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 Fully automated, online customizable analyzers facilitate Ap pli cations is meant to be a significant sales tool to help 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, facilitating sis that optimize efficiency, decrease chemical consump-more targeted and productive discussions between sales- tion and create a safer work environment. people and customers. Metrohm knows your industry, and we are an active partner in your process control with We back our systems with a team of experienced support our vast experience from thousands of installations personnel to offer you the full value chain of process around the globe. ana lytics: Additionally, attention is called to our Process Appli ca­ • Process Control tion Notes (PANs) at the beginning of each industry • Process Optimization chapter, be low the introduction. PANs are a short over- • An increased yield view about a specific process, problem (and its repercus- • Reduced operational cost sions), and the Metrohm Process Analytics solution. These are freely downloadable from www.metrohm.com. With our expertise and experience we do not just offer process analyzers, but an integrated solution to the end Process Solutions from Metrohm Process Analytics user. This helps optimizing process efficiency while reduc-Metrohm Process Analytics is the brand name represent- ing operation cost. Real time analysis as an integrated ing the well-known Metrohm Applikon wet chemistry part of process control and automation will help you in - pro cess ana lyzers as well as the Metrohm NIRSystems crease yields and improve production quality. ins truments for process analysis. Our process analyzers take the famous Metrohm laboratory solutions a step further, offering ana lytical systems for titration, spectros-For your information, this document has been made copy, electroche mis try, ion chromatography, photometry, interactive for easier usage on electronic devices. as well as ion selective measure ments. 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 http://www.metrohm. com/en/products/process­analyzers/process­ion­ chromatograph/. Table of Contents Chemical Industry: Chlor­Alkali Production 6­7 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 9­11 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 12­15 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 16­18 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 19­21 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 23­25 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 26­28 Pickling Process: 27 Waste Water: 27 Aluminum Milling: 27 Other Applications for the Steel / Metal Industry: 28 Galvanic / Metal Surface Industry 29­31 Waste Water: 31 Other Applications for the Galvanic / Metal Surface Industry: 31 Pulp and Paper Industry 32­33 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 34­36 Boiler Feed: 36 Cooling Water: 36 Waste Water: 36 Other Applications for the Energy / Power Industry: 36 Automotive and Aerospace Industry 37­38 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 39­40 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 41­43 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 44­45 Beverages: 45 Potato Products: 45 Waste Water: 45 Other Applications for the Food and Beverage Industry: 45 Industrial Waste Water 46­47 Environmental Sector 48­49 Potable (Drinking) Water: 49 River and Surface Waters: 49 Air Pollution: 49 Overview of Process Analyzers 50­51 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 (Cl ), which are then used impurities such as calcium and magnesium can shorten 2 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. Chlor­Alkali Chlor­Alkali Process Application Notes for the Chlor­Alkali Industry 07 • Chlor-alkali industry: Hardness in Brine. AN­PAN­1005 Sold and Installed Applications Brine Production: Secondary Purification Resin Treatment: • Alkalinity in Brine (Brine Production) • Hydroxide [OH-] + Carbonate [CO 2-] in Brine (Brine 3 • 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 [CO 2-] in Brine (Pretreat- • Hypochlorite [ClO-] + Sulfite [SO -] (Mercury Cell 3 3 ment Raw Brine) Effluent) • Hydroxide [OH-], Carbonate [CO 2-], + Calcium [Ca2+] • Sulfate [SO 2-], Chlorine [Cl ], + pH in waste water 3 4 2 in Brine (Brine Purification) (Effluent WWTP) • Hydroxide [OH-], Carbonate [CO 2-], + Hypochlorite 3 [ClO-] in Brine Other Applications for the Chlor­Alkali Industry: • Magnesium [Mg2+] in Brine (Brine Purification) • Ammonia [NH ], Total Alkalinity, Carbonate [CO 2-], 3 3 • Sodium Hydroxide [NaOH] in Brine (Brine Pre-Treatment) + Chloride [Cl-] in Brine • Sodium Hydroxide [NaOH], Chlorine [Cl ], + • Carbonate [CO 2-] in Overcarbonated Brine 2 3 Carbonate [CO 2-] in Brine (Brine Purification) 3 Chlorine Production: • Chloride [Cl-] in 50% Sodium Hydroxide [NaOH] (Chlorine production) • Chlorine [Cl ], Hydroxide [OH-], Carbonate [CO 2-], 2 3 Chloride [Cl-], + pH in Brine (Chlorine plant) • Potassium iodate [KIO ] in Brine (Chlorine production) 3 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 [Na CO ] in Brine 2 3 (Inlet Resin Treatment) • Chlorate [ClO -] in Brine (Inlet Membrane Electrolyzer) 3 • Chlorine [Cl ] in Brine (Outlet Membrane Electrolyzer) 2 Chlor­Alkali 08 Chemical Industry: Soda Ash Production Solvay Process Sold and Installed Applications Soda ash (sodium carbonate, Na CO ) is used as the pre- 2 3 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 [NaHCO ] (Soda Ash production) 3 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 [CO ] in soda (Soda Ash production) 2 duc tion process for soda ash is the Solvay process, which • Carbonate [CO 2-] in the Gas Scrubber Carbonization 3 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) bil lion 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 [NH ] / Ammonium [NH +] in brine 3 4 vay process, while the remaining 28% has been mi ned (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: • Chloride [Cl-] in effluent (WWTP) Process Application Notes for the Soda • Ammonia [NH ] / Ammonium [NH +] in waste water Ash Industry 3 4 (WWTP) • Analysis of Ammonia in the Preparation of Ammonia-Saturated Brine. Other relevant PANs can be found in the Chlor-Alkali AN­PAN­1025 Industry section. Soda Ash Polymers 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 branch gums. The polymerization reaction is the critical point in sites here: the production process, and poor-quality raw materials http://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. AN­PAN­1041 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 equip ment, 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 ly mer 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 [Cl ] in Incineration Furnace Waste • Monitoring the Degree of Cure of Resin-Coated 2 Treatment (PVC Production, WWTP) Fiberglass (NIRS) • Free Chlorine [Cl ] in PVC (PVC Production) 2 • Water [H O] content in 1,2-dichloroethane [C H Cl ] 2 2 4 2 (EDC/VCM production) Polymers Polymers Hydroxyl Number: 11 • Monitoring Hydroxyl Number and Acid Value in 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 creatand 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 http://www.metrohm.com/en/industries/chemical­ variety of applications in many areas. The following are a industry­basic­chemicals/chemical­standards selection of some of the more prominent chemical ma - nufacturing processes to which we have sold many appli- http://www.metrohm.com/en/industries/chemical­ cations: the cumene process which produces acetone industry­solvents/chemical­solvent­standards Chemicals Chemicals Process Application Notes for the Chemical Industry 13 • HPPO process for Propylene oxide (PO): Analysis of peroxide. AN­PAN­1007 • Cumene process: Analysis of Sulfuric Acid in Acetone and Phenol. AN­PAN­1008 • Caprolactam Production: Determination of Permanganate Absorption Number. AN­PAN­1011 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 [NH +] + Nitrite [NO -] in Caprolactam 4 2 low solubility in water. The exposure to low concentra- Production (Reactor) tions are enough to disrupt the endocrine system, espe- • Ammonium Sulfite [(NH ) SO ] in Caprolactam 4 2 3 cially for children, and could lead to developmental dis- Production (Reactor) orders in later years. • Hydroxylamine [NH OH] in Caprolactam Production 2 (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 [H SO ] in Phenol-Acetone/Phenol 2 4 (Reactor – Acetone + Phenol production) Applications for Caprolactam Process Waste: • Sulfuric Acid [H SO ], Sodium Phenolate [C H NaO], + • Ammonium [NH +] in Outlet WWTP (Effluent) 2 4 6 5 4 Sodium Hydroxide [NaOH] in process (Outlet Reactor) • Sodium hydroxide [NaOH] in Outlet Reactor (Caprolactam Outlet Reactor) Chemicals 14 HPPO Process – Propylene Oxide production Applications for the HPPO Process: Propylene oxide is an important product for the chemical • Hydrogen Peroxide [H O ] + Hydroquinone [C H O ] 2 2 6 6 2 industries because of its wide range of applications that (Reactor, Hydrogen peroxide production) are predominantly used in the polyurethane and solvent • Hydrogen Peroxide [H O ] in Anthraquinone [C H O ] 2 2 14 8 2 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 [H O ] in Condensate (Hydrogen 2 2 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 [H O ] in neutralized aqueous 2 2 Hydrogen peroxide present in a methanol solvent is used effluent (WWTP) as the sole oxidizing agent and is the critical feedstock • Hydrogen Peroxide [H O ] in waste water (Hydrogen 2 2 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 H O concentrations in 2 2 the primary reaction tank plays a vital role to ensure high PO yields while reducing costs with low feedstock consumption. Fertilizer manufacturing Fertilizer is used to supply essential nutrients for prolifera-tion of plant growth, leading to larger yields in the agricultural industry. Fertilizers can come from either natural (such as manure, bone meal, or compost) or synthetic sources. Primarily, synthetic fertilizers are made of nitrogen, 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. De ficiencies in these nutrients result in stunted growth, yellowed leaves, and an overall weak structure. The synthesis of the nitrogen component begins with ammonia (NH ) generally derived from the large-scale 3 Haber process, which is then reacted with nitric acid (HNO ) to create ammonium nitrate. Phosphorus can be 3 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 [H PO ] in Diammonium phosphate 3 4 from potassium chloride, generally granulated in order [(NH ) HPO ] production 4 2 4 for easier blending with the other compounds so that the • Phosphorus pentoxide [P O ] in Fertilizer Production 2 5 fertilizer can be easily and properly distributed. • Sulfate [SO 2-] in Fertilizer Production 4 • Sulfuric Acid [H SO ] in Phosphoric Acid [H PO ] for 2 4 3 4 Fertilizer Production (H PO Reactor) 3 4 Chemicals Chemicals Applications for Fertilizer Emission Control: NIRS Applications for the Chemical Industry: 15 • Ammonia [NH ] in Fertilizer Production (Emission 3 Control) This list is intended as a starting point but is not • Ammonia [NH ] + Nitrate [NO -] in Fertilizer comprehensive. Many determinations listed below 3 3 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 [NO -] in Fertilizer Production (effluents Solvent (NIRS) 3 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 [NH ] in process (MDEA Production) • Monitoring Water, Acetic Acid, Beta-Picoline and 3 • Caustic [NaOH] in process Dimethylacetamide in a Solvent Stream (NIRS) • Chlorine [Cl ] in Titanium(II) oxide [TiO ] (Titanium 2 2 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 [S O 2-] in process • Monitoring Hydroquinol Production in a Reaction 2 3 • 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 [CCl ] 4 by Karl Fischer Titration Mixtures: • Monitoring Methoxypropylamine and N,N Waste Water: Diethylaminoethanol in a Complex Mixture (NIRS) • Ammonia [NH ] in waste water (WWTP) 3 • 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 [Cl ] in condensing water (WWTP) 2 • Nitrate [N-NO -] in waste water (WWTP) 3 • Phosphate [P-PO 3-] in waste water (WWTP) 4 Chemicals 16 Petrochemical Industry A demanding industry Explosion­proof 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 stainless-steel explosion-proof version for Zone I or Zone II Lubricant of the global economy ac cord ing 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. http://www.metrohm.com/en/industries/ Petro Petro Process Application Notes for the Petrochemical Industry 17 • Sour Water Stripper (SWS): Analysis of hydrogen sulfide and ammonia in Sour Water. AN­PAN­1001 • Desalting Crude Oil – Analysis of Salt in Crude Oil. AN­PAN­1014 • Mercaptans and Hydrogen Sulfide Derived from Crude Oil According to ASTM D3227 and UOP163. AN­PAN­1026 • Inhibiting Polymerization: Monitoring the Concentration of TBC in Styrene According to ASTM D4590. AN­PAN­1027 • ASTM D8045: Online measurement of the acid number (AN) in oils with thermometric titration. AN­PAN­1037 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 [NO -] in waste water (WWTP) 2 purification process) • Total Nitrogen [TN] in water control • Sodium chloride [NaCl] in Crude Oil (Salt in crude) • Phenol [C H OH] in refinery waste water (WWTP) 6 5 • Water determination in Kerosene and Diesel • Phosphate [PO 3-] / Total Phosphate [TP] in waste 4 (Production and Purification Processes) water (water control, WWTP) • Sulfate [SO 2-] in waste water (Seawater treatment, 4 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 [NH ] / Ammonium [NH +] in Petrochemical • Sulfite [SO -] in waste water (WWTP) 3 4 3 water treatments (Acid water treatment, Sour Stripper water, Circulation water, Waste water, etc.) Other Applications for the Petrochemical • Carbonate [CO 2-] in water recovery process Industry: 3 • Chlorine [Cl ] in water treatment processes • 4-tertiary-butylcatechol [TBC] in Styrene (Styrene Inlet 2 (Cooling water) Storage Tank) • Fluoride [F-] in cooling water (Alkylation Unit) • Acetic Acid [CH COOH] in Petrochemical Processes 3 • 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 [NH ] / Ammonium [NH +] in waste water • Caustic [NaOH] in Diethylene Glycol [DEG] (Ethylene 3 4 • Ammonia [NH ] + Sulfide [S2-] in inlet of WWTP Glycol production, MEG Scrubber) 3 (Waste Water Treatment, Sour water) • Caustic [NaOH] in fuels (Refinery process) • Ammonium [NH +] + Hydrogen sulfide [H S] (WWTP) • Total Caustic [OH-] + Free Caustic [OH-] in Ethylene 4 2 • Barium [Ba2+] in waste water (WWTP) Scrubber Petro 18 • Chloride [Cl-], Iron [Fe2+], + pH in Distillate stream aromatics, naphthenes, and olefins; PIANO). Common (Overhead Condensing System of Crude Distillation die sel parameters measured with NIR include specific Unit) gra vity, 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 [H O ] in Dispensed/Recovery ga soline, biodiesel). 2 2 Liquid (Methanol/Propylene/H O/Propylene-Oxide 2 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 [H O] + Formic Acid [HCOOH] in Methanol • Monitoring a Gasoline Blend (NIRS) 2 (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 Semicon / Electronics 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 Semi conductor 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 & Hypo phos phite content. AN­PAN­1012 • Monitoring Tetramethylammonium Hydroxide (TMAH) in Developer. AN­PAN­1028 Sold and Installed Applications Aluminum Foil Etching: Wafer Etching: • Free and Total Acid in Etching bath (Aluminum Foil • Acid (Total) - (Phosphoric acid [H PO ], Nitric acid 3 4 for Electrolytic Capacitors, PCB) [HNO ] and Citric acid) in etching process (LCD 3 • Free and Total Acid + Ortho-Phosphate [P-PO ] in Manufacture) 4 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 [NO -] in etching baths (PCB, Etching 2 Bath) bath) • Phosphoric acid [H PO ] in Etching bath (Aluminum • Chloride [Cl-] in 50 to 80% Sulfuric Acid [H SO ] 3 4 2 4 Foil for Electrolytic Capacitors, PCB) (Waste H SO recycling system) 2 4 • Copper [Cu2+], Sulfuric acid [H SO ], + Chloride [Cl-] 2 4 Glass Etching: in etching bath (Micro-Chips, Etching bath) • Hydrofluoric acid [HF], Nitric acid [HNO ], + Sulfuric • Copper [Cu2+], Sulfuric acid [H SO ], + Sodium 3 2 4 acid [H SO ] in etching baths (LCD Display, Glass peroxosulfate [NaPS] in Etching Cleaner (BOC (Board 2 4 etching) On Chip)) • Nitric acid [HNO ], Sulfurous Acid [H SO ], + Hydro- • Hydrochloric acid [HCl], Aluminum Chloride [AlCl ], + 3 2 3 3 fluoric Acid [HF] in etching (LCD screen, Glass etching) Boric acid [B(OH) ] in process (Transistor & Resistors, 3 • Oxalic acid [H C O ] in etching process (LCD manufac-Etching bath) 2 2 4 turing) • Hydrofluoric Acid [HF] + Hydrochloric acid [HCl] • Sulfuric acid [H SO ] + Hydrogen Fluoride [HF] in (binary acid etchant) 2 4 process (Glass etching) • Hydrogen peroxide [H O ] + Hydrochloric acid [HCl] in 2 2 etching bath (Surface treatment, etching bath) Solar Etching: • Hydrogen Peroxide [H O ] + Sulfuric Acid [H SO ] in 2 2 2 4 • Hydrogen fluoride [HF], Hexafluorosilicic acid [H SiF ], Etchant (Touch Screen Panels, Monitoring Etchant, 2 6 Nitric Acid [HNO ], + Acetic Acid [CH COOH] (Wafer Etching Clean Bath) 3 3 texturing of solar panels) • Iron [Fe2+], Nickel [Ni2+], + Copper [Cu2+] in Etching • Hydrofluoric Acid [HF] + Nitric acid [HNO ] Etching Bath (Monitoring Etching Bath, SC1, SC2) 3 baths (Solar Cells, Etching Baths, Mixed acid etchant) • Methanesulfonic acid [MSA] + Hydrofluoric acid [HF] • Isopropyl alcohol [C H O] + Sodium hydroxide [NaOH] in MSA/HF storage tanks (Wafers, Etching baths) 3 8 in etching baths (Wafer Texturing, Etching bath) • Monitoring Etching Baths (NIRS) • Nitric acid [HNO ], Hydrogen fluoride [HF], + Hexa- • Monoethanolamine [MEA] + water [H O] in Alkaline 3 2 fluor osilicic acid [H SiF ] / Hydrochloric acid [HCl] + Photoetch (Flexible Electronic Circuitry) 2 6 Hydrogen fluoride [HF] / Potassium hydroxide [KOH] + • Nickel [Ni] + Hypophosphite [H PO -] in etching baths 2 2 Sodium hydroxide [NaOH] (Solar Panels, Etching (Etching baths) Texturing) • Nitric acid [HNO ] in etching bath (Etching) 3 • Potassium hydroxide [KOH], Isopropanol, + Hexa - • Sulfuric acid [H SO ], Hydrofluoric acid [HF], + 2 4 fluor osilicic acid [H SiF ] / Hydrochloric acid [HCl] + Hydrogen peroxide [H O ] in etching baths (Wafers, 2 6 2 2 Hydrogen fluoride [HF] / Hydrogen peroxide [H O ] Etching baths) 2 2 (Solar Panels, Etching Texturing) Semicon / Electronics Semicon / Electronics • Sulfuric acid [H SO ], Phosphoric acid [H PO ], Waste Water: 2 4 3 4 21 Hydrogen Peroxide [H O ], + Titanium in Etching bath • Ammonia [NH ] in waste water (WWTP) 2 2 3 (Copper Etchant, Mixing) • Ammonia [NH ], Fluoride [F-], + pH in Hydrofluoric 3 • 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 [H O ] in slurry 2 2 dehyde [CH O] in electroless Copper (BOC (Board On Copper waste treatment (Chip (Wafer), waste water 2 Chip)) treatment) • Dimethylamine borane [DMAB], Boric acid [B(OH) ], • Copper [Cu2+], Iron [Fe3+], + Nickel [Ni2+] in waste 3 Cobalt(II) sulfate [CoSO ], + pH in Cobalt plating bath water (WWTP) 4 (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 [CH O], Sodium hydroxide [NaOH], + • Hydrogen peroxide [H O ] in waste water (WWTP) 2 2 2 Dimethylamine borane [DMAB] in Cu plating solution • Nickel [Ni2+] in waste water (WWTP) (PCB, Copper Plating) • Nitrite [NO -] in waste water (Solar Panels, Detox 2 • Leveller in acid-Cu bath (Micro-Chips, Copper Plating Waste Water, WWTP) at Pilot Plant) • Phenol [C H OH] in waste water (Semiconductor, 6 5 • Nickel [Ni2+] + Hypophosphite [H PO -] in Nickel WWTP) 2 2 Plating Bath (Electroless Wafer Bumping, Nickel • Ortho-Phosphate [PO 3-] in waste water (WWTP, 4 Plating Bath) Outlet LED production) • Nickel [Ni2+] + Phosphoric acid [H PO ] (Nickel bath) • Sulfate [SO 2-] in waste water (Final Effluent 3 4 4 • 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 [NH ] in cooling water (Microchips • Hydrochloric acid [HCl] + Hydrogen Peroxide [H O ] 3 2 2 production) in SC2 Clean • Ammonium [NH +] in Chemical Dilution system (Semi- • Hydrofluoric acid [HF] in process water (Chemical 4 conductor parts) preparation, Dilution system, Blending) • Ammonium Hydroxide [NH OH] (Chemical distribution, • Hydrogen Peroxide [H O ] in CMP Slurry (Wafer 4 2 2 Blending system) polishing, Chemical Mechanical planarization) • Ammonium Hydroxide [NH OH] + Hydrogen Peroxide • Hydrogen Peroxide [H O ] + Ammonia [NH ] in 4 2 2 3 [H O ] in SC1 Clean reclaim water (Reclaim water) 2 2 • Benzotriazole (BTA) [C H N H] as Copper Corrosion • Hydrogen peroxide [H O ], pH, Temperature, + 6 4 3 2 2 Inhibitor in flexible circuitry Conductivity (CMP Slurry chemical blending) • Copper [Cu2+] + Hydrogen Peroxide [H O ] in SCW • Phosphoric acid [H PO ], Hydrogen peroxide [H O ], + 2 2 3 4 2 2 (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 Mining 23 Mining Industry Ever­increasing 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. AN­PAN­1002 • Zinc production: Analysis of Zinc, Sulfuric acid and Iron. AN­PAN­1006 • Analysis of Bayer Aluminate Liquors Using Thermometric Titration. AN­PAN­1034 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 [NH ] + Carbon Dioxide [CO ] (Nickel, 3 2 • Sulfuric acid [H SO ], Copper [Cu2+], Iron [Fe2+], Iron Leaching S/X Circuit) 2 4 [Fe3+], + BT (Copper refinery) • Metals (Total) + pH (Leach plant) • Silica [SiO ] in Ammonium sulfate [(NH ) SO ] in 2 4 2 4 Electrowinning Processes: Manganese processing (Leaching, Thickening, and • Acid, Chloride [Cl-], Iron [Fe2+], + Rx in Copper Purification) electro winning process (Electrolysis) • Sulfuric acid [H SO ], pH, Redox, + Chloride [Cl-] 2 4 • Chloride [Cl-] in Copper Electrolyte solution (Copper (Copper mining, Leaching) refinery, Electrolyte tanks) • Zinc [Zn2+] + Sulfuric Acid [H SO ] in process (Zinc 2 4 • Copper [Cu2+] from copper electrowinning (Copper production, zinc leaching) electro refining) • Copper [Cu2+], Sulfuric Acid [H SO ], + Chloride [Cl-] Nickel Mining & Purification: 2 4 in Electrolyte (Metallurgy company, Refinery Deep • Aluminum [Al3+] (Nickel Purification) Electrolyte Decopperization) • Ammonia [NH ] in process (Nickel, Solvent Extraction, 3 • Free Acid (Nitric Acid) [HNO ] in process (Uranium WWTP) 3 Processing, Uranium Extraction (Yellow Cake Process)) • Ammonia [NH ] + Carbon Dioxide [CO ] (Nickel, 3 2 • Sulfur Dioxide [SO ] in Electrolyte solution (Manganese, Leaching S/X Circuit) 2 SO Absorption into Feed Electrowinning) • Copper [Cu2+] in Nickel(II) sulfate [NiSO ] refining 2 4 • Sulfuric acid [H SO ] (Zinc purification, Copper Electro-process (Deep removal copper process) 2 4 winning, Copper Electro Refining) • Nickel [Ni2+] from purification processes (Nickel Purification) • Sulfide [S2-] gas in flue gas in acid smelter in Nickel mine (Nickel) • Zinc [Zn2+] (Nickel Purification) Mining Mining Platinum Refineries: 25 • Acid, pH, Redox, + Caustic [NaOH] in multiple sample • Cyanide, Free [CN-] in waste water (WWTP) streams (Platinum refineries) • Cyanide, total [TCN] in Process Waste (Polymetallic • Molar Ratio [Ni/NH ] (Platinum refineries) mining, Cyanide Destruction Plant) 3 • 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 [ZnSO ] (Zinc Purification, Plant (Nickel, PN Feed) 4 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 [PO 3-] in waste water 4 • Hydrogen Sulfide [H S] in Process (Zinc production) (Grit Chamber, precipitation of particles, WWTP) 2 • Hydrogen sulfide [H S] in zinc purification processes • Silica [SiO ] in waste water (Metallurgy company, 2 2 (Zinc purification) WWTP) • Iron [Fe2+] (Zinc purification) • Sulfate [SO 2-] in waste water 4 • Iron [Fe] + Sulfuric Acid [H SO ] in Electrolysis (Zinc • Sulfide [S2-] in waste water (Zinc & Lead Production, 2 4 production, Electrolysis) WWTP) • Sulfuric Acid [H SO ] in Electrolysis (Zinc production, 2 4 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 [H SO ] [Cl-] in process (Acid Recovery Plant) 2 4 in Electrolysis (Zinc production, Electrolysis) • Chromic acid [H CrO ] (Chrome production) 2 4 • Zinc [Zn2+] + Sulfuric Acid [H SO ] in process (Zinc • Dinitrogen trioxide [N O ] in H SO (Reactor, Sulfuric 2 4 2 3 2 4 production, zinc leaching) Acid by absorption of SO )2 • Hypochlorite [OCl-] in a scrubber system for exhaust Waste Water: gas (mining) • Ammonia [NH ] in process (Nickel, Solvent Extraction, • Metals (Total) and Acid in spent electrolyte (Autoclave 3 WWTP) Spent Electrolyte) • Cadmium [Cd] in Zinc sulfate [ZnSO ] (Zinc Purification, • Monitoring Moisture Content in Concentrated Iron 4 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 Hot vs. cold roll 27 warm, rolled out into increasingly thinner sheets, which Hot rolled steel is suitable for pipes, tubing, auto frames, 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 techniques 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. AN­PAN­1019 Sold and Installed Applications Pickling Process: • Acid (Total), Hydrogen fluoride [HF], + Nitric acid • Manganese [Mn2+] + Sulfate [SO 2-] in waste water 4 [HNO ] (Acid Pickling Stainless Steel) (Manganese Based Metals, WWTP) 3 • Hydrochloric acid [HCl] in Pickling solution (Pickling • Nickel [Ni2+] in ground/waste water (WWTP) bath) • Nitrate [NO -] in influent (Stainless Steel, WWTP) 3 • Hydrochloric acid [HCl] + Iron [Fe] in Pickling solution • pH, Free-Ammonia [NH ], + Total Ammonia [NH ] 3 3 (Pickling bath) in waste water (Steel, Waste De-Ammonization of • Hydrogen Peroxide [H O ] in Pickling solution (Stainless Coke plant) 2 2 Steel, Pickling process) • Sodium sulfate [Na SO ] in waste water (WWTP) 2 4 • Iron [Fe3+], Sulfuric Acid [H SO ], + Hydrogen Fluoride • Thiosulfate [S O 2-] in waste water (WWTP) 2 4 2 3 [HF] in pickling bath (Pickling bath) • Zinc [Zn2+] in waste water (Metal treatment, WWTP) • Zinc [Zn2+] + Sulfuric acid [H SO ] in waste water 2 4 Waste Water: (WWTP) • Ammonia [NH ] in waste water (WWTP) 3 • Ammonia [NH ], Nitrate [NO -], + Nitrite [NO -] in Aluminum Milling: 3 3 2 waste water (Steel, WWTP) • Aluminum [Al3+] + Caustic [NaOH] (Aluminum) • Ammonia [NH ], Phenol [C H OH], Cyanide [CN-], + • Fluoride [F-] in 2.5% Sulfuric Acid [H SO ] bath 3 6 5 2 4 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 [H SO ] + Aluminum [Al3+] in Aluminum 2 4 • 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 [H SO ] in water (Zinc extraction, metal 2 4 Manganese [Mn]/Phosphating Bath (Tubes for Crude recovery, Process water treatment) transport) • Sulfuric acid [H SO ] in Ammonium sulfate [(NH ) SO ] 2 4 4 2 4 • Ammonia [NH ] in Cokes Gas (Steel, Coking Plant) (Outlet reactor) 3 • Ammonia [NH ] + Sulfide [S2-] in Scrubber (Ammonia • Tin [Sn] + Sulfonic acid [R-S(=O) -OH] (Steel production) 3 2 Recovery plant) • Zinc [Zn2+], Nickel [Ni2+], + Nitrate [NO -] in zinc 3 • Total + Free Ammonia [NH ] in Stripper (Steel, Coking phosphating bath (Phosphate plating) 3 Plant, Waste water from Strippers) • Zinc [Zn2+] + Sulfuric acid [H SO ] in process (Steel, 2 4 • Calcium [Ca2+] (Aluminum Smelter, Dosing unit) Leaching) • Chloride [Cl-] in process water (Steel, cold mill 2) • Chromate [CrO 2-] in process (Steel, Metal Finishing) 4 • Copper [Cu2+] (Copper tubes) • Copper [Cu2+], Sulfuric Acid [H SO ], + Chloride [Cl-] in 2 4 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 [H S], Ammonia [NH ], + pH in Acid 2 3 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 [Na CO ], + Copper [Cu2+] in 2 3 Copper Plating Bath (Metal Wire Production) Steel / Metal Galvanic / 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 (Fe O ), hematite can be found here: 3 4 (Fe O ), goethite (FeO(OH)), and more. As a refined http://www.metrohm.com/en/industries/ 2 3 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, refinin 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 proof 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. Elec tro-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. Passi va-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- re habilitation 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. Phos phatization 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-Hot­dip 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. AN­PAN­1018 • Steel Industry: Analysis of Acids and Iron in Pickling Baths. AN­PAN­1019 Galvanic / Metal 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 [HNO ], + Titanium 3 (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 [NiSO ] + Cobalt Sulfate [CoSO ] in 4 4 • 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 [SO 2-] in waste water (WWTP) • Sodium Hydroxide [NaOH] + Ammonia [NH ] in 4 3 • 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 [H SO ] + Hydrogen Peroxide [H O ] in 2 4 2 2 (Etching bath) etching bath (Etching bath) • Boric Acid [B(OH) ], Aluminum [Al3+], + Nitric Acid • Tin [Sn] + Acid (Tin plating) 3 [HNO ] in plating bath (Plating bath control) • Zinc [Zn2+] in galvanic bath (Surface finish) 3 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 Pulp / Paper Process Application Notes for the Pulp and Paper Industry 33 • ABC Titration: Analysis of Alkali, Carbonate, hydroxide and sulfide in Pulping Liquors. AN­PAN­1004 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 [H O ] in bleaching solution 2 2 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 comin 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 [PO 3-] + Total Phosphate (TP) in 4 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 [CO ] in Treated/Recycled 2 • Determining Kappa Number in Pulp in Blowline Water (Water purification) Samples (NIRS) • Caustic [OH-], Carbonate [CO 2-], Hydrogen Sulfide 3 • Monitoring Kappa Numbers in Pulp-Cotton Linters [HS-], + Sulfate [SO 2-] in Black, Green & White Liquor 4 Mixtures (NIRS) (recovery process) • Silica [Si4+] (Pulp Process) Moisture Content: • Sodium Bisulfite [NaHSO ] in paper production (Paper 3 • Monitoring Moisture in Paper Coating Mixtures (NIRS) production) • Determining Moisture in Paper and Lacquer Weight • Sulfite [SO 2-] in process (Tannin production, Reactor) 3 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 Energy / Power tion. Nearly 50% of the unplanned downtimes in power power plant. This can be combated with an optimized 35 plants are caused by contaminants or problems with the feed water chemistry. On the one hand, the water must 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 con tinuously 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, ri cant 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. How ever, 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 http://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 CO captured (CO Loading). AN­PAN­1003 2 2 • Nuclear Power Plants: Analysis of Boric Acid in cooling water PWRs. AN­PAN­1013 • Flue-gas desulfurization; incineration process – Analysis of calcium and sulfate. AN­PAN­1015 • Power Plant: Analysis of Silica in boiler feed water. AN­PAN­1016 • Monitoring Flow Accelerated Corrosion & Metal Transportation in Power Plants: Online Ultratrace Measurements of Fe and Cu. AN­PAN­1032 • Power Generation: Analysis of the M-Number (Alkalinity) in cooling water. AN­PAN­1038 • Ammonia in cooling water of thermal power plants. AN­PAN­1040 • Online trace analysis of anions in the primary circuit of nuclear power plants. AN­PAN­1042 • Online trace analysis of cations in the primary circuit of nuclear power plants. AN­PAN­1043 • Online trace analysis of amines in the alkaline water-steam circuit of power plants. AN­PAN­1044 (no URL at this time) Energy / Power 36 Sold and Installed Applications Boiler Feed: Other Applications for the Energy / Power • Ammonia [NH ] in boiler feed water (Boiler Feed) Industry: 3 • Iron [Fe2+ / Fe3+] in boiler feed water (Boiler Feed) • Aluminum [Al3+] (Feed to softeners) • pH + Alkalinity in Boiler feed water (Boiler feed water, • Ammonia [NH ] in scrubber ash (Stack Scrubber 3 Neutralization process) control for Ash content) • Phosphate [PO 3-] (total and ortho) in water (Boiler • Calcium [Ca2+] + Sulfate [SO 2-] in process (Incinerator 4 4 feed water, Feed to softeners) plant) • Silica [Si4+] in Boiler Feed Water (Boiler Feed) • Carbon Dioxide [CO ] Loading in Organic Absorber 2 • 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 [NH ] in cooling water (Nuclear Power • Hardness [Ca2+ / Mg2+] in demi water plant 3 Plant, Cooling of Reactor) • Hypochlorite [NaOCl] in make-up water (Disinfection • Boric acid [B(OH) ] in heavy water / cooling water Treatment Monitoring) 3 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 [SiO ] in demi water (Boiler feed) 2 • 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 [NH +] in primary circuit 4 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 [NH ] in waste water treatment (WWTP) 3 • Total-Ammonia [NH ], Free-Ammonia [NH ], + pH in 3 3 waste water (Coking plant, De-Ammonization of waste water) • Chlorine [Cl ] in cooling water discharge (Cooling 2 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 [SO 2-] in waste water (WWTP) 3 • Volatile Fatty Acids (Anaerobic WWTP) Energy / Power Auto / Aero 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 Ma nufacturers’ 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) ] in Nickel [NiCl ] Electroplating Bath • Aluminum [Al3+], Copper [Cu], + Chromium [Cr3+ /Cr6+] 3 2 (Aerospace Engines, Nickel Electroplating Surface in Effluent (Airfighters production, Effluent WWTP) Treatment) • Fluoride [F-] in waste water (WWTP) • Chromium [Cr3+] in Chromic Acid [H Cr O ] Electro- • Iron, Total [Fe2+ / Fe3+] + Zinc [Zn2+] in Effluent (Air-2 2 4 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 [HNO ], Hydrofluoric Acid [HF] + Neutralizer in Etching treatment) 3 Baths (Blade production, Nickel Turbine Etching Baths) • Hydrofluoric acid [HF] (Car screen (glass)) • Caustic [NaOH], Nitric acid [HNO ], + Ammonium • Sodium Hydroxide [NaOH] in Scrubber (Scrubber, 3 Bifluoride [NH HF ] in Etching Baths Automotive parts for car & aviation industry) 4 2 (Blade production, Titanium Fan Blade Etching Baths) • Sulfuric acid [H SO ], Phosphoric Acid [H PO ], Total 2 4 3 4 Iron [Fe2+ / Fe3+], + Hydrochloric Acid [HCl] (Turbine Blade Production, Electrolytic Etching Baths) Zinc­Phosphatizing: • Acid [Free and total], Fluoride [F-], Zinc [Zn2+], + Accelerator (Zn-Phosphatizing Bath) • Acid [Free and total], Nitrite [NO -], + Zinc [Zn2+] 2 (Zn-Phosphatizing Bath) • Fluoride [F-] in Surface Treatment Bath (Cars, Zinc-Phosphatizing Bath) • Sulfuric acid [H SO ] + Zinc [Zn2+] (Phosphatizing bath) 2 4 Auto / Aero Textiles 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. pur poses – to decorate, to clothe, and to protect. Du ra - 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 exerelas ticity) 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- Auto / Aero Textiles 40 Process Application Notes for the Textile Industry • Viscose / Rayon production: Analysis of Sulfuric Acid and Zinc Sulfate. AN­PAN­1010 • Online Analysis of Indigo, Hydrosulfite, and Other Parameters in Textile Dye Baths. AN­PAN­1035 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 [SO -] in influentv WWTP (WWTP) tiate fiber types for carpet recycling. Blend analysis of 3 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 [H SO ] in Spin Bath (Fiber Production, (K-29, K49, and K129), nylon-6, nylon-6,6, silk, polyester, 2 4 Cellulose Fibers, Spin bath) cationic and disperse dyeable polyester, polypropylene, • Sulfuric acid [H SO ], Zinc sulfate [ZnSO ], + Sodium PVA and PVC. 2 4 4 sulfate [Na SO ] in Spin Bath (Fiber Production, Spin 2 4 bath) This list is intended as a starting point but is not comprehensive. Other Applications for the Textile Industry: • Hydroxide [OH-] + Carbonate [CO 2-] in cleaning Fiber Blends: 3 solution (Textile cleaning) • Monitoring Fiber Blends for Blend Ratios, Moisture • Indigo [C H N O ] + Hydrosulfite [S O 2-] (Textile and Finish (NIRS) 16 10 2 2 2 4 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 [H SO ] + Formaldehyde [CH O] in acid Nylon Thread (NIRS) 2 4 2 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 Pharma / Biochem 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 - iden tity, 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 me di-ing to both the directives of the ICH (International ci nal 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 Phar ma- ceutical branch sites here: http://www.metrohm.com/en/industries/ Pharma / Biochem 42 Sold and Installed Applications Waste Water: • Ammonia [NH ] in waste water (WWTP) 3 • Chemical Oxygen Demand [COD] in waste water influent WWTP) • Chloride [Cl-] in Outlet WWTP (WWTP, Hospitals) • Nitrite [NO -] in BioReactor (Inlet BioReactor, WWTP) 2 • Phosphate [P-PO ] in Final Effluent (Pharmaceutical, 4 WWTP) Other Applications for the Pharmaceutical / Biochemical Sector: • Ammonia [NH ] in Fermenter Cultures (Control of 3 Ammonia in Fermenter Cultures) • Calcium [Ca2+] in Bioreactor (Reactor) • Sodium hydroxide [NaOH] + Sodium Carbonate [Na CO ] in Scrubber (Biopolymer, Scrubber) 2 3 • 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 on line 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 ma copeia (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® soft ware 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 Pharma / Biochem This list is intended as a starting point but is not 43 comprehensive. 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 [CaCO ] in Antacid Powders and • Methylphenidate in Transdermal Patches (NIRS) 3 Tablets (NIRS) • Nicotine in Transdermal Patches (NIRS) • Magnesium Hydroxide [Mg(OH) ] in Antacid Powders • Nitroglycerine in Transdermal Patches (NIRS) 2 (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, heat ing, 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: http://www.metrohm.com/en/industries/ Food / Drinks Food / Drinks Process Application Notes for the Food and Beverage Industry 45 • Monitoring Peracetic Acid (PAA) in a Beverage Bottling Facility. AN­PAN­1029 • Effectively Monitoring Hydrogen Peroxide as a Delousing Agent in Salmon Farms. AN­PAN­1031 • Alkalinity & hardness in process and make-up water for the production of beer. AN­PAN­1036 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 [NH ] in food casings (Food casings) 3 • 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 [Cl ] in disinfection (Disinfection, Clean in 2 (Beverages (Soda), Water Purification System) Place) • Total Iron [Fe2+ / Fe3+] in ground water (Beverages, • Chlorine [Cl ] in Hypochlorite [ClO-] (Starch products, 2 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) [CH CO H] in beverage industry • Fluoride [F-] in toothpaste (Toothpaste, Dental rinsing) 3 3 filling systems (Aseptic Bottling Line) • Hydrogen peroxide [H O ] in seawater (Salmon 2 2 • Polyacrylamide (PAM) solution (Bottling plant) treatment) • Sulfide [S2–] (Beverage production) • Hypochlorite [OCl–] in bleach • Iodide [I–] (salt production) Potato Products: • Salt [NaCl] and vinegar [CH COOH] in mayonnaise 3 • 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 [H SO ] (Cellulose housing for food) 2 4 flume) • Sulfuric acid [H SO ], Ammonium Sulfate [(NH ) SO ], 2 4 4 2 4 • Total Phosphorus [P] (Potato processing) + total Sulfate [SO 2–] (Casings for sausage) 4 • Sodium dihydrogen pyrophosphate [Na H P O ] in • Sulfuric acid [H SO ] + Ammonium Sulfate [(NH ) SO ] 2 2 2 7 2 4 4 2 4 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 [NH +] in Inlet WWTP (Soya production, 4 WWTP) • Chemical Oxygen Demand [COD] (WWTP) • Fluoride [F–] in waste water (WWTP) • Nitrite [N-NO –] in Inlet WWTP (Soy production, WWTP) 2 • Phosphate [PO 3–] in waste water (Food, Milk, Inlet 4 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 irrigation, 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, http://www.metrohm.com/en/industries/ pesticides, drugs, hormones, heavy-metal compounds, environment­water/table_water_standards body care and synthetic products. WWTP WWTP Process Application Notes for the Waste Water Industry • Waste Water Treatment Plants: Nitrogen Removal – Simultaneously analysis of Ammonia, Nitrate and Nitrite. AN­PAN­1009 • Detecting Chromate (Cr(VI)) in Waste Water Streams. 47 AN­PAN­1030 • Ortho- and total phosphate phosphorus analysis online according to DIN EN ISO 6878:2004-09 (formerly DIN 38405-D11). AN­PAN­1039 Sold and Installed Applications • Alkalinity in Effluent WWTP (Waste water treatment • Phosphate [PO 3-], Total Phosphate [TP], + Chemical 4 (Nitrification), Effluent WWTP) Oxygen Demand [COD] in Surface water (Municipal • Ammonia [NH ] in effluent WWTP (Municipal WWTP) WWTP, Total Phosphate [TP] in Effluent WWTP 3 • Ammonia [NH ] + Sulfide [S2-] in waste water treat- (Outlet WWTP) 3 ment (Municipal Wastewater Treatment, WWTP) • Sodium [Na+] in waste water (Waste water) • Ammonium [NH +] in waste water effluent (Municipal • Volatile Fatty Acids in biomatrix (anaerobic WWT) 4 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-NH ] WWTP) 4 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 [H O ] + Peracetic acid [CH COOH] 2 2 2 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 [NO -], Nitrite [NO -], + Ortho-Phosphate [P-PO 3-] 3 2 4 in waste water (Municipal WWTP, Outlet WWTP) • Nitrite [NO -] in water treatment (Biological reactor) 2 • Nitrite [NO -], Nitrate [NO -], + Ammonium [NH +] in 2 3 4 waste water (WWTP) • Phenol [C H OH] in waste water (WWTP) 6 5 • Ortho-Phosphate [P-PO 3-] in outlet and effluent 4 WWTP (Municipal WWTP, Effluent WWTP) • Ortho-Phosphate [P-PO 3-] + Total-Phosphate [TP] in 4 effluent WWTP (Municipal WWTP, Effluent WWTP) 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. http://www.metrohm.com/en/industries/ Enviro Enviro Sold and Installed Applications 49 Potable (Drinking) Water: River and Surface Waters: • Aluminum [Al3+] in drinking water (Potable water) • Ammonia [NH ] + Nitrate [NO -] in river water (River 3 3 • Ammonia [NH ] in drinking water (Drinking water Water Monitoring) 3 monitoring) • Ammonium [NH +] in river water (River Water 4 • Ammonia [NH ] in tap water (outlet waste water, Monitoring) 3 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 [NO -] in drinking water (Drink water quality • Nickel [Ni2+] in surface water (Surface Water 2 self-monitoring) Monitoring) • Phenol [C H OH] in drinking water (Drinking water • Nitrate [NO -] in river water (River Water Monitoring) 6 5 3 monitoring) • Phenol [C H OH] in river and surface waters 6 5 (River Water Inlet, WWTP, Surface Water Monitoring) • Ortho-Phosphate [PO 3-] in river water (River Control, 4 River Water Monitoring) • Phosphate [PO 3-], Total Phosphate (TP), + Chemical 4 Oxygen Demand [COD] in surface water (Surface Water Monitoring) • Sulfate [SO 2-] in surface water (Environmental control 4 of river water, River Water Monitoring) • Zinc [Zn2+] in surface water (Surface Water Monitoring) Air Pollution: • Applications involving air quality are generally performed 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 Ex­proof Zone 1 or 2 û û û û û Process Analyzers Process Analyzers Wet chemical systems 51 Customizable, multi­stream Process Analyzers 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 Ex­proof Zone 1 or 2 û û û ü û û Reagent­free systems NIRS – Near Infrared Spectroscopy Process Analyzers Features NIRS XDS Process NIRS Pro Number of sample streams 1–9 1 Reagent­free 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 Long­distance measurement ü û Ingress Protection IP65/Nema 4X IP69K Ex­proof 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 www.metrohm.com G, CH-9100 Herisau ohm A witzerland by Metr , printed in S SW -02 Subject to change Layout by Ecknauer+Schoch A 8.000.5184EN – 2017 Document Outline Chemical Industry: Chlor-Alkali Production Process Application Notes for the Chlor-Alkali Industry Brine Production: Brine Purification: Chlorine Production: Ion Exchange Cell Membrane Electrolyzer: Secondary Purification Resin Treatment: Waste Water: Other Applications for the Chlor-Alkali Industry: Chemical Industry: Soda Ash Production Process Application Notes for the Soda Ash Industry Soda Ash production: Brine Preparation: Waste Water: Chemical Industry: Polymer Production Standards for quality control Process Application Notes for the Polymer Industry Applications for PVC: NIRS Applications for the Polymer Industry: Physical Characteristics (Thickness, Density, Viscosity): Monitoring Curing Rate: Hydroxyl Number: Moisture/Water Content: Comparison / Distinguishing: Monitoring Blend/Reaction Characteristics: Additives: Chemical Industry Standards for quality control Process Application Notes for the Chemical Industry Applications for Cumene Process: Applications for Cumene Process Waste: Applications for Polyamide/Caprolactam Production: Applications for Caprolactam Process Waste: Applications for the HPPO Process: Applications for HPPO Process Waste: Applications for Fertilizer Production: Applications for Fertilizer Emission Control: Other Applications for the Chemical Industry: Waste Water: NIRS Applications for the Chemical Industry: Surfactants: Moisture Analysis: Reaction Monitoring: Mixtures: Solvent purity and recovery: Petrochemical Industry Standards for quality control Process Application Notes for the Petrochemical Industry Biodiesel Production: Kerosene Production: Other Downstream Processes: Waste Water: Other Applications for the Petrochemical Industry: NIRS Applications for the Petrochemical Industry: Semiconductor / Electronics Industry Process Application Notes for the Semiconductor / Electronics Industry Aluminum Foil Etching: Glass Etching: Solar Etching: Wafer Etching: Photolithography: Plating Baths: Waste Water: Other Applications for the Semiconductor/ Electronics Industry: Mining Industry Process Application Notes for the Mining Industry Copper Mining & Purification: Electrowinning Processes: Gold Mining & Purification: Leaching Processes: Nickel Mining & Purification: Platinum Refineries: Zinc Mining & Purification: Waste Water: Other Applications for the Mining Industry: Steel / Metal Industry Process Application Notes for the Steel / Metal Industry Pickling Process: Waste Water: Aluminum Milling: Other Applications for the Steel / Metal Industry: Galvanic / Metal Surface Industry Process Application Notes for the Galvanic / Metal Surface Industry Waste Water: Other Applications for the Galvanic / Metal Surface Industry: Pulp and Paper Industry Process Application Notes for the Pulp and Paper Industry Bleaching Process: Waste Water: Other Applications for the Pulp and Paper Industry: NIRS Applications for the Pulp and Paper Industry: Kappa Number: Moisture Content: Energy / Power Industry Standards related to the energy and power industry Process Application Notes for the Energy / Power Industry Boiler Feed: Cooling Water: Waste Water: Other Applications for the Energy / Power Industry: Automotive and Aerospace Industry Electroplating Surface Treatment: Etching Baths: Zinc-Phosphatizing: Waste Water: Other Applications for the Automotive and Aerospace Industry: Textile Industry Process Application Notes for the Textile Industry Acrylic Fiber Production: Cellulose Fiber Production: Spin Bath Process: Other Applications for the Textile Industry: NIRS Applications for the Textile Industry: Fiber Blends: Finishing: Fire Resistance: Heatset Monitoring: Pharmaceutical / Biochemical Sector Standards for different pharmacopoeia Waste Water: Other Applications for the Pharmaceutical / Biochemical Sector: NIRS Applications for the Pharmaceutical Industry: Active Ingredients (API) / Content Uniformity: API - Antacids: API - Cough Syrup: API - Foot Powder: API - Transdermal Patches: Drying: Food and Beverage Industry Standards related to the food and beverage industry Process Application Notes for the Food and Beverage Industry Beverages: Potato Products: Waste Water: Other Applications for the Food and Beverage Industry: Industrial Waste Water Standards for water analysis Process Application Notes for the Waste Water Industry Sold and Installed Applications Environmental Sector Standards for environmental analysis Potable (Drinking) Water: River and Surface Waters: Air Pollution: Overview of Process Analyzers Wet chemical systems: Single method Process Analyzers Wet chemical systems: Customizable, multi-stream Process Analyzers Reagent-free systems: NIRS Process Analyzers