nearly all manufactured caprolactam is used for the syn-
motive and electronics to the food and beverage indus- thesis of Nylon-6.
tries.
Applications for Polyamide/Caprolactam
Bisphenol-A (BPA) is found in many hard plastics, such as Production:
water bottles, baby bottles, and even within the lining in • Acid Number in Anolon (Cyclohexanone before
food and beverage containers. This compound has often Oxidation step)
been in the news in recent years because it has been • Alkalinity in cooling water (Chemicals, Cooling water
found to mimic the effects of estrogen in the endocrine for Refinery Facility)
system, and leaches out from the plastic despite having • Ammonium [NH4+] + Nitrite [NO2-] in Caprolactam
low solubility in water. The exposure to low concentra- Production (Reactor)
tions are enough to disrupt the endocrine system, espe- • Ammonium Sulfite [(NH4)2SO3] in Caprolactam
cially for children, and could lead to developmental dis- Production (Reactor)
orders in later years. • Hydroxylamine [NH2OH] in Caprolactam Production
(Reactor)
Applications for Cumene Process: • Kjeldahl-N + Acid Value in Caprolactam Production
• Caustic [NaOH] in Phenol (Phenol Production) • Permanganate Index in Caprolactam Production
• Monitoring Parts per million (PPM) Levels of Moisture (Caprolactam Purification, End product)
in Phenol (NIRS) • pH (Acidity) in Caprolactam Production (Reactor)
• Sulfuric Acid [H2SO4] in Phenol-Acetone/Phenol
(Reactor – Acetone + Phenol production) Applications for Caprolactam Process Waste:
• Sulfuric Acid [H2SO4], Sodium Phenolate [C6H5NaO], + • Ammonium [NH4+] in Outlet WWTP (Effluent)
Sodium Hydroxide [NaOH] in process (Outlet Reactor) • Sodium hydroxide [NaOH] in Outlet Reactor
(Caprolactam Outlet Reactor)

Chemicals
14 HPPO Process – Propylene Oxide production
Propylene oxide is an important product for the chemical
Applications for the HPPO Process:
• Hydrogen Peroxide [H2O2] + Hydroquinone [C6H6O2]
industries because of its wide range of applications that (Reactor, Hydrogen peroxide production)
are predominantly used in the polyurethane and solvent • Hydrogen Peroxide [H2O2] in Anthraquinone [C14H8O2]
industries. The total PO market is still growing and so is (Hydrogen peroxide production)
the need for a cost efficient and environmentally friendly • Hydrogen Peroxide [H2O2] in Condensate (Hydrogen
production process. Today’s industry leading technology peroxide production)
process «HPPO» (Hydrogen Peroxide to Propylene Oxide) • Monitoring Peroxide in a Reaction Stream (NIRS)
yields PO from propene and hydrogen peroxide using a
titanium silicate catalyst, leaving water as a byproduct. Applications for HPPO Process Waste:
• Hydrogen Peroxide [H2O2] in neutralized aqueous
Hydrogen peroxide present in a methanol solvent is used effluent (WWTP)
as the sole oxidizing agent and is the critical feedstock • Hydrogen Peroxide [H2O2] in waste water (Hydrogen
and parameter to measure the complete conversion rate peroxide production, WWTP)
to PO. Therefore there is a high demand for accurate and
robust online process monitoring throughout the entire
reaction process. Measuring the H2O2 concentrations in
the primary reaction tank plays a vital role to ensure high
PO yields while reducing costs with low feedstock con-
sumption.

Fertilizer manufacturing
Fertilizer is used to supply essential nutrients for prolifera-
tion of plant growth, leading to larger yields in the agri-
cultural industry. Fertilizers can come from either natural
(such as manure, bone meal, or compost) or synthetic
sources. Primarily, synthetic fertilizers are made of nitro-
gen, phosphorus, and potassium compounds, though
single-nutrient fertilizers are also available on the market.
Synthetic fertilizers can be easily modified to better meet
the nutritional needs of individual crops and soils. De­­fi­
ciencies in these nutrients result in stunted growth, yel-
lowed leaves, and an overall weak structure.

The synthesis of the nitrogen component begins with

ammonia (NH3) generally derived from the large-scale
Haber process, which is then reacted with nitric acid
(HNO3) to create ammonium nitrate. Phosphorus can be
derived from mineral sources with acid digestion, and
can be made into either ammonium phosphate or triple Applications for Fertilizer Production:
superphosphate (TSP). The potassium component comes • Phosphoric acid [H3PO4] in Diammonium phosphate
from potassium chloride, generally granulated in order [(NH4)2HPO4] production
for easier blending with the other compounds so that the • Phosphorus pentoxide [P2O5] in Fertilizer Production
fertilizer can be easily and properly distributed. • Sulfate [SO42-] in Fertilizer Production
• Sulfuric Acid [H2SO4] in Phosphoric Acid [H3PO4] for
Fertilizer Production (H3PO4 Reactor)

Chemicals
Applications for Fertilizer Emission Control:
• Ammonia [NH3] in Fertilizer Production (Emission
NIRS Applications for the Chemical Industry:
15
Control) This list is intended as a starting point but is not
• Ammonia [NH3] + Nitrate [NO3-] in Fertilizer comprehensive. Many determinations listed below
Production (Waste water recovery) could also be applied to other chemicals and pro­
• Chloride [Cl-] in Fertilizer Production (WWTP) ­ducts.
• Chloride [Cl-] in Outlet Anion Exchange Column
(Quality control, water after column with anion Surfactants:
exchange resin) • Monitoring Surfactants in a Water/Isopropyl Alcohol
• Fluoride [F-] in Fertilizer Production (WWTP, Emission Mixture (NIRS)
Control) • Monitoring the Presence of a Surfactant in a Water
• Nitrate [NO3-] in Fertilizer Production (effluents Solvent (NIRS)
treatment)
• Total Phosphate in Fertilizer Production (WWTP) Moisture Analysis:
• Silica [Si] in Outlet Anion Exchange Column (Quality • Monitoring Low Level Moisture in Ethylenediamine
control, water after column with anion exchange (NIRS)
resin) • Monitoring the Levels of Water and Fluorosulfonic
Acid in a Mixed Hydrofluoric/Sulfuric Acid Stream
Other Applications for the Chemical Industry: (NIRS)
• Ammonia [NH3] in process (MDEA Production) • Monitoring Water, Acetic Acid, Beta-Picoline and
• Caustic [NaOH] in process Dimethylacetamide in a Solvent Stream (NIRS)
• Chlorine [Cl2] in Titanium(II) oxide [TiO2] (Titanium
Oxide production) Reaction Monitoring:
• Hexavalent Chromium [Cr6+] in waste water (Chromic • Monitoring the Hydrolysis Reaction of Polyvinyl
Acids production) Alcohol (NIRS)
• Hydrochloric acid [HCl] in process water (Herbicides, • Monitoring the Chemical Reaction of Nonene with
Acid Adjust Tank) Diphenylamine (NIRS)
• Hypochlorite [ClO-] + Thiosulfate [S2O32-] in process • Monitoring Hydroquinol Production in a Reaction
• P&M Number in Demi water (Demi Water plant, Stream (NIRS)
Decarbonization) • Monitoring Bromine Number (Degree of Unsaturation)
• Sodium hydroxide [NaOH] in Caustic Scrubber during the Hydrogenation of a Polyalphaolefin (NIRS)
• Water determination in Carbon Tetrachloride [CCl4]
by Karl Fischer Titration Mixtures:
• Monitoring Methoxypropylamine and N,N
Waste Water: Diethylaminoethanol in a Complex Mixture (NIRS)
• Ammonia [NH3] in waste water (WWTP)
• Chemical Oxygen Demand [COD] in waste water Solvent purity and recovery:
(WWTP) • Monitoring Glycol Purity (NIRS)
• Chloride [Cl-] in waste water (Final Effluent discharge) • Monitoring the Levels of Toluene in an Organic
• Cyanide [CN-] in influent WWTP (Chemicals, WWTP) Solvent (NIRS)
• Fluoride [F-] in Recycled water (Fluorinated Polymers,
WWTP)
• Free Chlorine [Cl2] in condensing water (WWTP)
• Nitrate [N-NO3-] in waste water (WWTP)
• Phosphate [P-PO43-] in waste water (WWTP)

Chemicals
16

Petrochemical Industry

A demanding industry Explosion-proof systems for petrochemistry

Crude oil is a highly complex mixture of hydrocarbons In many cases, the IP66-NEMA4 housing of our Process
and other compounds that through desalting, distillation Analyzers will be sufficient. In some cases in the petro-
and conversion is transformed into higher quality hydro- chemical industry, however, explosion-proof systems are
carbons. This refining is demanding and requires precise required. For those circumstances, the Metrohm Process
and reliable analysis. Analytics 2045TI Ex proof Analyzer is available in a stain­
less-steel explosion-proof version for Zone I or Zone II
Lubricant of the global economy ac­­cord­ing to the European explosive atmosphere direc-
Nowadays crude oil, which consists of at least 500 differ- tives (ATEX).
ent components, is processed by distillation and refining
to produce liquefied gas, gasoline, diesel, heating fuel, Standards for quality control
and lubricants as well as a large variety of other products. The importance of petroleum products is reflected by the
As the «lubricant» of the global economy, crude oil is large number of standards relating to them. Metrohm
omnipresent. It covers approximately 40% of our energy instruments comply with numerous petrochemical stan-
demand and is used in the chemical industry for the dards, which can be found within the three Petrochemical
production of plastics, textiles, dyes, cosmetics, fertiliz- branch sites here:
ers, detergents, building materials, and pharmaceuticals. www.metrohm.com/en/industries/

Petro
Process Application Notes for the Petrochemical Industry 17
• Sour Water Stripper (SWS): Analysis of hydrogen sulfide and ammonia in Sour Water.
AN-PAN-1001
• Desalting Crude Oil – Analysis of Salt in Crude Oil.
AN-PAN-1014
• Mercaptans and Hydrogen Sulfide Derived from Crude Oil According to ASTM D3227
and UOP163. AN-PAN-1026
• Inhibiting Polymerization: Monitoring the Concentration of TBC in Styrene According
to ASTM D4590. AN-PAN-1027
• ASTM D8045: Online measurement of the acid number (AN) in oils with
thermometric titration. AN-PAN-1037

Sold and Installed Applications

Biodiesel Production:
• Acid number + Potassium in biodiesel • Calcium [Ca2+] in reactor WWTP (reactor WWTP)
• Acidity + moisture in biodiesel • Chemical Oxygen Demand [COD] in refinery waste
water (WWTP)
Kerosene Production: • Chloride [Cl-] in refinery waste water (WWTP)
• Mercaptans + Total Acidity in Kerosene (Kerosene • Nitrite [NO2-] in waste water (WWTP)
purification process) • Total Nitrogen [TN] in water control
• Sodium chloride [NaCl] in Crude Oil (Salt in crude) • Phenol [C6H5OH] in refinery waste water (WWTP)
• Water determination in Kerosene and Diesel • Phosphate [PO43-] / Total Phosphate [TP] in waste
(Production and Purification Processes) water (water control, WWTP)
• Sulfate [SO42-] in waste water (Seawater treatment,
Other Downstream Processes: WWTP)
• Free and Total Acid determination in Refinery Processes • Sulfide [S2-] in refinery waste water (Stripped water,
(Water Carbonate Removal) WWTP)
• Ammonia [NH3] / Ammonium [NH4+] in Petrochemical • Sulfite [SO3-] in waste water (WWTP)
water treatments (Acid water treatment, Sour Stripper
water, Circulation water, Waste water, etc.) Other Applications for the Petrochemical
• Carbonate [CO32-] in water recovery process Industry:
• Chlorine [Cl2] in water treatment processes • 4-tertiary-butylcatechol [TBC] in Styrene (Styrene Inlet
(Cooling water) Storage Tank)
• Fluoride [F-] in cooling water (Alkylation Unit) • Acetic Acid [CH3COOH] in Petrochemical Processes
• Hypochlorite [ClO-] in Cooling water system • Acid number in synthetic light oil (Synthol reactor)
• Moisture in gasoline • Amine strength (Amine Production)
• P&M value in water (Water Carbonate Removal) • Bromide [Br-] Index + Bromine number in Petro­
chemical Processes (LAP Production, Naphtha Cracker)
Waste Water: • Carbonyl number in oxo-alcohols
• Ammonia [NH3] / Ammonium [NH4+] in waste water • Caustic [NaOH] in Diethylene Glycol [DEG] (Ethylene
• Ammonia [NH3] + Sulfide [S2-] in inlet of WWTP Glycol production, MEG Scrubber)
(Waste Water Treatment, Sour water) • Caustic [NaOH] in fuels (Refinery process)
• Ammonium [NH4+] + Hydrogen sulfide [H2S] (WWTP) • Total Caustic [OH-] + Free Caustic [OH-] in Ethylene
• Barium [Ba2+] in waste water (WWTP) Scrubber

Petro
18 • Chloride [Cl-], Iron [Fe2+], + pH in Distillate stream
(Overhead Condensing System of Crude Distillation
aromatics, naphthenes, and olefins; PIANO). Common
die­­sel parameters measured with NIR include specific
Unit) gra­­­­vity, viscosity, flash point, cold filter plugging point
• Cobalt [Co2+] in Petrochemical Hydrotreating (CFPP), pour point, and cloud point. Also possible to
Processes (Petrochemical production, Desulfurization monitor with NIRS: crude oil distillation, gasoline blend-
process) ing, diesel blending, and biofuels blending (ethanol in
• Hydrogen peroxide [H2O2] in Dispensed/Recovery ga­­soline, biodiesel).
Liquid (Methanol/Propylene/H2O/Propylene-Oxide
mixture) This list is intended as a starting point but is not
• Iron [Fe2+], Chloride [Cl-], + pH in Distillate stream comprehensive. Many determinations listed below
(CDU Crude Distillation Unit) could also be applied to other chemicals and pro­
• Methoxyethanol in aircraft fuel ­ducts.
• Saponification value in various petrochemical products
(Petrochemical process) • Monitoring the Alkylation Process (NIRS)
• Water [H2O] + Formic Acid [HCOOH] in Methanol • Monitoring a Gasoline Blend (NIRS)
(Water Removal Process) • Monitoring the Level of Rolling Oil in a Rolling Oil
Emulsion (NIRS)
NIRS Applications for the Petrochemical Industry: • Monitoring a Mixture of Pentane, Pentane, and
NIR Spectroscopy can monitor many processes in the Pentyne (NIRS)
Petrochemical sector. Gasoline parameters measured • Monitoring the Pour Point of Lube Oils (NIRS)
with NIR cover research octane (RON, ASTM D2699), • Monitoring Saponification Value in Various Oil
motor octane (MON, ASTM D2700), and road octane Products (NIRS)
number (RdON), and volume percentage or even mole • Monitoring Surfactants in Oil (NIRS)
percent of individual components (paraffins, isoparaffins,

Petro
 19

Semiconductor / Electronics Industry

Semiconductors in everyday use Record sales in 2014, slowdown in 2015

Semiconductors are the fundamental components of According to the Semiconductor Industry Association,
modern electronic goods. With the advent of the digital 2014 was a record year, with worldwide sales totaling
age and now the current «Internet of Things», smaller, US $ 335.8 billion, increasing by 9.9 percent from 2013.
faster, and more powerful processors are in constant In 2015, global sales were strong through June, but fell
demand for many goods and services. The semiconduc- for the rest of the year. This resulted in a net increase of
tor industry is largely responsible for improving many 1.1% from 2014, totaling US $ 337.3 billion. World
aspects of society as many services have been digitized Semi­conductor Trade Statistics projects a modest 0.3%
and interlinked (e.g. Big Data, smart grids). Without suf- increase in market growth for 2016, and up to 3.1% in
ficient processing power, a service can be rendered ob­­ 2017.
solete as new technologies are introduced daily. Security,
health care, energy efficiency, and many other sectors
benefit greatly from improvements within the semicon-
ductor industry.

Semicon / Electronics
20 Process Application Notes for the Semiconductor / Electronics Industry
• Electroless Nickel Plating; Semiconductor, PCB industry Analysis of Nickel ion &
Hypo­phos­phite content. AN-PAN-1012
• Monitoring Tetramethylammonium Hydroxide (TMAH) in Developer.
AN-PAN-1028

Sold and Installed Applications

Aluminum Foil Etching: Wafer Etching:

• Free and Total Acid in Etching bath (Aluminum Foil • Acid (Total) - (Phosphoric acid [H3PO4], Nitric acid
for Electrolytic Capacitors, PCB) [HNO3] and Citric acid) in etching process (LCD
• Free and Total Acid + Ortho-Phosphate [P-PO4] in Manufacture)
Etching bath (Aluminum Foil for Electrolytic Capacitors, • Total Acid in etching baths (Touch Panel, Etching bath)
PCB) • Acidity in etching baths (Copper bath)
• Chloride [Cl-] in Etching bath (Aluminum Foil Etching • Acidity + Nitrite [NO2-] in etching baths (PCB, Etching
Bath) bath)
• Phosphoric acid [H3PO4] in Etching bath (Aluminum • Chloride [Cl-] in 50 to 80% Sulfuric Acid [H2SO4]
Foil for Electrolytic Capacitors, PCB) (Waste H2SO4 recycling system)
• Copper [Cu2+], Sulfuric acid [H2SO4], + Chloride [Cl-]
Glass Etching: in etching bath (Micro-Chips, Etching bath)
• Hydrofluoric acid [HF], Nitric acid [HNO3], + Sulfuric • Copper [Cu2+], Sulfuric acid [H2SO4], + Sodium
acid [H2SO4] in etching baths (LCD Display, Glass peroxosulfate [NaPS] in Etching Cleaner (BOC (Board
etching) On Chip))
• Nitric acid [HNO3], Sulfurous Acid [H2SO3], + Hydro­ • Hydrochloric acid [HCl], Aluminum Chloride [AlCl3], +
fluoric Acid [HF] in etching (LCD screen, Glass etching) Boric acid [B(OH)3] in process (Transistor & Resistors,
• Oxalic acid [H2C2O4] in etching process (LCD manufac- Etching bath)
turing) • Hydrofluoric Acid [HF] + Hydrochloric acid [HCl]
• Sulfuric acid [H2SO4] + Hydrogen Fluoride [HF] in (binary acid etchant)
process (Glass etching) • Hydrogen peroxide [H2O2] + Hydrochloric acid [HCl] in
etching bath (Surface treatment, etching bath)
Solar Etching: • Hydrogen Peroxide [H2O2] + Sulfuric Acid [H2SO4] in
• Hydrogen fluoride [HF], Hexafluorosilicic acid [H2SiF6], Etchant (Touch Screen Panels, Monitoring Etchant,
Nitric Acid [HNO3], + Acetic Acid [CH3COOH] (Wafer Etching Clean Bath)
texturing of solar panels) • Iron [Fe2+], Nickel [Ni2+], + Copper [Cu2+] in Etching
• Hydrofluoric Acid [HF] + Nitric acid [HNO3] Etching Bath (Monitoring Etching Bath, SC1, SC2)
baths (Solar Cells, Etching Baths, Mixed acid etchant) • Methanesulfonic acid [MSA] + Hydrofluoric acid [HF]
• Isopropyl alcohol [C3H8O] + Sodium hydroxide [NaOH] in MSA/HF storage tanks (Wafers, Etching baths)
in etching baths (Wafer Texturing, Etching bath) • Monitoring Etching Baths (NIRS)
• Nitric acid [HNO3], Hydrogen fluoride [HF], + Hexa­ • Monoethanolamine [MEA] + water [H2O] in Alkaline
fluor­osilicic acid [H2SiF6] / Hydrochloric acid [HCl] + Photoetch (Flexible Electronic Circuitry)
Hydrogen fluoride [HF] / Potassium hydroxide [KOH] + • Nickel [Ni] + Hypophosphite [H2PO2-] in etching baths
Sodium hydroxide [NaOH] (Solar Panels, Etching (Etching baths)
Texturing) • Nitric acid [HNO3] in etching bath (Etching)
• Potassium hydroxide [KOH], Isopropanol, + Hexa­- • Sulfuric acid [H2SO4], Hydrofluoric acid [HF], +
fluor­osilicic acid [H2SiF6] / Hydrochloric acid [HCl] + Hydrogen peroxide [H2O2] in etching baths (Wafers,
Hydrogen fluoride [HF] / Hydrogen peroxide [H2O2] Etching baths)
(Solar Panels, Etching Texturing)

Semicon / Electronics
• Sulfuric acid [H2SO4], Phosphoric acid [H3PO4],
Hydrogen Peroxide [H2O2], + Titanium in Etching bath
Waste Water:
• Ammonia [NH3] in waste water (WWTP)
21
(Copper Etchant, Mixing) • Ammonia [NH3], Fluoride [F-], + pH in Hydrofluoric
• Tin [Sn2+] + Copper [Cu2+] in etching bath (Integrated Acid Waste (HFW) (WWTP)
Circuits (PCB), Sn/Cu Plating bath) • Boron [B] in waste water (Glass Thinning in LCD
• Tin [Sn2+] + Free Acid in Tin Plating baths (Etching Industry, WWTP)
baths, Electronic components) • Cadmium [Cd] in waste water (Solar Panels, WWTP)
• Calcium [Ca2+] in waste water (WWTP)
Photolithography: • Chemical Oxygen Demand [COD] in waste water
• Tetramethylammonium hydroxide [TMAH] in (Chip (Wafer), Solar Panels, WWTP)
Developer (LCD Screen, Photoresist, Developer • Chloride [Cl-] in waste water (WWTP)
Recycling System) • Hexavalent Chromium [Cr6+] in waste water (PCB
• Monitoring Tetramethylammonium Hydroxide [TMAH] Industrial, Electroplating Products, WWTP)
in Water (NIRS) • Copper [Cu2+] in waste water (PCB Industrial, CCW,
Chip (Wafer), WWTP)
Plating Baths: • Copper(I) [Cu+] and Copper(II) [Cu2+] in waste water
• Copper [Cu2+] in plating (Electroless Copper Plating, (PCB Industrial, WWTP)
Flexible PCB) • Copper [Cu2+] + Cobalt [Co2+] in waste water (Chip
• Copper [Cu2+] in Zinc Electrolyte (Zinc electrolysis) (Wafer), Heavy Metals Waste Treatment, WWTP)
• Copper [Cu2+], Sodium hydroxide [NaOH], + Formal­ • Copper [Cu2+] + Hydrogen Peroxide [H2O2] in slurry
dehyde [CH2O] in electroless Copper (BOC (Board On Copper waste treatment (Chip (Wafer), waste water
Chip)) treatment)
• Dimethylamine borane [DMAB], Boric acid [B(OH)3], • Copper [Cu2+], Iron [Fe3+], + Nickel [Ni2+] in waste
Cobalt(II) sulfate [CoSO4], + pH in Cobalt plating bath water (WWTP)
(Chip manufacturing, plating baths) • Cyanide [CN-] in waste water (Electroplating Products,
• EDTA in Cu Bath (PCB production) WWTP)
• Glycolic Acid + pH in Cu-Electro plating bath (Chip • Fluoride [F-] in waste water (Chip (Wafer), Semi­
manufacturing, plating baths) conductor, Solar Cells, WWTP)
• Formaldehyde [CH2O], Sodium hydroxide [NaOH], + • Hydrogen peroxide [H2O2] in waste water (WWTP)
Dimethylamine borane [DMAB] in Cu plating solution • Nickel [Ni2+] in waste water (WWTP)
(PCB, Copper Plating) • Nitrite [NO2-] in waste water (Solar Panels, Detox
• Leveller in acid-Cu bath (Micro-Chips, Copper Plating Waste Water, WWTP)
at Pilot Plant) • Phenol [C6H5OH] in waste water (Semiconductor,
• Nickel [Ni2+] + Hypophosphite [H2PO2-] in Nickel WWTP)
Plating Bath (Electroless Wafer Bumping, Nickel • Ortho-Phosphate [PO43-] in waste water (WWTP,
Plating Bath) Outlet LED production)
• Nickel [Ni2+] + Phosphoric acid [H3PO4] (Nickel bath) • Sulfate [SO42-] in waste water (Final Effluent
• Tin [Sn2+] + Free Acid in Tin Plating baths (Etching monitoring, WWTP)
baths, Electronic components) • Tin [Sn2+], Lead [Pb], + Copper [Cu2+] in waste water
• Tin [Sn2+] + Copper [Cu2+] in etching bath (Integrated (WWTP)
Circuits (PCB), Sn/Cu Plating bath)

Semicon / Electronics
22 Other Applications for the Semiconductor/
Electronics Industry:
• Ammonia [NH3] in cooling water (Microchips • Hydrochloric acid [HCl] + Hydrogen Peroxide [H2O2]
production) in SC2 Clean
• Ammonium [NH4+] in Chemical Dilution system (Semi­ • Hydrofluoric acid [HF] in process water (Chemical
conductor parts) preparation, Dilution system, Blending)
• Ammonium Hydroxide [NH4OH] (Chemical distribution, • Hydrogen Peroxide [H2O2] in CMP Slurry (Wafer
Blending system) polishing, Chemical Mechanical planarization)
• Ammonium Hydroxide [NH4OH] + Hydrogen Peroxide • Hydrogen Peroxide [H2O2] + Ammonia [NH3] in
[H2O2] in SC1 Clean reclaim water (Reclaim water)
• Benzotriazole (BTA) [C6H4N3H] as Copper Corrosion • Hydrogen peroxide [H2O2], pH, Temperature, +
Inhibitor in flexible circuitry Conductivity (CMP Slurry chemical blending)
• Copper [Cu2+] + Hydrogen Peroxide [H2O2] in SCW • Phosphoric acid [H3PO4], Hydrogen peroxide [H2O2], +
(Slurry Copper Waste) (Ion exchange Treatment, Chip Copper [Cu2+] (semiconductors)
wafer) • Silica [Si4+] in make-up water (Solar Cells, Make-up
• Copper [Cu2+], Zinc [Zn2+], Nickel [Ni2+], Free and Total water)
Acid (Zinc, Acid baths) • Sodium [Na+] in Make-up Water (Solar Cells, Make-up
• Hydrochloric acid [HCl] in recovery systems (TMAH water)
Recovery System, Wafers) • Sodium hydroxide [NaOH] in cleaner for Electroless
• Hydrochloric acid [HCl] + Germanium [Ge] Copper Wet Bench
(Germanium purifying)

Semicon / Electronics
 23

Mining Industry

Ever-increasing demands
Mining produces both common and rare elements which the ore, the ore is ground up and allowed to mix with the
are then refined and used in all kinds of other industries, solution, such as in gold cyanidation where cyanide is
from creating jewelry to the manufacture of electronics. used to leach gold. The cyanide lowers the amount of
The global mining industry is undergoing massive expan- oxygen in the water considerably which can affect the
sion to meet the increasing demand for minerals and rate of leaching, but this waste water has severe conse-
metals. This expansion is taking place in an environment quences for the environment and must first be treated
where costs of capital, labor, raw materials and other with oxidants to decrease its toxicity.
inputs are all rising, demanding that operations must be
run at optimum efficiency. Electrowinning can be used instead of ion exchange
resins to recover materials, in fact – this is the only pro-
Extraction and refining cess to refine aluminum from ore. In this case, the semi-
In order to extract some materials, a process known as saturated leaching solution is electrolyzed and the mate-
«leaching» is performed by introducing a leaching solu- rial (such as copper or gold) is electroplated on a large
tion (such as hydrochloric acid, sulfuric acid, or nitric scale. Some metals need subsequent reduction to be
acid) into bore holes and fracture lines in the ground. The refined, while others can deposit at the bottom of the
solution is pumped out after a certain amount of time plating tank and form anodic sludge, which also requires
and allowed to flow through ion exchange resins to con­ further treatment before the refined material can be
centrate the material (such as uranium). In some situa- used.
tions, rather than pumping the carrier solution down into

Mining
24 Quality control with chemical analysis
Accurate and reliable chemical analysis plays a crucial remediation processes require chemical analysis to ensure
role in meeting these challenges. It is required to keep that environmental impact is minimal. For the mining
mining and refining operations running at peak efficiency, industry, continuous control of the production process,
as well as ensuring that raw materials and products are the quality of the product, and the composition of any
of the specified quality. Moreover, waste streams and waste streams is of utmost importance.

Process Application Notes for the Mining Industry

• Hydrometallurgical Process: Analysis of Free, Total & WAD Cyanide in gold leach slurry
& wastewater. AN-PAN-1002
• Zinc production: Analysis of Zinc, Sulfuric acid and Iron.
AN-PAN-1006
• Analysis of Bayer Aluminate Liquors Using Thermometric Titration.
AN-PAN-1034

Sold and Installed Applications

Copper Mining & Purification: Gold Mining & Purification:

• Chloride [Cl-] in Copper Electrolyte solution (Copper • Cyanide, Free [CN-] in gold mining (Gold winning,
refinery, Electrolyte tanks) WWTP)
• Copper [Cu2+] in refining processes (Copper electro • Cyanide, total [TCN] (Gold mining, Detoxination Plant
refining, Nickel purification, Refinery Deep Electrolyte (CIP/CIL Plant))
Decopperization, Smelter, Metal recovery) • Cyanide, Weak Acid Dissociable [CN-WAD] (Gold
• Copper [Cu2+] + Iron [Fe3+] (Copper mining) mine, WWTP, Gold winning, Electroplating)
• Metals (Cadmium [Cd] / Cobalt [Co] / Copper [Cu] /
Germanium [Ge] / Antimony [Sb]) (Metal Purification, Leaching Processes:
Recovery) • Ammonia [NH3] + Carbon Dioxide [CO2] (Nickel,
• Sulfuric acid [H2SO4], Copper [Cu2+], Iron [Fe2+], Iron Leaching S/X Circuit)
[Fe3+], + BT (Copper refinery) • Metals (Total) + pH (Leach plant)
• Silica [SiO2] in Ammonium sulfate [(NH4)2SO4] in
Electrowinning Processes: Manganese processing (Leaching, Thickening, and
• Acid, Chloride [Cl-], Iron [Fe2+], + Rx in Copper Purification)
electro­winning process (Electrolysis) • Sulfuric acid [H2SO4], pH, Redox, + Chloride [Cl-]
• Chloride [Cl-] in Copper Electrolyte solution (Copper (Copper mining, Leaching)
refinery, Electrolyte tanks) • Zinc [Zn2+] + Sulfuric Acid [H2SO4] in process (Zinc
• Copper [Cu2+] from copper electrowinning (Copper production, zinc leaching)
electro refining)
• Copper [Cu2+], Sulfuric Acid [H2SO4], + Chloride [Cl-] Nickel Mining & Purification:
in Electrolyte (Metallurgy company, Refinery Deep • Aluminum [Al3+] (Nickel Purification)
Electrolyte Decopperization) • Ammonia [NH3] in process (Nickel, Solvent Extraction,
• Free Acid (Nitric Acid) [HNO3] in process (Uranium WWTP)
Processing, Uranium Extraction (Yellow Cake Process)) • Ammonia [NH3] + Carbon Dioxide [CO2] (Nickel,
• Sulfur Dioxide [SO2] in Electrolyte solution (Manganese, Leaching S/X Circuit)
SO2 Absorption into Feed Electrowinning) • Copper [Cu2+] in Nickel(II) sulfate [NiSO4] refining
• Sulfuric acid [H2SO4] (Zinc purification, Copper Electro­ process (Deep removal copper process)
winning, Copper Electro Refining) • Nickel [Ni2+] from purification processes (Nickel
Purification)
• Sulfide [S2-] gas in flue gas in acid smelter in Nickel
mine (Nickel)

Mining
• Zinc [Zn2+] (Nickel Purification)
Platinum Refineries:
• Acid, pH, Redox, + Caustic [NaOH] in multiple sample • Cyanide, Free [CN-] in waste water (WWTP)
25
streams (Platinum refineries) • Cyanide, total [TCN] in Process Waste (Polymetallic
• Molar Ratio [Ni/NH3] (Platinum refineries) mining, Cyanide Destruction Plant)
• Cyanide, Weak Acid Dissociable [CN-WAD] in waste
Zinc Mining & Purification: water (WWTP)
• Acid + Iron [Fe2+] in Zinc Mining • Fluoride [F-] in waste water (Waste water treatment)
• Acidity in zinc production processes (Zinc Purification) • Hydrochloric acid [HCl] in Waste Water Treatment
• Cadmium [Cd] in Zinc sulfate [ZnSO4] (Zinc Purification, Plant (Nickel, PN Feed)
WWTP) • Manganese [Mn2+] in Waste Water Treatment Plant
• Cobalt [Co2+] in Zinc Electrolyte (Zinc electrolysis) (Nickel, PN Feed)
• Cobalt [Co2+] in Zinc-plant liquid purification (Zinc plant) • Metals (Total) in effluent (Waste water treatment)
• Copper [Cu2+] + Iron [Fe3+] (Copper mining) • Phosphate [PO43-] in waste water
• Hydrogen Sulfide [H2S] in Process (Zinc production) (Grit Chamber, precipitation of particles, WWTP)
• Hydrogen sulfide [H2S] in zinc purification processes • Silica [SiO2] in waste water (Metallurgy company,
(Zinc purification) WWTP)
• Iron [Fe2+] (Zinc purification) • Sulfate [SO42-] in waste water
• Iron [Fe] + Sulfuric Acid [H2SO4] in Electrolysis (Zinc • Sulfide [S2-] in waste water (Zinc & Lead Production,
production, Electrolysis) WWTP)
• Sulfuric Acid [H2SO4] in Electrolysis (Zinc production,
Electrolysis) Other Applications for the Mining Industry:
• Zinc [Zn2+] + Manganese [Mn2+] in Electrolysis (Zinc • Acid and Chloride [Cl-] in copper electrolyte solution
production, Electrolysis) • Acidity (Total + Free), Zinc [Zn], Iron [Fe], + Chloride
• Zinc [Zn2+], Manganese [Mn2+], + Sulfuric Acid [H2SO4] [Cl-] in process (Acid Recovery Plant)
in Electrolysis (Zinc production, Electrolysis) • Chromic acid [H2CrO4] (Chrome production)
• Zinc [Zn2+] + Sulfuric Acid [H2SO4] in process (Zinc • Dinitrogen trioxide [N2O3] in H2SO4 (Reactor, Sulfuric
production, zinc leaching) Acid by absorption of SO2)
• Hypochlorite [OCl-] in a scrubber system for exhaust
Waste Water: gas (mining)
• Ammonia [NH3] in process (Nickel, Solvent Extraction, • Metals (Total) and Acid in spent electrolyte (Autoclave
WWTP) Spent Electrolyte)
• Cadmium [Cd] in Zinc sulfate [ZnSO4] (Zinc Purification, • Monitoring Moisture Content in Concentrated Iron
WWTP) Ore Samples (NIRS)
• Calcium [Ca2+] in waste water (Zinc Copper mining, • Sodium Hydrosulfide [NaHS] in copper production
WWTP) (Molybdenum selection)
• Hexavalent Chromium [Cr6+] in Waste Water Treatment
Plant (Nickel, PN Feed)

Mining
26

Steel / Metal Industry

An industry with nerves of steel

The Metals industry, and steel in particular, is responsible 1250 °C) into the furnace, eventually forming liquid «pig
for creating the infrastructure that our modern world iron» and lighter slag as a byproduct. The iron is collected
depends on. Steel is essentially a form of iron, combined and lime powder added to reduce the sulfur content in
with a small amount of carbon (typically less than 1%), order to preserve ductility in the final product.
which is refined for strength and formability. In 2014,
according to the World Steel Association, 51.2% of When the refined iron is reheated prior to steelmaking,
global steel production went toward construction proj- scrap steel is added to help control the temperature due
ects, such as houses and skyscrapers. China is the largest to oxidation of impurities in the mixture. Pure oxygen is
steel producer in the world, followed by Japan, India, the added in the blast furnace to the liquid pig iron, oxidizing
US, and Russia. In 2015, world crude steel production the impurities into slag, and eventually the mixture
slowed, with a change of -2.8% compared to 2014. reaches a final temperature of 1650 °C. Excess carbon is
also removed via vacuum degassing.
Bessemer Process
The industrial production of steel is performed via the Metal alloys can be created with other elements like
Bessemer process, patented in the 1850’s. Iron from iron titanium, manganese, or aluminum, which can be added
ore, coal converted to coke (pure carbon) at 1100 °C, to de-oxidize and improve the ductility of steel for
and limestone are blended, sintered (a process also used example. Inert gases such as argon are bubbled through
in lead and copper production), and poured into a blast the hot mixture to stir and ensure homogeneity in com-
furnace. The iron is released and combined with carbon position and temperature, as well to float out remaining
by the coking process and injection of hot air (around impurities into the slag above.

Steel / Metal
The liquid steel is then poured into casts and while still
warm, rolled out into increasingly thinner sheets, which
Hot vs. cold roll
Hot rolled steel is suitable for pipes, tubing, auto frames,
27
can then be further treated based on customer requests. rail cars, and construction and agricultural equipment.
Pickling baths with hydrochloric acid are used to remove Cold rolled steel is better suited for exposed automotive
the oxide layer which formed on the surface during the body parts, appliance cabinets, office furniture, and elec-
hot strip mill. The cold mill squeezes the sheets of steel tric motors. Cold rolled steel is harder, and sometimes
even further, giving a smooth finish and increasing the must go through an additional heat treating process
steel’s strength. called annealing to restore its formability. Surfacing tech-
niques such as galvanization are used to make metal
corrosion- and heat-resistant. Metal surfacing informa-
tion can be found in the following chapter.

Process Application Notes for the Steel / Metal Industry

• Steel Industry: Analysis of Acids and Iron in Pickling Baths.
AN-PAN-1019

Sold and Installed Applications

Pickling Process:
• Acid (Total), Hydrogen fluoride [HF], + Nitric acid • Manganese [Mn2+] + Sulfate [SO42-] in waste water
[HNO3] (Acid Pickling Stainless Steel) (Manganese Based Metals, WWTP)
• Hydrochloric acid [HCl] in Pickling solution (Pickling • Nickel [Ni2+] in ground/waste water (WWTP)
bath) • Nitrate [NO3-] in influent (Stainless Steel, WWTP)
• Hydrochloric acid [HCl] + Iron [Fe] in Pickling solution • pH, Free-Ammonia [NH3], + Total Ammonia [NH3]
(Pickling bath) in waste water (Steel, Waste De-Ammonization of
• Hydrogen Peroxide [H2O2] in Pickling solution (Stainless Coke plant)
Steel, Pickling process) • Sodium sulfate [Na2SO4] in waste water (WWTP)
• Iron [Fe3+], Sulfuric Acid [H2SO4], + Hydrogen Fluoride • Thiosulfate [S2O32-] in waste water (WWTP)
[HF] in pickling bath (Pickling bath) • Zinc [Zn2+] in waste water (Metal treatment, WWTP)
• Zinc [Zn2+] + Sulfuric acid [H2SO4] in waste water
Waste Water: (WWTP)
• Ammonia [NH3] in waste water (WWTP)
• Ammonia [NH3], Nitrate [NO3-], + Nitrite [NO2-] in Aluminum Milling:
waste water (Steel, WWTP) • Aluminum [Al3+] + Caustic [NaOH] (Aluminum)
• Ammonia [NH3], Phenol [C6H5OH], Cyanide [CN-], + • Fluoride [F-] in 2.5% Sulfuric Acid [H2SO4] bath
Thiocyanate [SCN-] in effluent WWTP (Outlet WWTP (Aluminum Annealing Line)
Cokes plant) • Fluoride [F-] + Free and Total Acid in etching bath
• Chemical Oxygen Demand [COD] (BDS, WWTP) (Aluminum plates, Aluminum Coating Baths)
• Chloride [Cl-] in waste water (Effluent WWTP) • Sulfuric acid [H2SO4] + Aluminum [Al3+] in Aluminum
• Hexavalent Chromium [Cr6+] in waste water (WWTP, etching bath (Aluminum Cast Line, Al anodization)
Steel, Aluminum metal bashing)
• Cyanide, total [TCN] in waste water (WWTP)
• Fluoride [F-] in industrial waste water (WWTP)
• Iron [Fe2+] in waste water (Steel, WWTP)
• Total Iron [Fe2+ / Fe3+] in waste water (Steel/Metal,
WWTP)

Steel / Metal
28 Other Applications for the Steel / Metal Industry:
• Total Acid (TA), Free Acid (FA), + Iron [Fe2+] in • Sulfuric acid [H2SO4] in water (Zinc extraction, metal
Manganese [Mn]/Phosphating Bath (Tubes for Crude recovery, Process water treatment)
transport) • Sulfuric acid [H2SO4] in Ammonium sulfate [(NH4)2SO4]
• Ammonia [NH3] in Cokes Gas (Steel, Coking Plant) (Outlet reactor)
• Ammonia [NH3] + Sulfide [S2-] in Scrubber (Ammonia • Tin [Sn] + Sulfonic acid [R-S(=O)2-OH] (Steel production)
Recovery plant) • Zinc [Zn2+], Nickel [Ni2+], + Nitrate [NO3-] in zinc
• Total + Free Ammonia [NH3] in Stripper (Steel, Coking phosphating bath (Phosphate plating)
Plant, Waste water from Strippers) • Zinc [Zn2+] + Sulfuric acid [H2SO4] in process (Steel,
• Calcium [Ca2+] (Aluminum Smelter, Dosing unit) Leaching)
• Chloride [Cl-] in process water (Steel, cold mill 2)
• Chromate [CrO42-] in process (Steel, Metal Finishing)
• Copper [Cu2+] (Copper tubes)
• Copper [Cu2+], Sulfuric Acid [H2SO4], + Chloride [Cl-] in
Copper Plating bath (Copper Foil Plating Bath)
• Copper [Cu2+] + Tin [Sn4+] in Etching baths (Steel wire
for Tire, Etching process)
• Hydrochloric acid [HCl] + Aluminum [Al3+] (House
Cooking Equipment, Etching bath)
• Hydrochloric acid [HCl] + Iron [Fe] (Carbon Steel
production)
• Hydrogen Sulfide [H2S], Ammonia [NH3], + pH in Acid
Stripper (Steel, Outlet Acid Scrubber)
• Iron [Fe] + Chloride [Cl-] (Steel, Cold mill 2)
• Silica [Si4+] (Steel, Cold mill 2)
• Sodium [Na+] in water (Steel, Demi Water plant)
• Sodium Hydroxide [NaOH], Sodium Cyanide [NaCN],
Sodium Carbonate [Na2CO3], + Copper [Cu2+] in
Copper Plating Bath (Metal Wire Production)

Steel / Metal
 29

Galvanic / Metal Surface Industry

Corrosion
In the earth’s crust, many metals are found in their oxi- preserved. More information about our atline and online
dized, ore state. Iron for example, is found naturally in a products and services for metal surface finishing analysis
multitude of oxide forms as magnetite (Fe3O4), hematite can be found here:
(Fe2O3), goethite (FeO(OH)), and more. As a refined www.metrohm.com/en/industries/
metal, iron is especially vulnerable to corrosion, which is
visible as red-brown colored rust. The iron is only trying Surfacing
to revert back to its oxide form. Considering the immense Corrosion- and heat-resistant properties are highly valued
amount of time and energy funneled into mining, refin- in the metal industry. The thin plating of one metal on
ing, and producing metals, protection against corrosion top of another can take advantage the oxidized coating
from the air, water, and other harsh environments is a that results, shielding the base layer from the environ-
top priority. ment. Immersion of steel sheets (or other metals or alloys)
in baths of molten zinc for galvanization makes the sur-
Nothing lasts forever face rust resistant. Galvannealing combines the process
Despite the various types of surfacing techniques avail- of galvanizing (hot-dip) and then immediately annealing
able, rusting and corrosion are inevitable over the life- the steel inline, creating a matte finish which is resistant
time of the refined metal. Wet, salty environments such to corrosion and can be easily painted. This type of steel
as areas near the ocean, or cold climates where salt is is used in many industries, including automotive, because
used to de-ice roads, decrease the effectiveness of pro- of its lifetime and paintability. Aluminum coated steel is
tective metal coatings due to the high electrical conduc- also used in the automotive industry and other industries
tivity of saltwater. Corrosion rates are increased in these for long-life parts which can withstand high heat. Elec­tro­
environments, which is why rusted automobiles are more galvanizing (electrolytic plating) of cold rolled steel with
prevalent in cold, northern climates compared to hot, dry zinc or a Zn/Ni mixture is another option to provide a
climates where the protective layer on the body is more non-reactive surface.

Galvanic / Metal
30 Passivation and Anodizing
Passivation is the state in which a metal surface is shield- be used instead in these situations. The Brooklyn Bridge,
ed from some environmental forces such as air and built in 1883, was the first bridge to use hot-dip galva-
water, usually by an applied oxide coat made of a base nized steel wire for its suspension cables. At the time, it
material. This oxide coat strengthens and protects the was 50% longer than any other bridge constructed,
metal surface, while inhibiting deeper corrosion. Passi­va­ making it the longest in the world. The suspension cables
tion can occur naturally or result from applying a micro- were found to be in good condition after the bridge’s
coating on the metal’s surface. Anodizing is an electro- re­­habilitation more than 100 years later.
lytic passivation process which can increase the thickness
of the oxide layer, increasing the resistance to corrosion. Thermal diffusion galvanization
Anodized materials are able to be easily painted and Also known as dry galvanizing, this form diffuses a zinc
glued due to the porous qualities of the surface. Both alloy coating on iron or copper-based materials. Zinc
aluminum (including its alloys) and steel are common powder and metal parts are sealed and tumbled in a
metal surfaces which use anodization and passivation for rotating drum at about 300 °C, where the zinc evapo-
protection. rates and diffuses into the substrate. Thermal diffusion
galvanization can provide better corrosion resistance
Galvanization than hot-dip galvanization in many cases, as well as emit
Galvanization, originally invented in India, is an anti- less waste products.
corrosive measure taken with iron and steel (and other
metals) by applying a protective zinc coating. Protection Phosphatizing
against the elements occurs by forming a coat of rust- The phosphatizing process produces a hard, electrically
resistant zinc over the iron (or other metal) which does non-conducting surface coating that adheres tightly to
not allow oxidation to occur, and the zinc also acts as a the underlying metal. This layer protects the metal from
sacrificial anode which still protects the underlying metal corrosion and improves the adhesion of paints and or­­
in the event of a scratch or gouge in the galvanized sur- ganic finishes to be subsequently applied. Phos­phatization
face. Electrogalvanization (electrolytic plating) results in a consists of two parts: an etching reaction with phos-
thinner layer, which is beneficial for automotive manu- phoric acid which increases the surface roughness, and a
facturers and other industries which apply additional second reaction at the surface between the alkali phos-
rust-proof paint as protection. This is not limited to steel phates and the previously generated metal ions. This
– aluminum, copper and many other types of metals and coating is quite thin and offers only basic corrosion pro-
alloys can be galvanized as well. tection. The addition of metal cations such as Zn2+, Mn2+,
and Ca2+ to the phosphatizing bath results in the forma-
Hot-dip galvanization tion of very resistant zinc phosphates with a coating thick­
Hot-dip galvanization is the most common method of ness between 7 and 15 times thicker, perfectly suited for
galvanization. This method utilizes a bath of molten zinc, outdoor use.
in which the metal parts are dipped into, coating them
with a thick protective layer. Constant exposure to a cor- This is not an exhaustive list of metal surface
rosive environment (such as salt water) will eventually treatments.
corrode hot-dip galvanized steel, but stainless steel can

Process Application Notes for the Galvanic / Metal Surface Industry

• Galvanic Industry – Metal Surface Treatment Aluminium etching/anodizing for analysis
of Acids, Bases and Aluminium. AN-PAN-1018
• Steel Industry: Analysis of Acids and Iron in Pickling Baths.
AN-PAN-1019

Galvanic / Metal
Sold and Installed Applications 31
Waste Water:
• Hexavalent Chromium [Cr6+] in waste effluent • Copper [Cu2+] in Electrolysis Bath (Copper alloys,
(Effluent monitoring, WWTP) Electrolysis Bath)
• Total Chromium [Cr6+ / Cr3+] in final waste effluent • Hydrofluoric acid [HF], Nitric Acid [HNO3], + Titanium
(Mechanical Components for Aviation Industry, [Ti] in Plating baths (Titanium, Plating Bath Quality
WWTP) Control)
• Copper [Cu+ / Cu2+] in final waste effluent (Mechanical • Nickel [Ni] + Copper [Cu] (Inkjet Printer Heads, Plating
Components for Aviation Industry, WWTP) line)
• Free Cyanide [CN-] in final effluent (WWTP) • Nickel Sulfate [NiSO4] + Cobalt Sulfate [CoSO4] in
• Total Cyanide [TCN] in effluent (plating company, etching baths (Cathode materials for Lithium-Ion
WWTP) secondary battery, Etching baths)
• Digester Unit for final waste effluent (Mechanical • Potassium hydroxide [KOH] in scrubber (Carbon
Components for Aviation Industry, WWTP) Dioxide Scrubber)
• Nickel [Ni2+] in waste water (Chrome / Nickel Plating, • Sodium Hydroxide [NaOH] in etching baths (Cathode
Mechanical Components for Aviation Industry, materials for Lithium-Ion secondary battery, Etching
WWTP) baths)
• Sulfate [SO42-] in waste water (WWTP) • Sodium Hydroxide [NaOH] + Ammonia [NH3] in
• Zinc [Zn2+] in waste water (Steel, WWTP) etching baths (Cathode materials for Lithium-Ion
secondary battery, Etching baths)
Other Applications for the Galvanic / Metal • Sodium hydroxide [NaOH] + Calcium [Ca2+] in process
Surface Industry: (Sodium Monochromate)
• Acids, Sodium Hydroxide [NaOH], + Aluminum [Al3+] • Sulfuric acid [H2SO4] + Hydrogen Peroxide [H2O2] in
(Etching bath) etching bath (Etching bath)
• Boric Acid [B(OH)3], Aluminum [Al3+], + Nitric Acid • Tin [Sn] + Acid (Tin plating)
[HNO3] in plating bath (Plating bath control) • Zinc [Zn2+] in galvanic bath (Surface finish)

Galvanic / Metal
32

Pulp and Paper Industry

Paper or plastic? Kraft Process

The Pulp and Paper industry is one of the largest indus- The breakdown process from solid wood to sheet of
tries in the world, taking in more than 40% of all indus- paper involves quite a number of preparative steps. The
trial wood traded globally. This industry is responsible for main process which converts wood into pulp is named
creating products such as paper-based packaging, matte the Kraft process, which utilizes white liquor (a mixture
and glossy paper, tissues, toilet paper, and so on. A major of sodium hydroxide and sodium sulfide) to break down
benefit for the use of paper products is that they can the lignin and cellulose linkages. Trees are pulverized into
generally be recycled. Though recycling paper materials wood chips, which are then steamed to force out air
is a feasible option most of the time, paper fibers lose pockets. The wood chips are saturated with a mixture of
quality over successive cycles, and so new pulp (a paper chemicals (liquors) and cooked in pressurized digesters.
precursor) will always be in need. The high pH, pressure, and temperature allow lignin and
hemicellulose to break down, and the resulting pulp is
then sieved, washed, and sometimes bleached. The
chemical liquors are processed and recovered for further
use, where possible, considering their adverse environ-
mental effects.

Pulp / Paper
Process Application Notes for the Pulp and Paper Industry 33
• ABC Titration: Analysis of Alkali, Carbonate, hydroxide and sulfide in Pulping Liquors.
AN-PAN-1004

Sold and Installed Applications

Bleaching Process: NIRS Applications for the Pulp and Paper

• Caustic [NaOH] in Hypochlorite [ClO-] (Bleach Industry:
production) The Pulp and Paper industry has used NIR analysis for
• Residual Peroxide [H2O2] in bleaching solution many years providing qualitative and quantitative infor-
(Bleaching Mechanical Produced Pulp, Bleaching mation about incoming timber materials and lignin con-
process) tent. Discriminant NIR analysis can be used to determine
species: hardwoods from softwoods, and sapwoods from
Waste Water: heartwoods. Common paper and pulp attributes mea­­
• Chemical Oxygen Demand [COD] in waste water sured with NIR include: kappa number, lignin content,
(WWTP) kraft pulp yield, tall oil, moisture, resin, brightness, wood
• Chemical Oxygen Demand [COD], pH, + Conductivity species, hardwood/softwood ratio, coatings, and com-
in waste water (WWTP) ponent analysis (clay, titanium dioxide, fillers, ash, etc.).
• P&M Number + Hardness [Ca2+ / Mg2+] in waste water
(WWTP) This list is intended as a starting point but is not
• Ortho Phosphate [PO43-] + Total Phosphate (TP) in comprehensive.
waste water (WWTP)
Kappa Number:
Other Applications for the Pulp and Paper • Determining Kappa Number in Blended Wood Pulp
Industry: Samples (NIRS)
• Dissolved Carbon Dioxide [CO2] in Treated/Recycled • Determining Kappa Number in Pulp in Blowline
Water (Water purification) Samples (NIRS)
• Caustic [OH-], Carbonate [CO32-], Hydrogen Sulfide • Monitoring Kappa Numbers in Pulp-Cotton Linters
[HS-], + Sulfate [SO42-] in Black, Green & White Liquor Mixtures (NIRS)
(recovery process)
• Silica [Si4+] (Pulp Process) Moisture Content:
• Sodium Bisulfite [NaHSO3] in paper production (Paper • Monitoring Moisture in Paper Coating Mixtures (NIRS)
production) • Determining Moisture in Paper and Lacquer Weight
• Sulfite [SO32-] in process (Tannin production, Reactor) on Backed Paper (NIRS)

Resin Levels:
• Monitoring Wax and Phenolic Resin Content in Wood
Fiber (NIRS)
• Monitoring Percent Resin and Percent Volatiles in
Paper Material (NIRS)

Pulp / Paper
34

Energy / Power Industry

Increasing energy consumption Process water: Water circuits in thermal power

Humans are set apart from other organisms in many plants
ways, among them is the drive and knowledge to create Thermal power plants use the heat generated by com-
and harness excess energy. We have the capacity now to bustion or nuclear fission to produce steam, which is fed
develop power plants which convert kinetic (wind, into a turbine driving a generator that converts the me­­
water) and thermal energy (nuclear energy, chemical chanical energy into electrical energy. Downstream of
energy) into electrical power which improves our lives the turbine, the steam is converted to water in a con-
immensely. However, energy supply has become a major denser. This water is held in a feed tank from where it is
issue of modern times. It is well-known that the burning pumped back into the steam boiler. Cooling water flows
of unclean fuel sources such as fossil fuels for energy is through the condenser in a separate circuit and removes
now putting our climate in danger. The rapid increase in the heat of condensation released by the steam via a
the Earth’s population, which is growing by about 80 heat exchanger. Nuclear power plants with pressurized
million every year, has led to rising energy consumption. water reactors have an additional water circuit known as
Calculations by the International Energy Agency (IEA) the primary circuit.
predict that the global energy demand will increase by
about 65% by 2035. A major fraction of the required An optimized water chemistry is essential
energy will continue to be provided by fossil fuel-fired The water chemistry depends on the type of power
and nuclear power plants, despite climate talks. plant, the cooling circuit design, and the construction
materials. Every cooling circuit has a unique design and
its own analytical requirements. A well-devised water
chemistry ensures safe and efficient power plant opera-

Energy / Power
tion. Nearly 50% of the unplanned downtimes in power
plants are caused by contaminants or problems with the
power plant. This can be combated with an optimized
feed water chemistry. On the one hand, the water must
35
chemistry of the water-steam circuit, with corrosion being be ultrapure and on the other, the addition of condition-
the primary factor. ing agents (phosphates, oxygen scavengers) must be
con­­tinuously monitored.
High-purity steam is essential if the steam turbine is to
operate efficiently and trouble-free. Cooling water is Turbine and lubricating oils
used to condense the exhaust steam from the turbine to Turbine and lubricating oils are exposed to extreme con-
water, which can then be returned and used as feed ditions in power plants. New power plant technologies
water. Continuous circulation of the cooling water in­­ and improvement of the efficiencies of gas and steam
creases the concentration of contaminants. This necessi- turbines present ever greater requirements regarding lub­
tates water analyses to monitor and control corrosion, ri­cant performance. Key parameters to be determined
and deposition processes taking place in the cooling are the acid and base numbers as well as the water con-
water circuit. How­ever, the purity requirements of cool- tent using Karl Fischer titration. Numerous international
ing water are much lower compared to those of the standards define the requirements and test procedures
boiler feed water. for in-service maintenance of the turbines.

Corrosion of metals in power plants is a commonly oc­­ Metrohm instruments comply with numerous standards
curring phenomenon due to the continuous contact of related to the energy and power industry, which can be
the metal with a corrosive environment. The very high found within the Energy and Power Plant branch sites
temperatures in the steam generator lead to corrosion here:
and deposits that severely reduce the efficiency of the www.metrohm.com/en/industries/

Process Application Notes for the Energy / Power Industry

• Carbon Capture Plants, Power Generation Industry: Measurement of the «rich» and «lean»
Amine Concentration and the amount of CO2 captured (CO2 Loading). AN-PAN-1003
• Nuclear Power Plants: Analysis of Boric Acid in cooling water PWRs.
AN-PAN-1013
• Flue-gas desulfurization; incineration process – Analysis of calcium and sulfate.
AN-PAN-1015
• Power Plant: Analysis of Silica in boiler feed water.
AN-PAN-1016
• Monitoring Flow Accelerated Corrosion & Metal Transportation in Power Plants:
Online Ultratrace Measurements of Fe and Cu. AN-PAN-1032
• Power Generation: Analysis of the M-Number (Alkalinity) in cooling water.
AN-PAN-1038
• Ammonia in cooling water of thermal power plants.
AN-PAN-1040
• Online trace analysis of anions in the primary circuit of nuclear power plants.
AN-PAN-1042
• Online trace analysis of cations in the primary circuit of nuclear power plants.
AN-PAN-1043
• Online trace analysis of amines in the alkaline water-steam circuit of power
plants. AN-PAN-1044

Energy / Power
36 Sold and Installed Applications

Boiler Feed: Other Applications for the Energy / Power

• Ammonia [NH3] in boiler feed water (Boiler Feed) Industry:
• Iron [Fe2+ / Fe3+] in boiler feed water (Boiler Feed) • Aluminum [Al3+] (Feed to softeners)
• pH + Alkalinity in Boiler feed water (Boiler feed water, • Ammonia [NH3] in scrubber ash (Stack Scrubber
Neutralization process) control for Ash content)
• Phosphate [PO43-] (total and ortho) in water (Boiler • Calcium [Ca2+] + Sulfate [SO42-] in process (Incinerator
feed water, Feed to softeners) plant)
• Silica [Si4+] in Boiler Feed Water (Boiler Feed) • Carbon Dioxide [CO2] Loading in Organic Absorber
• Sodium [Na+] in Boiler Feed Water (Boiler Feed) Liquid (Carbon Dioxide Capture System)
• Chloride [Cl-] in condensate return (Energy production)
Cooling Water: • Free acidity in Uranyl Nitrate (fuel rod production)
• Ammonia [NH3] in cooling water (Nuclear Power • Hardness [Ca2+ / Mg2+] in demi water plant
Plant, Cooling of Reactor) • Hypochlorite [NaOCl] in make-up water (Disinfection
• Boric acid [B(OH)3] in heavy water / cooling water Treatment Monitoring)
of Nuclear Power Plants (Cooling water circuit) • Iron [Fe2+ / Fe3+] in process water (Coal-fired Power
• Heavy Metals [Ni + Fe + Zn + Cu] in Cooling Water Plant, Process Water)
(Coal Plant – Electricity, Cooling water circuit) • Silica [SiO2] in demi water (Boiler feed)
• P&M number in cooling water (Preparation cooling • Determination of Uranium prior to discharge to
water) WWTP (Effluent from Ion Exchange Column)
• Potassium [K+] + Ammonium [NH4+] in primary circuit
cooling water (Nuclear Power Plant, Primary Circuit
Water)
• Sulfide [S2-] in cooling water (Nuclear Power Plant,
Cooling Water)
• TAC, pH, + Total Hardness [Ca] in cooling water
(riverwater) (Inlet Cooling Water)

Waste Water:
• Ammonia [NH3] in waste water treatment (WWTP)
• Total-Ammonia [NH3], Free-Ammonia [NH3], + pH in
waste water (Coking plant, De-Ammonization of
waste water)
• Chlorine [Cl2] in cooling water discharge (Cooling
Water discharge, WWTP)
• Chemical Oxygen Demand [COD] in waste water
(WWTP)
• Hexavalent Chromium [Cr6+] in surface water (Heavy
Metals monitoring)
• Copper [Cu+ / Cu2+] in outlet waste water (WWTP)
• Sulfite [SO32-] in waste water (WWTP)
• Volatile Fatty Acids (Anaerobic WWTP)

Energy / Power
 37

Automotive and Aerospace Industry

Transportation: Driving societal growth Automotive Industry

Trading and mixing of ideas between different locales In Europe alone, about 75% of all goods (which account
and cultures would be so much more difficult without for 90% of the value of all goods in Europe) are trans-
automobiles and airplanes. Transportation and mobility ported over land by commercial vehicles. The Automotive
are vital to modern society. Our earliest ancestors walked industry is estimated to account for 4-6% of the Euro­­
endlessly as nomads until we formed agricultural societ- pean GDP by offering 12.1 million direct and indirect
ies – taming the land and animals alike. We learned to jobs. The EU is responsible for producing a major portion
make animals work for us, which lessened our burdens of the world’s automobiles, and as such, invests signifi-
and freed up more time for other pursuits. Sailing ruled cant amounts of time and capital (€ 41.5 billion annually)
as a form of transport for centuries, both for trading and into research and development in this industry. In 2014,
emigration purposes. Eventually, the Industrial Revolution the EU produced 25% of the world’s passenger cars and
came in the middle of the 19th century, and machines, 23% of motor vehicles overall. Production from the
production lines, and factories became more and more Americas in 2014 stood at about 23%, while Asia led the
prevalent in our lives. The automotive industry was born, way with 50% of all passenger car production. In 2015,
and soon after came aerospace. Eventually, we even the EU output for passenger car increased by 6.2% com-
travelled outside of our own planetary boundaries. pared to 2014, with a total of about 15.9 million cars
manufactured. The market is expected to increase mod-
estly in 2016 according to the European Automobile
Ma­­nufacturers’ Association (ACEA).

Auto / Aero
38 Aerospace Industry
The Aerospace industry in the EU is the world leader in in this sector are highly valued, and this is reflected in
the production of civil aircraft. Overall, the industry pro- both the quality and volume of aerospace products
vided more than 573,000 jobs in the European Union in which are exported worldwide.
2014, and generated €199.4 billion in turnover, which
was a 1% increase from the previous year. The division of A detailed description of the many metal surfac­
turnover revenue within the EU aerospace industry is bal- ing techniques available for this industry can be
anced almost equally between military (48.7%) and civil found in previous sections.
(51.3%) sectors. Research, development, and innovation

Sold and Installed Applications

Electroplating Surface Treatment: Waste Water:

• Boric Acid [B(OH)3] in Nickel [NiCl2] Electroplating Bath • Aluminum [Al3+], Copper [Cu], + Chromium [Cr3+ /Cr6+]
(Aerospace Engines, Nickel Electroplating Surface in Effluent (Airfighters production, Effluent WWTP)
Treatment) • Fluoride [F-] in waste water (WWTP)
• Chromium [Cr3+] in Chromic Acid [H2Cr2O4] Electro­ • Iron, Total [Fe2+ / Fe3+] + Zinc [Zn2+] in Effluent (Air­
plating Bath (Aerospace Engines, Chromium Electro­ fighters production, WWTP)
plating Surface Treatment)
Other Applications for the Automotive and
Etching Baths: Aerospace Industry:
• Caustic [NaOH] in Electrolytic Clean, Nitric Acid • Caustic [NaOH] in Surface Treatment Bath (Car, Surface
[HNO3], Hydrofluoric Acid [HF] + Neutralizer in Etching treatment)
Baths (Blade production, Nickel Turbine Etching Baths) • Hydrofluoric acid [HF] (Car screen (glass))
• Caustic [NaOH], Nitric acid [HNO3], + Ammonium • Sodium Hydroxide [NaOH] in Scrubber (Scrubber,
Bifluoride [NH4HF2] in Etching Baths Automotive parts for car & aviation industry)
(Blade production, Titanium Fan Blade Etching Baths)
• Sulfuric acid [H2SO4], Phosphoric Acid [H3PO4], Total
Iron [Fe2+ / Fe3+], + Hydrochloric Acid [HCl] (Turbine
Blade Production, Electrolytic Etching Baths)

Zinc-Phosphatizing:
• Acid [Free and total], Fluoride [F-], Zinc [Zn2+], +
Accelerator (Zn-Phosphatizing Bath)
• Acid [Free and total], Nitrite [NO2-], + Zinc [Zn2+]
(Zn-Phosphatizing Bath)
• Fluoride [F-] in Surface Treatment Bath (Cars, Zinc-
Phosphatizing Bath)
• Sulfuric acid [H2SO4] + Zinc [Zn2+] (Phosphatizing bath)

Auto / Aero
 39

Textile Industry

Origins of textiles and clothing

Humans have been creating textiles and clothing for thermia and worse, which is why it is advised to wear
about 8,000 years, intended as protection from the har­ fabrics made from synthetics because they keep the skin
sher elements. Fabric can be used for many different dry and allow the water to evaporate easier.
pur­­poses – to decorate, to clothe, and to protect. Du­­ra­­
bility, texture, weight, and even the source are important Creation of synthetic textiles begins with a polymeriza-
characteristics. There is a dizzying array of clothing made tion process in which the resulting liquid is forced through
from textiles available in nearly every size, color, and shape tiny holes (called spinnerets, similar to those of spiders)
created from both natural and synthetic fibers. and forms small threads. These tiny threads are then
dyed and woven into fabric. There are many types of
Natural vs. Synthetic Sources synthetic fibers, such as nylon, polyester, acetate, spandex,
There are many ways to create fabric, but certain charac- acrylic, and rayon (viscose). Kevlar, Twaron, and other
teristics may be desired over others. Sports enthusiasts, para-aramid fibers which are man-made are strong
and mountaineers in particular, know that the breath- enough to withstand bullets. The properties (such as
ability of certain fabrics can help or hinder during exer- elas­ticity) of these synthetic materials can be modified
tion. Sweating is a natural way of losing heat through the much easier than for natural fibers. In 2016, we now
evaporation of water from our skin. Natural fibers, such have many items which are even created from graphene
as cotton, will soak up the water, holding it against the (carbon fiber), one of the strongest, lightest materials
skin, offering no respite from overheating. In cold cli- known.
mates, this wet layer against the skin can lead to hypo-

Textiles
40 Process Application Notes for the Textile Industry
• Viscose / Rayon production: Analysis of Sulfuric Acid and Zinc Sulfate.
AN-PAN-1010
• Online Analysis of Indigo, Hydrosulfite, and Other Parameters in Textile Dye Baths.
AN-PAN-1035

Sold and Installed Applications

Acrylic Fiber Production: NIRS Applications for the Textile Industry:

• Cyanide [CN-] in waste water (WWTP) NIR has been long used in the textile industry to differen-
• Sulfite [SO3-] in influentv WWTP (WWTP) tiate fiber types for carpet recycling. Blend analysis of
different polymer fibers can be analyzed with NIR. Real-
Cellulose Fiber Production: time analysis of the application of polyvinyl alcohol (PVA
• Chemical Oxygen Demand [COD] in waste water or PVOH) sizing to warp yarn has been done with NIR
(Fiber production, Discharge waste water) online process analyzers. Common fibers identified with
NIR include: cotton/linen, merchandized cotton, acrylic,
Spin Bath Process: modified acrylic, acetate, triacetate, Nomex®, Kevlar®
• Sulfuric acid [H2SO4] in Spin Bath (Fiber Production, (K-29, K49, and K129), nylon-6, nylon-6,6, silk, polyester,
Cellulose Fibers, Spin bath) cationic and disperse dyeable polyester, polypropylene,
• Sulfuric acid [H2SO4], Zinc sulfate [ZnSO4], + Sodium PVA and PVC.
sulfate [Na2SO4] in Spin Bath (Fiber Production, Spin
bath) This list is intended as a starting point but is not
comprehensive.
Other Applications for the Textile Industry:
• Hydroxide [OH-] + Carbonate [CO32-] in cleaning Fiber Blends:
solution (Textile cleaning) • Monitoring Fiber Blends for Blend Ratios, Moisture
• Indigo [C16H10N2O2] + Hydrosulfite [S2O42-] (Textile and Finish (NIRS)
Production, Indigo dye bath) • Distinguishing Between Nylon, Polyester, and Poly­
• Determining moisture and oil content in wool samples propylene Threads (NIRS)
(NIRS)
• Sodium Hypochlorite [NaOCl] in bleaching solution Finishing:
(Fiber Production, Bleaching) • Quantitative Determination of Bond and Finish on
• Sulfuric acid [H2SO4] + Formaldehyde [CH2O] in acid Nylon Thread (NIRS)
bath (Fiber cloths, Acid bath) • Measuring Finish on Crimped and Uncrimped Fibers,
and Total Solids in Bath Liquor (NIRS)
• Monitoring Oil Finish on Nylon Fibers (NIRS)
• Monitoring Resin Content in a Textile Finishing Bath
(NIRS)

Fire Resistance:
• Monitoring the Amount of PBI During the Batch
Production of Fire Retardant Fabric (NIRS)

Heatset Monitoring:
• Qualitative Monitoring of Heatset Temperature of
Nylon (NIRS)

Textiles
 41

Pharmaceutical / Biochemical Sector

Determination of active ingredients, excipients, Pharmacopoeias and drug safety

and impurities According to the World Health Organization (WHO),
Pharmaceutical analysis provides information on the specifications and test methods for commonly used ac­­
iden­­­­tity, purity, content and stability of starting materials, tive ingredients and excipients are outlined in detail in
excipients, and active pharmaceutical ingredients (API). A monographs contained in the national pharmacopoeias
distinction is made between analysis of the pure active of more than 38 countries. These include the United
pharmaceutical ingredients used to cure, soothe, pre- States Pharmacopeia (USP), the European Pharmacopoeia
vent, or identify illnesses and diseases (active ingredient (Ph.Eur.), derived from a harmonization of the regulations
analysis) and analysis of drug products (drug product of a number of individual states, and the Japanese Phar­­
analysis). Drug products come in various forms (oint- macopoeia (JP), to name just a few examples. The phar-
ments, tinctures, pills, lotions, suppositories, infusions, macopoeias are official compendia containing statutory
drops, etc.) and consist of the pharmaceutically active requirements pertaining to identity, content, quality, pu­­
substance and at least one pharmaceutical excipient. rity, packaging, storage, and labeling of APIs and other
Impurities are mainly introduced during the synthesis of products used for therapeutic purposes. They are essen-
the active ingredient, and are usually monitored accord- tial for anyone seeking to produce, test, or market me­­di­
ing to both the directives of the ICH (International ci­nal products.
Conference on Harmonisation of Technical Requirements
for Registration of Pharmaceuticals for Human Use) and Metrohm instruments comply with numerous pharmaco-
the pharmacopoeias. poeia standards, which can be found within the Phar­ma­
ceutical branch sites here:
www.metrohm.com/en/industries/

Pharma / Biochem
42 Sold and Installed Applications

Waste Water:
• Ammonia [NH3] in waste water (WWTP)
• Chemical Oxygen Demand [COD] in waste water
influent WWTP)
• Chloride [Cl-] in Outlet WWTP (WWTP, Hospitals)
• Nitrite [NO2-] in BioReactor (Inlet BioReactor, WWTP)
• Phosphate [P-PO4] in Final Effluent (Pharmaceutical,
WWTP)

Other Applications for the Pharmaceutical /

Biochemical Sector:
• Ammonia [NH3] in Fermenter Cultures (Control of
Ammonia in Fermenter Cultures)
• Calcium [Ca2+] in Bioreactor (Reactor)
• Sodium hydroxide [NaOH] + Sodium Carbonate
[Na2CO3] in Scrubber (Biopolymer, Scrubber)
• Salt [NaCl] + pH in perfusion solutions (Perfusion
solutions, Filling bags)

NIRS Applications for the Pharmaceutical

Industry:
Specifications and test methods for the commonly used With the PAT (process analytical technology) initiative,
active ingredients and excipients are monographed in the FDA aims to bring about an increase in efficiency in
detail in national pharmacopeias in more than 38 states pharmaceutical production, including a trend away from
according to the World Health Organization (WHO). NIRS final checks towards real-time process analysis and con-
has emerged as a powerful tool for the analysis of phar- trol. The future is quality by design, compared to to­­
maceuticals. The manufacture of pharmaceutical prod- day’s techniques of quality by testing. The initiative re­­
ucts from raw material identification to the measurement quires rapid analytical techniques that allow comprehen-
of content uniformity of dosage forms can be assisted by sive on­­line and inline monitoring of the manufacturing
the implementation of NIR methods. The FDA and Euro­ process. To this end, NIRS is the most powerful analytical
pean Union health guidelines have increased the work- tool that is currently dominating all PAT projects.
load and rigor associated with receiving inspection,
blending, and content assay. With the advent of 100% NIRS is described in the European (Ph.Eur.) and Japanese
container testing for receiving inspection of raw materi- (JP) Pharmacopoeia as well as in the United States Phar­­
als in Europe and Canada, NIR technology can reduce the ma­­copeia (USP). The Vision® software used by Metrohm
time and skill level required to meet the increased chal- Process Analytics NIR Analyzers is available in two ver-
lenge of compliance. Common pharmaceutical applica- sions: for general use but also in a pharmaceutical ver-
tions using NIR include: receiving inspection of excipients sion which complies with FDA standards – fully validated
and active pharmaceutical ingredients (API), blend uni- and 21 CFR Part 11 compliant. The Vision® soft­­ware for
formity, granulation, drying and coating, and particle size chemical/pharmaceutical NIR data analysis is available as
verification analysis. Additionally, NIR is an invaluable tool a single- or multi-user version.
for the detection of counterfeit drug products and the
determination of water and residual solvent content.

Pharma / Biochem
This list is intended as a starting point but is not
comprehensive.
43
Active Ingredients (API) / Content Uniformity: API – Foot Powder:
• Erythromycin A in Fermentation Broth (NIRS) • Aluminum Chlorohydrate in Foot Powder (NIRS)
• Naproxen in Tablets (NIRS) • Salicylic Acid in Foot Powder (NIRS)

API – Antacids: API – Transdermal Patches:

• Calcium Carbonate [CaCO3] in Antacid Powders and • Methylphenidate in Transdermal Patches (NIRS)
Tablets (NIRS) • Nicotine in Transdermal Patches (NIRS)
• Magnesium Hydroxide [Mg(OH)2] in Antacid Powders • Nitroglycerine in Transdermal Patches (NIRS)
(NIRS)
• Polydimethylsiloxane in Antacid Liquids (NIRS) Drying:
• Moisture in Bleomycin Sulfate (NIRS)
API – Cough Syrup: • Moisture in Lyophilized Products (NIRS)
• Acetaminophen in Cough Syrup (NIRS) • Moisture in Aspirin Granulations and Tablets (NIRS)
• Dextromethorphan in Cough Syrup (NIRS) • Monitoring granulation and drying in fluid bed dryers
• Doxylamine Succinate in Cough Syrup (NIRS) (NIRS)
• Pseudoephedrine in Cough Syrup (NIRS)

Pharma / Biochem
44

Food and Beverage Industry

You are what you eat... Process control in food production

Beyond their nutritive value, foods and beverages are It is a long way before a raw material becomes a finished
consumed for their taste or flavor. Increasingly, they are product in the food industry. Numerous production steps,
also a source for maintaining health and enhancing our such as pulverization, filtration, fermentation as well as
well-being via high-quality nutrition. At the same time, heat­ing, cooking, pasteurization, sterilization or distilla-
with an ever-increasing number of processed foods, food tion, are involved in the preparation of a product and to
quality and safety aspects are becoming more important. make it storable. In addition to the statutory final inspec-
All the more because foods are highly complex materials tion and testing, control of the different production steps
– prone to degradation and contamination – that con- also has an important role, which is to maximize through­
tain myriads of compounds. put and yield of a product. Valuable time is lost if the
product cannot be further processed or packaged while
Analytical chemistry ensures that consumers obtain safe samples from the various production steps are being
and sanitary food in compliance with regulatory require- tested in the laboratory. It is thus a great advantage if
ments. Nutrient information, food traceability, and pro- these analyses can be performed directly at the process
tection against fraud are further challenges. From the site while production goes on uninterrupted.
process point of view, analytical chemistry supports the
manufacturer to improve yields and optimize quality by Metrohm instruments comply with numerous standards
offering robust, efficient, and sensitive instrumentation. related to the food and beverage industry (including the
FDA regulation Title 21 CFR Part 11) which can be found
within the Food and Beverage branch sites here:
www.metrohm.com/en/industries/

Food / Drinks
 Process Application Notes for the Food and Beverage Industry 45
• Monitoring Peracetic Acid (PAA) in a Beverage Bottling Facility.
AN-PAN-1029
• Effectively Monitoring Hydrogen Peroxide as a Delousing Agent in Salmon Farms.
AN-PAN-1031
• Alkalinity & hardness in process and make-up water for the production of beer.
AN-PAN-1036

Sold and Installed Applications

Beverages: Other Applications for the Food and Beverage

• Alkalinity in process and make-up water (Beverages, Industry:
Water treatment, Make-up water) • Ammonia [NH3] in food casings (Food casings)
• Free + Total Alkalinity of brewing water • Calcium [Ca2+] in process (Pectin solution, Calcium
• Calcium [Ca2+] in water (Beer, Water control) removal)
• Hardness [Ca2+ / Mg2+] in carbonated beverages • Chlorine [Cl2] in disinfection (Disinfection, Clean in
(Beverages (Soda), Water Purification System) Place)
• Total Iron [Fe2+ / Fe3+] in ground water (Beverages, • Chlorine [Cl2] in Hypochlorite [ClO-] (Starch products,
Groundwater inlet, Water control) Hypochlorite production)
• Lactic Acid in Raw Milk • Citric/Malic Acid in Pickling Solution (Dried fruit,
• Manganese [Mn2+] in water (drinking water, inlet raw Pickling solution)
water, Potable water purification, Dairy products) • FFA (Free Fatty Acids) and soap in edible oils
• Peracetic Acid (PAA) [CH3CO3H] in beverage industry • Fluoride [F-] in toothpaste (Toothpaste, Dental rinsing)
filling systems (Aseptic Bottling Line) • Hydrogen peroxide [H2O2] in seawater (Salmon
• Polyacrylamide (PAM) solution (Bottling plant) treatment)
• Sulfide [S2–] (Beverage production) • Hypochlorite [OCl–] in bleach
• Iodide [I–] (salt production)
Potato Products: • Salt [NaCl] and vinegar [CH3COOH] in mayonnaise
• Calcium [Ca2+] in blanching water (Potato chips production
processing) • Sodium [Na+] in Pickling Solution (Dried fruit, Pickling
• Chloride [Cl–] in potato chips production (Potato chips, solution)
Potato production) • Sodium hydroxide [NaOH] (Cellulose housing for food)
• Glucose in process (Potato Chips, French fries, Water • Sulfuric acid [H2SO4] (Cellulose housing for food)
flume) • Sulfuric acid [H2SO4], Ammonium Sulfate [(NH4)2SO4],
• Total Phosphorus [P] (Potato processing) + total Sulfate [SO42–] (Casings for sausage)
• Sodium dihydrogen pyrophosphate [Na2H2P2O7] in • Sulfuric acid [H2SO4] + Ammonium Sulfate [(NH4)2SO4]
deep-frozen potato products (blanching process) in process (Casings for sausage)
• Total Chlorine for disinfection processes
Waste Water: (Dosing disinfection of boiling water, Meat products)
• Ammonium [NH4+] in Inlet WWTP (Soya production,
WWTP)
• Chemical Oxygen Demand [COD] (WWTP)
• Fluoride [F–] in waste water (WWTP)
• Nitrite [N-NO2–] in Inlet WWTP (Soy production, WWTP)
• Phosphate [PO43–] in waste water (Food, Milk, Inlet
WWTP, Outlet WWTP)

Food / Drinks
46

Industrial Waste Water

Harmful substances in water

Water is the source and basis of all life. It is essential for Because of the associated health risks, the World Health
metabolism and is our most important foodstuff. As a Organization (WHO) has issued guideline values for about
solvent and transporting agent it carries not only the vital 200 substances found in water. These guideline values,
minerals and nutrients, but also, increasingly, harmful together with the hydrogeological conditions of the va­­
pollutants, which bioaccumulate in aquatic or terrestrial rious countries, form the basis for the setting of country-
organisms. There are roughly 1700 substances, mainly of specific limits. That is why water is the subject of a host
anthropogenic origin, that can today be detected in of laws, regulations, and standards in most countries.
water. As a source of food and energy, during use in irri­
­gation, as a solvent, cleaning agent, or coolant, and also Metrohm instruments comply with numerous water ana­
as a means of transportation and discharge system for ­lysis standards, which can be found here:
effluents, water becomes contaminated with fertilizers, www.metrohm.com/en/industries/
pesticides, drugs, hormones, heavy-metal compounds, environmental/environment-water/table_
body care and synthetic products. water_standards/

WWTP
 Process Application Notes for the Waste Water Industry
• Waste Water Treatment Plants: Nitrogen Removal – Simultaneous analysis of
Ammonia, Nitrate, and Nitrite. AN-PAN-1009
• Detecting Chromate (Cr(VI)) in Waste Water Streams.
AN-PAN-1030 47
• Ortho- and total phosphate phosphorus analysis online according to DIN EN ISO
6878:2004-09 (formerly DIN 38405-D11). AN-PAN-1039

Sold and Installed Applications

effluent WWTP (Municipal WWTP, Effluent WWTP)
• Alkalinity in Effluent WWTP (Waste water treatment • Phosphate [PO43-], Total Phosphate [TP], + Chemical
(Nitrification), Effluent WWTP) Oxygen Demand [COD] in Surface water (Municipal
• Ammonia [NH3] in effluent WWTP (Municipal WWTP) WWTP, Total Phosphate [TP] in Effluent WWTP
• Ammonia [NH3] + Sulfide [S2-] in waste water treat- (Outlet WWTP)
ment (Municipal Wastewater Treatment, WWTP) • Sodium [Na+] in waste water (Waste water)
• Ammonium [NH4+] in waste water effluent (Municipal • Volatile Fatty Acids in biomatrix (anaerobic WWT)
WWTP) (Water treatment, WWTP)
• Calcium [Ca2+] in waste water (Waste water Treatment) • Zinc [Zn], Lead [Pb], Cadmium [Cd], + Copper [Cu]
• Chemical Oxygen Demand [COD] in waste water in WWTP (Waste Incineration, WWTP)
(WWTP) • Zinc [Zn2+] in waste water (Steel wire for Tire, Effluent
• Chemical Oxygen Demand [COD] + Ammonia [N-NH4] WWTP)
in municipal wastewater (Outlet WWTP)
• Hexavalent Chromium [Cr6+] in waste water (Waste This is not an exhaustive list. Each industry also
water Treatment, Municipal + Industrial) has some examples of specific waste water
• Copper [Cu+ / Cu2+] in waste water (Outlet WWTP) treatment.
• Free Cyanide [CN-] in Influent + Effluent WWTP
(WWTP, Outlet WWTP)
• Fluoride [F-] in waste water (Effluent WWTP)
• Heavy metals [Cu, Zn, Cd, Pb] in waste water treatment
(WWTP)
• Hydrogen Peroxide [H2O2] + Peracetic acid [CH2COOH]
in waste (Oxidative Substances, WWTP)
• Total Iron [Fe2+ / Fe3+] in water treatment process
(Water treatment, WWTP)
• Manganese [Mn2+] in waste water effluent (Municipal
WWTP)
• Nickel [Ni2+] in waste water (Steel wire for Tire,
Effluent WWTP)
• Nitrate [NO3-], Nitrite [NO2-], + Ortho-Phosphate [P-PO43-]
in waste water (Municipal WWTP, Outlet WWTP)
• Nitrite [NO2-] in water treatment (Biological reactor)
• Nitrite [NO2-], Nitrate [NO3-], + Ammonium [NH4+] in
waste water (WWTP)
• Phenol [C6H5OH] in waste water (WWTP)
• Ortho-Phosphate [P-PO43-] in outlet and effluent
WWTP (Municipal WWTP, Effluent WWTP)
• Ortho-Phosphate [P-PO43-] + Total-Phosphate [TP] in

WWTP
48

Environmental Sector

The importance of environmental analysis Air

The rapid growth in the world population has led to The atmosphere is an important thermal buffer against
sharp increases in the consumption of energy and re­­ space, and protects the earth from cosmic radiation. It is
sources and in the production of consumer goods and the place where clouds are formed and water is present
chemicals. It is estimated that there are a total of 17 mil- there in all its physical states. Thus it is a heterogeneous
lion chemical compounds on the market, including as mixture of finely dispersed, solid or liquid particles in a
many as 100,000 that are produced on a large industrial gas (air). Its constituents are characterized by extreme
scale. Substances introduced into the environment are mobility, enter our bodies easily through breathing, and
distributed among the environmental compartments water influence the climate and weather. Filter methods, and
(hydrosphere), soil (pedosphere), rock (lithosphere), and air aerosol and gas collectors bring the constituents of air
(atmosphere), as well as among the organisms living on into the aqueous phase, which is preferable for chemical
them (biosphere). analysis.

Water We can only protect the environment and its inhabitants

As its physical state changes, water passes through all if we know the type and quantity of these contaminants.
spheres. It is the most frequently analyzed environmental This requires internationally accepted standards, in which
compartment and is also the easiest, because – unlike air limits and test methods are defined. Metrohm instru-
or soil – it already exists in the liquid phase. If drinking ments comply with numerous environmental standards,
water samples are to be analyzed, sample preparation is which can be found within the three Environmental
usually not necessary; however, it is usually unavoidable branch sites here:
in the case of wastewater samples. www.metrohm.com/en/industries/

Enviro
Sold and Installed Applications 49
Potable (Drinking) Water: River and Surface Waters:
• Aluminum [Al3+] in drinking water (Potable water) • Ammonia [NH3] + Nitrate [NO3-] in river water (River
• Ammonia [NH3] in drinking water (Drinking water Water Monitoring)
monitoring) • Ammonium [NH4+] in river water (River Water
• Ammonia [NH3] in tap water (outlet waste water, Monitoring)
WWTP) • Boron in Surface Water (Surface Water Monitoring)
• Boron for water in desalination plants (Water treatment • Cadmium [Cd], Lead [Pb], Copper [Cu], + Zinc [Zn]
process) in river and surface waters (River Water Monitoring,
• Chloride [Cl-] in outlet Carbon Filter (Drinking water, Surface Water Monitoring)
Outlet Carbon Filter) • Chloride [Cl-] in surface water (Surface Water
• Free Cyanide [CN-] in drinking water (Drinking water Monitoring)
monitoring) • Hexavalent Chromium [Cr6+] in surface and river
• Fluoride [F-] in drinking water (Drinking water waters (River Water Monitoring, Surface Water
monitoring) Monitoring)
• Iron(II) [Fe2+] + Iron(III) [Fe3+] in drinking water (Drinking • Copper [Cu+ / Cu2+] in surface water (Surface Water
water treatment) Monitoring)
• Langelier Saturation Index (Hardness) in drinking • Free Cyanide [CN-] in river and surface waters
water (Potable water) (River Water Monitoring, Surface Water Monitoring)
• Manganese [Mn2+] in outlet drinking water (Outlet • Manganese [Mn2+] in surface water (Surface Water
to Storage, Potable water) Monitoring)
• Nitrite [NO2-] in drinking water (Drink water quality • Nickel [Ni2+] in surface water (Surface Water
self-monitoring) Monitoring)
• Phenol [C6H5OH] in drinking water (Drinking water • Nitrate [NO3-] in river water (River Water Monitoring)
monitoring) • Phenol [C6H5OH] in river and surface waters
(River Water Inlet, WWTP, Surface Water Monitoring)
• Ortho-Phosphate [PO43-] in river water (River Control,
River Water Monitoring)
• Phosphate [PO43-], Total Phosphate (TP), + Chemical
Oxygen Demand [COD] in surface water (Surface
Water Monitoring)
• Sulfate [SO42-] in surface water (Environmental control
of river water, River Water Monitoring)
• Zinc [Zn2+] in surface water (Surface Water Monitoring)

Air Pollution:
• Applications involving air quality are generally per-
formed with PILS or MARGA Analyzers.

Enviro
50

Overview of Process Analyzers from

Metrohm Process Analytics
Whatever your project requirements and budget, tive and customizable analyzer to cover all your process
Metrohm Applikon has the right analyzer and monitoring monitoring needs. We also offer environmental solutions
solution for you. From our low cost, single-stream-dedi- such as MARGA (Monitor for AeRosols and Gases in
cated Plug and Analyze series to our multi-stream, multi- Ambient air), and near-infrared spectroscopy (NIRS) ana-
purpose ADI 2045 range we provide you with an innova- lyzers.

Wet chemical systems

Single method Process Analyzers

Features Alert 2003 ICON ADI 2016 ADI 2018 ADI 2019

Number of sample streams 1–2 1–2 1 1–2 1

Ion Selective Electrodes ü û û ü û
Colorimetry û ü û û ü
Titration û û ü û û
Karl Fischer Titration û û ü û û
Infrared Detection û û û û û
Modular Configuration û û ü ü ü
Ex-proof Zone 1 or 2 û û û û û

Process Analyzers
Wet chemical systems
Customizable, multi-stream Process Analyzers
51
ADI ADI ADI ADI Process IC
Features 2035
2045PL 2045TI 2045TI Ex 2045VA ONE/TWO
Number of sample streams 1–10 1–10 1–10 1–10 1–10 1–20
Ion Selective Electrodes ü ü ü ü û û
Colorimetry ü ü ü ü û û
Titration ü ü ü ü û û
Karl Fischer Titration ü ü ü ü û û
Voltammetric Analysis û û û û ü û
Ion Chromatography û û û û û ü
Modular Configuration ü ü ü ü ü ü
Ex-proof Zone 1 or 2 û û û ü û û

Reagent-free systems
NIRS – Near Infrared Spectroscopy Process Analyzers

Features NIRS XDS Process NIRS Pro

Number of sample streams 1–9 1

Reagent-free ü ü
Wavelength range 800–2200 nm 1100–1650 nm
Transmittance Mode ü û
Transflectance Mode ü ü
Reflectance Mode ü ü
Immersion Mode ü ü
Direct Light/Non Contact option ü ü
Single fiber option ü û
Microbundle option ü ü
Dedicated Sample Interfaces* ü ü
Long-distance measurement ü û
Ingress Protection IP65/Nema 4X IP69K
Ex-proof Zone 1 or 2 ü û
Acquisition Time 20–30 seconds < 1 second

* Collection probes, probes with purging options, angled fibers, and other customizable solutions are available.
Preconditioning systems and shelters can also be custom-built by Metrohm.

Process Analyzers
Subject to change
Layout by Ecknauer+Schoch ASW, printed in Switzerland by Metrohm AG, CH-9100 Herisau
8.000.5184EN – 2017-02

www.metrohm.com