ne) means or another. If the product is to be subjected to flash pasteurisation, it will be chilled and carbonated after that. In the alternative postmix system, concentrated syrup containing all the required ingredients except the majority of water and carbon dioxide is prepared. Such syrup will typically be between 15% and 20% of the final volume and will frequently be subjected to flash pasteurisation before dilution. Water for addition is separately chilled and carbonated then, using a proportioning system, the two components are blended in the required and closely controlled amounts. The carbonated product is then fed to the required filler. The process of carbonation involves either injecting the gas into a stream of water or product or adding it to the static liquid in a pressurised vessel. Counter-pressure filling systems are frequently used. An alternative system is based on liquid level in ‘roe Pen ded G Oo 5Counter-pressure filling systems are frequently used. An alternative system is based on liquid level in the container. Product is usually filled at a cool temperature to minimise the loss of CO) during the process and transit to the capper. Depending on the ingredients and formulation filled, capped products may be subjected to in-pack pasteurisation in a tunnel unit. This would usually be an alternative to flash pasteurisation. Pasteurisation is now widely used as it provides greater assurance of safety and protection from microbial spoilage although with simple flavoured carbonated products produced in a plant with good hygiene standards, risks are low if pasteurisation is not carried out. Pasteurisation is essential when ingredients such as fruit juices are incorporated. Flash pasteurisation involves the use of a heat exchanger to rapidly raise a stream of product to a temperature between about 85° and 95 °C for a period of around 15-20 s followed by a rapid cooling. The alternative tunnel process @igaap)s1. G Oo 515-20 s followed by a rapid cooling. The alternative tunnel process involves passing filled and closed product through a chamber where heated and cooling water sprays sequentially act as the transfer medium. Product temperature is raised more slowly to typically around 70 °C, held for around 20 min and then cooled to ambient. Filled products are likely to have moisture on them either as a result of condensation on a cold bottle or from the water sprays in a tunnel unit. It is almost always desirable to remove surface moisture using an air blast as it may interfere with subsequent label application and/or weaken secondary packaging. After pasteurisation, filled and dried bottles are labelled if necessary, collated and packed as required into the stock keeping units (SKUs) such as packs containing 6, 9 12 or 24 bottles. The use of plastic sleeve labels pre-applied to bottles before filling provides an alternative. If cans are to be used, they are supplied pre-printed to the filling plant. Increasingly, the use of asqmgasB]INe Ge) G Oo 5Increasingly, the use of aseptic filling systems provides an attractive, if expensive, means of packaging products without any need for the use of preservatives. In such a system, PET bottles are blown from heated ‘preforms’ (see Packaging) using sterile air. The heated bottles may then be injected with a small amount of hydrogen peroxide which flashes off and provides a very effective sterilisation of the inside of the container. Bottles then continue in a sterile atmosphere provided by air or steam to the integrated filler, where the pasteurised and carbonated product is introduced and the containers capped. CRT Rene Carbonated Beverages Ibrahim M. Abu-Reidah, in Trends in Non- alcoholic Beverages, 2020 G oO 5Abstract Carbonated non-alcoholic soft drinks are an important sector of worldwide beverage markets. They are produced by adding carbon dioxide gas either directly to the beverage or to water used to dilute a concentrated syrup. Carbon dioxide may come from a variety of industrial sources but it should comply with appropriate standards. Carbonation levels vary depending on product type. Typical ingredients are discussed as are types of packaging. During filling and processing, most products are subject to pasteurisation to ensure microbiological safety and stability. Carbonated natural mineral water is also discussed briefly. Keywords Beverages; Carbon dioxide; Filling: Formulation; Natural mineral water: Packaging types; Pasteurisation; Production Introduction G Oo 5Introduction This article deals with carbonated soft drinks and carbonated (or sparkling) bottled water. It does not include carbonated alcoholic drinks although the underlying science and technology is mostly applicable. Carbonated soft drinks are a very important sector of the global drinks market and in 2013 some 196 billion litres were consumed. The first carbonated drinks were produced in the eighteenth century when a young watchmaker and amateur scientist, Jacob Schweppe, perfected an efficient system for producing carbonated mineral water. He founded the Schweppes Company in Geneva but moved the business to London in 1790. Carbonated products are now available worldwide in many different packaging formats including glass and PET (polyethylene terphthalate) bottles and cans. Carbon Dioxide In order to manufacture G Oo 51 Carbon Dioxide In order to manufacture a carbonated beverage, it is necessary to inject carbon dioxide gas (CO,) into the liquid product before packaging. Carbon dioxide gas is heavier than air having a density of 1.98 kg m° at 298 K. It is colourless odourless and non toxic although can cause death by suffocation if present at high levels. The gas is easily liquefied by compression and cooling. A quick decompression of liquid CO, causes rapid expansion with some evaporation. This removes sufficient heat to allow the reminder to become solid carbon dioxide or ‘dry ice.” The gas is very soluble in water; the amount increasing with reducing temperature. When CO; is dissolved in water, it produces carbonic acid which gives products their characteristic acidic and biting taste. An essential requirement for successful carbonation is to exclude air/oxygen as far as possible. Air has only about 2% of the solubility in water of CO, which means that any air contained within the beverage will times its own volume of G Oo 5 FEEDBACK GDThe level of carbonation varies with product types with around 4.0-7.0 g per 1(2-3.5 volumes) of added CO, being typical. For so called mixer drinks mostly intended to be added to alcoholic spirits such as gin, 9-10 g CO> per lis normally added. These high levels of CO, are only achievable by paying scrupulous attention to removing as much air/oxygen as possible from the product during both manufacture and packaging. Except in the case of naturally carbonated mineral water (see Natural Mineral Water) CO, is obtained from commercial suppliers. The gas is manufactured or obtained as a by-product from a number of different industrial processes (see Table 1). Table 1. Various carbon dioxide production systems Feedstock By-product Throughput from tonne/h CO» from Brewing fara) O 5Beverage Formulation and Composition Soft drinks are typically formulated to offer the consumer a taste of fruit, particularly orange or lemon, or spices and herbs as in a cola drink. The underlying taste will be a balanced blend of sweetness and sharpness with flavour and colour being added to meet the required product characteristics. Ingredients such as preservatives and antioxidants may be added to enhance the keeping qualities of the product. Other widely used ingredients are described below. The traditional source of sweetness is carbohydrate, mainly sucrose or high fructose corn syrup (HFCS). Glucose syrup, which usually contains a wide range of carbohydrates of differing molecular weight, is used in energy drinks where a lower sweetness level is required for a given level of carbohydrate addition. A typical beverage would contain around 10-12.5 % w/v of sucrose or HFCS. Alternative intense sweeteners are also widely used. Depending "ey substance. these mav pro Wiliam ~ G Oo 3Ce ee) cack Alternative intense sweeteners are also widely used. Depending on the particular substance, these may provide up to 500 times the sweetness of sucrose per unit weight. Because of worldwide concerns about excessive calorie intake and the associated diseases of obesity and diabetes, intense sweeteners are increasingly used to provide all or part of the sweetness in beverages. The most widely used intense sweeteners include the synthetic substances saccharin, cyclamates, aspartame, acesulfame K, and sucralose. A natural intense sweetener extracted from the leaves of the plant Stevia rebaudiana and marketed as Stevia, is now widely permitted. To provide the acidity or sharpness of beverages, organic acids such as citric or malic acids are used. Citric acid is usually the preferred ingredient in fruit-flavoured drinks as it normally available at lower cost than alternatives. In cola drinks, phosphoric acid is normally employed. The ratio between sweetness and sharpness determines the] QO nhannntamintin nf tha annd G Oo 5characteristic of the product. When carbonated products are formulated, it is usual to reduce slightly the level of added acid compared with the level that would be employed in a non carbonated drink. This is to recognise that when carbon dioxide is dissolved in water carbonic acid is formed in equilibrium with CO, and contributes to the acidity and sharpness of taste. Products must be formulated to have a pH value less than 4.0 to avoid risk of pathogenic microorganisms being present although the addition of CO, practically ensures this pH level will not be exceeded. A wide range of permitted flavours and colourings are available for use in products. Flavourings are usually a solution of aroma substances from either natural or synthetic sources dissolved in a permitted solvent, usually ethanol. Alternative solvents may be employed to comply with cultural or religious needs. When a carbonated drink is formulated, the amount of flavouring used, typically around 0.1% w/v, may need to be adjusted to account for the potential volatilising effect of CO, gas when the product is served. it): 7\Ce eee) cacti Colourings used are increasingly from natural sources. Carotenoids. anthocyanins and caramels are the most widely used. Specific synthetic food azo dyes are also widely permitted and used. Despite their permitted status, some synthetic colourings are claimed to be associated with hyperactivity in children and many major retailers now refuse to sell drinks containing them. Fruit juices, mainly added in the form of concentrates, are also widely used as ingredients in fruit drinks. Typical use will be between 2 and 10% by volume of the product when calculated as reconstituted juice. A potential problem when fruit juices are used in carbonated drinks is that any particulate material can provide a nucleation point for release of CO, when the container is opened and gas pressure is released. This can cause the product to gush out of the container uncontrollably with the potential for damage to both consumer and surrounding property. For this reason particulate ingredients from any source are usually avoided. Traditionally, preservativ (ayy [oy nd dnd ta ant Aninten ta mi G Oo 5Traditionally, preservatives have been added to soft drinks to minimise the risk of microbial spoilage. The most widely used are benzoic and sorbic acids added as their sodium or potassium salts. Dimethyl dicarbonate is also used but must be injected directly into a stream of product. The once widely used sulphur dioxide (SO.) is now only permitted in small amounts in very limited circumstances. Because of concerns about daily intake of SO» in EU countries, it is possible that its future use in soft drinks may be completely eliminated. Carbon dioxide itself has effective preservative properties as it suppresses the growth of yeast that forms the gas as a metabolite. It is very effective against mould spoilage since most moulds require the presence of oxygen to develop. Increasingly, the use of in-pack pasteurisation or aseptic filling (see Product Manufacture) renders the use of preservatives unnecessary. Anti-oxidants such as ascorbic acid (vitamin C) are often added to improve stability of colour and iar G Oo 5Anti-oxidants such as ascorbic acid (vitamin C) are often added to improve stability of colour and flavour. Other ingredients may include vitamins, minerals and herbal extracts. Nutritional and health claims permitted for products are very tightly controlled by legislation. Product Manufacture Manufacture of carbonated beverages involves several distinct stages. The first is to mix all the required ingredients, except as noted below, in an appropriate vessel. Because as indicated in Carbon Dioxide above, air and oxygen ingress must be kept to an absolute minimum, mixing should be very carefully controlled so as to avoid vortexing or other operations which draw air into the mix. After ensuring the mix complies with required quality parameters it is then carbonated. Carbonated beverages are manufactured by one of two basic methods. The premix system involves mixing all the required ingredients for the beverage and then the final volume of product i reeDBack © | G Oo 5In the alternative postmix system, concentrated syrup containing all the required ingredients except the majority of water and carbon dioxide is prepared. Such syrup will typically be between 15% and 20% of the final volume and will frequently be subjected to flash pasteurisation before dilution. Water for addition is separately chilled and carbonated then, using a proportioning system, the two components are blended in the required and closely controlled amounts. The carbonated product is then fed to the required filler. The process of carbonation involves either injecting the gas into a stream of water or product or adding it to the static liquid in a pressurised vessel. Counter-pressure filling systems are frequently used. An alternative system is based on liquid level in the container. Product is usually filled at a cool temperature to minimise the loss of COz during the process and transit to the capper. Depending on the Fagan FEEDBACK © | G Oo 5Depending on the ingredients and formulation filled, capped products may be subjected to in-pack pasteurisation in a tunnel unit. This would usually be an alternative to flash pasteurisation. Pasteurisation is now widely used as it provides greater assurance of safety and protection from microbial spoilage although with simple flavoured carbonated products produced in a plant with good hygiene standards, risks are low if pasteurisation is not carried out. Pasteurisation is essential when ingredients such as fruit juices are incorporated. Flash pasteurisation involves the use of a heat exchanger to rapidly raise a stream of product to a temperature between about 85° and 95 °C for a period of around 15-20 s followed by a rapid cooling. The alternative tunnel process involves passing filled and closed product through a chamber where heated and cooling water sprays sequentially act as the transfer medium. Product temperature is raised more slowly to typically around 70 °C, held for around 20 min and then cooled to FEEDBACK () G Oo 5oe Filled products are likely to have moisture on them either as a result of condensation on a cold bottle or from the water sprays ina tunnel unit. It is almost always desirable to remove surface moisture using an air blast as it may interfere with subsequent label application and/or weaken secondary packaging. After pasteurisation, filled and dried bottles are labelled if necessary, collated and packed as required into the stock keeping units (SKUs) such as packs containing 6, 9 12 or 24 bottles. The use of plastic sleeve labels pre-applied to bottles before filling provides an alternative. If cans are to be used, they are supplied pre— printed to the filling plant. Increasingly, the use of aseptic filling systems provides an attractive, if expensive, means of packaging products without any need for the use of preservatives. In such a system, PET bottles are blown from heated ‘preforms’ (see Packaging) using sterile air. The heated bottles may then be injected with a small amount of hydrogen peroxide which flashes off and provides Toe O 5oe) Bottles then continue in a sterile atmosphere provided by air or steam to the integrated filler, where the pasteurised and carbonated product is introduced and the containers capped. Packaging Traditionally, glass bottles were the preferred form of packaging for carbonated beverages. They are still preferred today in many applications, usually to enhance a brand image or to provide longer shelf life. There are disadvantages of weight and brittleness but provided effective closures are correctly applied, the retention of gas is excellent. Oxygen ingress is also effectively minimised. Unless appropriately tinted, oversleeved or covered with a large label, glass allows ingress of light which may damage the product and affect shelf life. Cans are also widely used for carbonated beverages. Most cans are now made from two pieces of aluminium; the body produced by a process of “drawing and wall ironing” and the can end applied after filling. Cans are now eon G Oo 3oe Cans are also widely used for carbonated beverages. Most cans are now made from two pieces of aluminium; the body produced by a process of “drawing and wall ironing” and the can end applied after filling. Cans are now almost always pre-printed and only the data relating to traceability and product durability is applied at or immediately after filling, usually by an ink-jet labeller. Provided can ends are correctly applied and steps taken to minimise the risk of corrosion, cans provide arguably the best protection of a carbonated product as they do not allow ingress of light or oxygen. In most markets, the majority of carbonated products are packed in PET bottles. Typical sizes range from 250 ml to 2.0 1. PET bottles are manufactured in a two stage process. So called ‘preforms’ are made by an injection moulding operation with the required amount of plastic. The preform also incorporates the neck finish with screw thread. Preforms, which may be stored for future use, are then fed into heated moulds of the required design in the stretch-blowing operalizaap):) eS) G Oo 5For small bottles the weight of plastic used is typically around 15-25 g but many manufacturers try to reduce bottle weight to below 12 g and then rely on the pressure in the carbonated beverage to provide mechanical strength. Shelf-life of carbonated drinks in PET is shorter than for products packaged in glass or cans. This is due to the loss of CO, through container walls. For a typical 21PET bottle weighing 43 g, a loss of some 15-16% of gas may be expected to occur within 8 weeks of bottling. For a 250 ml bottle, this loss may be expected to occur within 6 weeks. CO, loss may be further minimised by incorporating into the PET, at a cost premium, other polymers with better gas retention characteristics. Oxygen ingress can also occur with corresponding deterioration of product. Closures for carbonated products may be either metal or plastic but all now incorporate tamper evidence. Aluminium is normally used for metal closures as it is highly malleable whilst high density polyethylene (HDPE) is normally used for PET bottle closures. G Oo 3Because the nature of glass bottle production can lead to minor variations in moulding, metal caps are usually preferred. Caps without a screw thread are applied to bottle tops and by use of a rotating chuck on the capping machine, are formed to fit the exact profile of the screw thread on each bottle. A gas tight seal is obtained by incorporating a plastic sealant into the cap at manufacture. The sealant also acts to protect the cap against corrosion from ingredients. Since PET bottle moulds give bottles with tighter manufacturing tolerances, plastic caps are usually moulded to the exact thread profile required. In the past a small number of serious injuries have been caused when closures on carbonated drinks have been suddenly and explosively released causing them to become missiles. Most bottle moulds now incorporate vertical slots into the screw threads to which closures are applied. On initial release, this allows venting of excess gas pressure whilst the closure is still attached to the container body and an explosive cap release can ayaa) G Oo 5Natural Mineral Water Natural mineral water is a product description protected by law in European Union countries. It describes a natural water source of confirmed exceptional stability and purity which must be bottled at source. Such water may be sold still (ie., not carbonated) or with CO, added. In the latter case it must be described as “carbonated natural mineral water.” Natural mineral waters originate underground and are exploited from springs, wells or other underground sources. In certain sources, the water may be found with significant quantities of naturally occurring carbon dioxide present. If bottled as such it must be described as “Naturally carbonated natural mineral water.” It may also be possible to capture the natural source of CO, and re-inject into the water prior to bottling. Further Reading Ashurst and Hargitt, 2009 Hiig=sp)s1\e\qnes) G Oo 5Biochemical oxygen demand ma Biochemical oxygen demand (BOD) is the amount of dissolved oxygen (00) needed (Le demanded) by aerobic biological organisms to break down organic material. pres temperature ove: a specific time peiod. The BOD value is most commonly expressed in miligrams of oxygen consumed par Itre of sample during § days of incubation at 20°C and is often used as a tina given water sample at certain surrogate of the degree of organic pollution of water il BOD reduction is used as a gauge of the effectiveness of wastewater sament plants, BOD of wastewater effluents is used to indicate the shorttern impact on the oxygen levels of the receiving water BOD analysis is similar in function to chemical oxygen demand (COD) analysis in that both measure the amount of organic comaounds in wate. However, COD analysis is less specific, since it measures everything that can be chemically oxidized rather than just levels of biologically oxidized organic matter jackground c Most natural waters contain small quantities of crganic compounds. ‘Aquatic microorganisms have evolved to use some of these cempounds as food. Microorganisms living in oxygenated waters use dissolved oxygen to oxidatively degrade the organic compounds, réeasing er which is used for growth and reproduction . Populations of these ‘microorganisms tend to increase in proportion to the amount of food available. This microbial metabolism creates an oxygen demand Proportional to the amount of organic compounds useful as food, Under some circumstances, mictobial metabolism can con: cxygen faster than atmospheric oxygen can dissolve into the water or the autotrophic community (algae, cyanobacteria and maccophy’all PD Background ? Most natural small quantities of organic compounds, Aquatic microorganisms have evolved to use some of these compounds as food, Microorganisms living in oxygenated waters use dissolved oxygen to oxidatively degrade the organic compounds, réeasing enesuy which is used for growth and reproduction Populations of these ‘microorganisms tend to increase in proportion to the amount of food available. This microbial metabolism creates an oxygen demand Proportional to the amount of organic compounds useful as food, Under some circumstances, mictabial_metabolis ved ‘can consume diss cxygen faster than atmosoheric oxygen can dissolve into the water or the autotrophic community (algae, cyanobacteria and maccophytes) can produce. Fish and aquatic insects may die when oxygen is depleted by microbial. metabolism, Biochemical oxygen demand is the amount of oxygen required for rricrobial metabolism of organic compounds in wate, This demand occurs over Some variable period of time depending on temperature, nutent concentrations, and the enzymes available to indigenous ‘microbial populations, The amount of oxygen required 10 completely oxidize the organic compounds to carbon dioxide and water through generations of microbial growth, death, decay, and cannibalism is total biochemical oxygen demand (total B00). Total BOD is of more sigifieance to food webs than to water quality. Dissolved oxygen epletion is most likey to become evident during the initial aquatic ‘microbial population explosion in response to a large amount of erganic ‘materia, If the microbial population deoxygenates the water, however, that lack of oxygen imposes a limit on population growth of aerobic aquatic microbial organisms resulting in a longer tem food surplus and oxygen defi. | standard temperature at which BOD testing should be cared out was first proposed by the Royal Commission on Sewage Disposal in its eighth report in 1912: (©) An effluent in order to comply with the general standard must not contain as discharged more than 3 parts per 100,000 of suspended matter, and with its suspended matters included must not take up at 65°F more than 2.0 parts per 100,000 of dissolved oxygen in 5 days. This general standard should be prescribed either by Statute or by order of the Central Authority, and should he subject to modifications by that Authority after an interval of not less than ten years.all PD This was later standardised at 68°F and then 20°C, This temperature may be signficamty different from the temperature of the natural ewironment of the water being tested. Although the Royal Commission on Sewage Disposal proposed 5 days as fan adequate test period for rivers of the United. Kingdom of Grest Britain and Keland, longer periods were investigated for North American fivers, Incubation periods of 1, 2,§, 10 and 20 days were being used into the mdzotn cemury."! Keeping alssolved cxygen available at the chosen temperature, investigators found up to 99 percent of total 800 was exerted within 20 days, 90 percent within 10 days, and approximately 68 percent within 5 days. variable microbial popul shifts to nitifying bacteria limit test reproducibility for periods greater than 5 days. The Sdlay test protocol with acoeptaaly reproducible results ‘emphasizing carbonaceous BOD has been endorsed by the United States Emironmental Protection Agency (EPA). This Seay BOD test resuit may be described as the amount of oxygen required for aquati ‘microorganisms to stablize decomposable organic matter under aerobic conditions." stabilization, in this context, may be perceived in general terms 2s the conversion of food to living aquatic fauna, Athough these fauna vill continue to exert biochemical oxygen demand as they die, that tends to occur within a more stable evolved ecosystem including fs} higher to measurements at a w A comprehensive History and review of Biochenical Oxygen Denand over the last 180 years has been published with 2100 references (Baird and Smith, 2002 Third Century of Biochenical Oxygen Denand, Water Environment Federation, Alexandria Virginia, TSBN1-57278-1994)all PD The Royal Commission on River Pollution, established in 1865, and the cal in 1898 led to the selection in 1908 of BOD. 2s the definitive test for organic pila formation of the Royal Commission of rivers, Five days was chosen as an appropriate test period because this Is supposedly the longest time that river water takes to travel from source to estuary inthe UK.. Inits sixth report the Royal Commission recommended that the standard set should be 15 parts by weight per milion of wates. 7! However, in te Ninth report the commission had revised the recommended standard An effluent taking up 2-0 parts dissolved oxygen per 100,000 would be found by a simple calculation to require dilution with at least & volumes of river water taking up not to take up more than 0.4 part, Our experience indicated that in a large majority of cases the volume 2 part if the resulting mixture was of river water would exceed 8 times the volume of effluent, and that the figure of 2-0 parts dissolved oxygen per 100,000, which had been shown to be practicable, would be a safe figure to adopt for the purposes of a general standard, taken in conjunction with the condition that the effluent should not contain more than 3-0 parts per 100,000 of suspended solids. This was the comerstone 20:30 (BOD:Suspended Solids) + full ification standard which was used as a yardstick in the UK. up to the 1970s for sewage works efflent quali The United States includes BOD eluent limitations in its s went regulations. Secondary sewage teatment is generally expected to remove 85 percent of the BOD mensured in sewage and produce effluent BOD concentrations with a 30-day average of less than 30/mg/L and a 7-day average of less than 45 mg/L. The reguiations also describe "weatment equivalent to secondary treatment” as removing 65 percent of the BOD and producing effluent BOD concentrations with @ $0day average less than 45 mg/L and a 7-day average less than 65 mg/L. Typical values Most pristine rivers will have a Sday carbonaceous 80D below 1 mail Moderately polluted rivers may have @ BOD value in the range of 2 to Bmg/L. Rivers may be considered severely polluted when BOD values exceed &ma/L Municipal sewage that is efficiently teated_by aall PD Typical values Most pristine rivers wil have a Sday carbonacsous 80D below 1 mg/l. Moderately polluted rivers may have @ BOD value in the range of 2 to Bmg/L. Rivers may be considered severely palluted when BOD values exceed mg/L.) taunicipal sewage that is efficiently treated by a vee-stage process would have a value of about 20™mg/L or less. Untreated sewage varies, but averages eround 600mg/L. in Europe and as low as 200 mg/L in the US, oF where there is severe groundwater tee infilation/inflow . The generally lower values in the US. derive from the much greater water use per capita than in other parts of the word, Use in sewage treatment The B00 is used in measuring waste loadings to treatment plants and in evaluating the BODremoval efficiency of such treatment systems, Methods nkler published the methodology of a simple, accurate and direct dissolved oxygen analytical procedure in 1888," since that time, the analysis of dissolved oxygen levels for water has been key to the determination of surface water. The Winkler method i still one of only two analytical techniques used to calibrate oxygen electrode meters; the other procedure is based on oxygen solubility at satura on as per There are two recognized methods for the measurement of dissolved oxygen for BOD and a number of other methods not curenty Intemationally recognised as standard methods Dilution methodall PD This standard method is recognized by EPA which is labeled Method 52108 in the Standard Methods fo Examination of Water and wastewater |"! in order to obtain BOD ., dissolved oxygen (00) concentrations in a sample must be measured before and after the Incubation period, and appropriately adusted by the sample corresponding dilution factor, This analysis is performed using 300 ml Incubation bottles in which buffered dilution water is dosed with seed microorganisms and stored for § days in the dark room at 20°C to prevent DO production via photosynthesis. The bottles have traditionally been made of glass, which required cleaning and rinsing between samples. A SM 52108 approved. aisposable, plastic BOD boitle is available which eliminates this step. In addition to the various ditions of BOD samples, this procedure requires dilution water blanks, glucose lutamic acid (@GA) contiols, and seed controls, The ditto blank is used to confirm the quality of the dition water that is used to dilute the other samples. This is necessary because impurities in the s in the results. The GGA dilution water may cause significant alteratio contol is a standardized solution to determine the quality of the seed, where its recommended 80D 5 concentration is 198 mg/l + 30.5 mg/L For measurerient_ of carbonaceous BOD (c80D), a ntiteation inhibitor Is added after the lution water has been added to the inhibitor hinders the oxidation of ammonia nitrogen, which nitrogenous. BOD (n80D). When performing the BOD, test, itis tice to measure only cBOD because nitrogenous demand does not reflect the oxygen demand from organic matter. This Is because nBOD is generated by the breakdown of proteins, whereas ©800 Is produced by the breakdown of organic molecules 00 seated by + unseeded: BOD, — (2a = Ps) o P Do — Ds) — (Bo — Bs) + sc BoD, = (22 Bs) (Bo — Bt Dp is the dissolved oxygen (00) of the diluted solution after aration (9) Ds is the 00 of the diluted solution aftr $day incubation (mg) Piis the decimal dilution factor Bp is te DO of dited seed sample after preparation (m/l Bs; isthe 00 of dilute seed sample after 5 day incubation (mg/) fi the ratio of ceed volume in di B00 test on seed ion soltion to seed volume in Manometric method ?eall PD anomeric method o This method is limited to the measurement of the caxygen consumgtion due only to carbonaceous oxidation. Ansnonia oxidation is inhibited The sample is kopt in a sealed container fitted with a pressure sensor A substance that absorbs carton dioxide (typically lithium hyeroxide) is added in the container above the sample level, The sample is stored in conditions identical to the dilution method. Oxygen is consumed and, as ammonia oxidation is inhibited, carbon dioxide is released. The total amount of gas, and thus the pressure, decreases because carbon dioxide is absorbed. From the drop of pressure, the sensor electronics computes and displays the consumed quantity of oxygen. The main advantages of this method compared to the dilution method «simplicity: no dilution of sample required, no seeding no biank sample direct reading of BOD value * continuous display of BOD value at the current incubation time Alternative methods Biosensor Jn alterative to measute BOD is the development of biosensors, which are devices for the detection of an analyte that combines a biological component with a physicochemical detector component. Enzymes are the most widely used biological sensing elements in the fabrication of biosensors, Their ag eatin in biosensor construction is limited by the tedious, timeconsuming and costly enzyme purification methods Microorganisms provide an ideal altemative to these bottlenecks, 12) Many micro organisms useful for BOD assessment. are relatively easy to ‘maintain in pure cultures, grow and harvest at low cast. Moreover, the tse of micrabes in the field of biosensors has opened up new possibilities and advantages such as ease of handling. preparation and low cost of device A number of pure cultures, 9. Tih sporon lus cereus, Klebsiella oxytoca Pseudomonas sp. etc individually, have beon used by many workers for the construction of BOD biosensor, On the other hand, many workers have imroblized activated sludge, or 2 mixture of two or three bacterial species and cutaneum, Ba various membranes for the construction of BOD biosensor, The mast commonly used membranes were polyvinyl alcohol, porous hycropilic membranes etcall PD ‘A defined microbial consortium can be formed by conducting a systematic study, Le pretesting of selected microorganisms for use as 1 seeding material in BOD analysis of a wide variety of industial eluents, Such a formulated consortium can be immobilized on suitable membrane, ie. charged nylon membrane Charged nylon membrane is suitable for microbial immobilization, due to the specific binding between negatively charged bacterial cll and positively charged nylon membrane. So the advantages of the nylon membrane over the other membranes are: The dual binding, ie. Adsorption as well as entrapment, thus resulting in a more stable immobilized membrane Such specific Microbial consortium based BOD analytical devices, may find great application in monitoring of the degree of polutant strength, in aide variety of industrial waste water within a very short time, (9) Biosensors can be used to indirectly measure BOD via a fast (usually <30 min) to be determined BOD substitute and a coresponding calibyation curve method (pioneered. by Karube et al, 1977) Consequently, biosensors are now commercially available, but they do lirted run lengths due to the need for reactivation, and the inabily to respond to changing quality characteristics as would normally occur in wastewater treatment streams; eg. diffusion processes of the biodegradable organic matter into the membrane and different responses by different microbial species which lead to problems with have several limitations such as thet high maintenance cost the reproducibility of result (Pract et al, 1995). Another important limitation is the uncertainty associated with the calibration function for Transiating the BOD substtute into the real BOD (Rustum et al, 2008) Fluorescent [A surrogate to BOD has been developed using a resazurin derivative which reveals the extent of oxygen uptake by microorganisms for cxganic matter mineralization. ["4l p crossvalidation performed on 109 samples in Europe and the United States showed a stict statistical equivalence between results fram both methods, "5! ‘an electrode was been developed based on the luminescence emission of a photoactve chemical compound and the quenching of that cmission by oxygen. This quenching photophysics mechanism is described by the Stem-Volmer equation for dissolved oxygen in a solution: h/I = 1+ Ksy (0, + T: Luminescence in the presence of oxygenA buffer solution (more precisely, pH buffer or hydrogen ion buffer) is an aqueous solution consisting of a mixture of a weak acid and its conjugate base, or vice versa. Its pH changes very little when a small amount of strong acid or base is added to it. Buffer solutions are used as a means of keeping pH at a nearly constant value in a wide variety of chemical applications. in nature, there are many systems that use buffering for pH regulation. For example, the bicarbonate buffering system is used to regulate the pH of blood, and bicarbonate also acts as a buffer in the ocean. Principles of buffering s < 100 £ 10 gy 80 2 B60 8 5 g 40 6 3 E 20 2 ba & 0 Oo 04 08 titre volume / ml Simulated titration of an acidified solution of a weak acid (pK, = 4.7) with alkali Buffer solutions resist pH change because of an equilibriumyd Buffer solutions resist pH change because of an equilibrium between the weak acid HA and its conjugate base A Poe HA =H™+A When some strong acid is added to an equilibrium mixture of the weak acid and its conjugate base, hydrogen ions (H *) are added, and the equilibrium is shifted to the left, in accordance with Le Chatelier’s principle. Because of this, the hydrogen ion concentration increases by less than the amount expected for the quantity of strong acid added Similarly, if strong alkali is added to the mixture, the hydrogen ion concentration decreases by less than the amount expected for the quantity of alkali added. The effect is illustrated by the simulated titration of a weak acid with pK, = 4.7. The relative concentration of undissociated acid is shown in blue, and of its conjugate base in red. The pH changes relatively slowly in the buffer region, pH= pK, #1, centered at pH = 4.7, where [HA] = [A]. The hydrogen ion concentration decreases by less than the amount expected because most of the added hydroxide ion is consumed in the reaction OH +HA‘h H,0 +A” and only a little is consumed in the neutralization reaction (which is the reaction that results in an increase in pH) OH +H*'h HAO. Once the acid is more than 95% deprotonated, the pH rises rapidly because most of the added alkali is consumed in the neutralization reaction.What is the procedure for cleaning RO membranes? What CIP chemicals should be used? mi 1 ling should be performed with high and low pH CIP chemicals. The high pH cleaning should always be performed first to penetrate and disperse biological or organic foulants. Specialty high pH cleaning chemicals more effectively penetrate heavy organic and biological foulants, making them more effective then commonly used CIP chemicals such as sodium hydroxide. While many choose the lowest cost CIP chemicals, their annual cost will end up being significantly higher because of the higher frequency of cleaning; this incurs more labor costs, chemical costs, and downtime. It’s always best to perform a cleaning study to ensure that the membrane performance is fully restored after CIP.oes The use of citric acid is recommended prior to high pH cleaning by some companies, due to its chelating properties. We strongly recommend against this practice - Organic foulants lose their anionic charge if a low pH cleaning is performed first, and since some permeate is almost always produced during CIP, the foulants will be compacted into the membrane and become more difficult to penetrate. What is the Best Method for Cleaning RO Membranes? Membrane CIP results will be best if each stage is cleaned individually. This will allow for the maximum flow velocity during cleaning. If both stages of a system with a 2:1 array are cleaned simultaneously, each pressure vessel in the second stage will receive twice the flow velocity as the first stage. This would cause membrane telescoping in the second stage if the first stage elements are cleaned at optimal flow velocity. Alternately, by basing the flow velocity on the second stage, the first stage membranes would not receive sufficient surface scouringoes) Performing RO Membrane Cleaning The total volume in the system should always be considered when determining how much CIP chemicals to add. You can use the AWC RO CIP Calculator to help you calculate the correct amount of chemical When performing a cleaning of a RO system, the first 20% of the cleaning solution is flushed through the membranes directly to drain, instead of circulating. This will prevent contamination of the cleaning solution with loose foulants and large suspended solids The remaining solution is then circulated through the system while carefully monitoring the pressure differential (dP). dP should not exceed 10 PSI (0.69 bar) per membrane element. Every 30 - 60 minutes, the circulation can be stopped to allow the membranes to “soak” for about 30 - 60 minutes. Circulation should then be started again to flush off the disintegrated foulant and to bring fresh cleaning chemical to the membrane surface. pH should be checked every 15- 30 minutes during circulation. If the pH of the cleaning solution has changed,foes) Soaking and circulating can be repeated alternately until cleaning is complete. Low pH cleaning is determined to be complete when the pH stabilizes, but the length of a high pH cleaning should be based on a predetermined time. The length of time required or optimal CIP results can either be obtained by trial and error, or by performing a cleaning study. A high pH cleaning is usually performed at a pH of 11 - 12 using a cleaning chemical such as AWC C-236 for silica, AWC C-237 for biofouling or AWC C-227 for heavy organics fouling. More chemical is added during the cleaning every time the pH drops below 11 If the solution becomes very dark or turbid, it should be drained and a new cleaning solution should be prepared. A low pH cleaning should be performed at a pH of 2 - 3 using CIP chemicals such as AWC C-234 or AWC C-235 (phosphorous free). If the pH of the cleaning solution increases above 3 at any time during the cleaning, more cleaning chemical must be added to reduce the pH to its target range of 2-3Chal ts Can Sulfuric acid or HCI be used with the addition of Citric acid for the control of iron and other scales in a reverse osmosis plant? Using citric acid is very expensive. If the water source contains oxygen, has been exposed to oxidizers, or ferric based coagulants have been used, the iron will be in the ferric state and can typically be controlled by dosing sulfuric acid to reduce the pH to ~6 and dosing antiscalant. If the water does not contain any dissolved oxygen, most of the iron will be in the Ferrous state. Ferrous ions are extremely soluble and easily controlled by most antiscalants without acid However, in many cases, some soluble oxygen will be present. It only takes 0.1 ppm dissolved oxygen to oxidize 0.7 ppm of ferrous ions to the ferric state.When the water source is from a deep aquifer, we assume anaerobic conditions where all iron will be in the ferrous state (as long as the water goes directly to the RO with no holding tanks and no dosing of chlorine or other oxidizers). When the water source is from a surficial aquifer, oxygen will be present and iron can be assumed to be in the ferric state. Ferric iron can be controlled to a certain extent using antiscalant without pH reduction, but the antiscalant demand becomes significant; antiscalants have a higher affinity to trivalent metal hydroxides than other surfaces. They will therefore preferentially adsorb to colloidal ferric hydroxide while allowing calcium carbonate and other sparingly soluble salts to precipitate and form scale on the membrane surface Some smaller plants use greensand filters for iron control and they are very effective; iron concentrations are typically reduced to below 0.1 ppm. But they are a significant capital expense, require a large footprint, and they do require maintenance to operate efficiently.7:05 @® Chal its What is the relationship between pH and alkalinity? How are they different? How does temperature affect ataT-aaeg What is the relationship between pH and alkalinity? In simple terms, pH is the concentration of acid protons [H+]. On the other hand, the alkalinity of a solution is its ability to neutralize acids. Alkalinity consists of ions that incorporate acid protons into their molecules so that they are not available as a free acid that can lower the pH. This is known as buffering For example acid reacts with CO to make HCO4~, and converts PO 42 to HPO 4~ This makes it so that a significantly higher quantity of acid is required to lower the pH compared to a solution that does not contain these ions. Deionized water can drop from pH 7 to pH 2 with just one drop of acid, while natural well water may require 200 —What is Alkalinity? Alkalinity consists primarily of carbonate, bicarbonate, phosphate, borate, orthosilicate, sulfides, and organic acids. Most people refer to alkalinity as the concentrations of carbonate (CO) and bicarbonate (HCO ~) ions, which are the buffers that are typically present in the highest concentrations in natural waters. Bicarbonate in particular, is the strongest buffer (largest Ka value) and the effect of other buffers becomes insignificant in its presence. At very high pH, like pH 12, the hydroxide ion [OH~] concentration is so high that it takes a significant amount of acid to neutralize enough of them before the pH drops. For that reason, hydroxides (OH) are considered as contributors to alkalinity above ~pH 10.5 At very low pH, hydronium ion [H*] concentrations are very high, and as a result, a much higher concentration of acid is required to further lower the pH. Higher temperature shifts the equation to the right, slightly increasing the carbonate to bicarbonate ratio. At the same time, the acid (H*) concentration increases slightly which causes a slight drop in pH. This means that a warmer solution can have better buffering+ HCO; = CO3* +H The opposite happens at lower temperature. In reverse osmosis (RO) and nanofiltration (NF) membrane systems, bicarbonate is the primary driver behind the increased pH in the concentrate relative to the feed. Bicarbonates increase in concentration as they are rejected by the membrane, while CO, concentrations remain constant since gases are not rejected. The increased ratio between bicarbonate and carbonic acid results in a shift to the left, absorbing more free acids and thereby increasing the pH. HCO; « HCO; +H* *4HCO3 and CO, are used interchangeably because HCO, converts instantly to CO», AWC provides the membrane community with chemical solutions. Be sure to contact us today at (813)246-5448 so we can help you optimize your RO membrane system operation. ea)Can | use citric acid to descale/clean a reverse osmosis (RO) Membrane? Citric acid is an organic acid that is often used for removal of calcium carbonate scale and iron hydroxide. Citric acid is not very effective at removing phosphate salts such as calcium and iron phosphates. It cannot be used to dissolve sulfate scales or silica, arthé taai€stive for biofilm removal. controlled by d the pH to ~6 4ften recommended for val, it is not very effective due If the water doion of the carboxylic acid oxygen, most ¢PS in natural organic matter (evry wicure OW PH environment created by citric acid. For this reason, attempting to clean at low pH when organics are present can compact the NOM into the membrane, resulting in a foulant that is more difficult to clean, or even irreversibleOne) Citric acid is an organic acid that is often used for removal of calcium carbonate scale and iron hydroxide. Citric acid is not very effective at removing phosphate salts such as calcium and iron phosphates. It cannot be used to dissolve sulfate scales or silica, arthis igaffestive for biofilm removal controlled by d the pH to ~6 4ften recommended for val, it is not very effective due If the water doion of the carboxylic acid oxygen, most ¢PS in natural organic matter Geom urure OW PH environment created by citric acid. For this reason, attempting to clean at low pH when organics are present can compact the NOM into the membrane, resulting in a foulant that is more difficult to clean, or even irreversible Certain anti-caking agents present in citric acid can act as membrane foulants, and it is therefore always safer to use specialty RO sanitizing agents. Furthermore, in the United States, citric acid prices have been inflated due to anti-dumping duties imposed on imports. For this reason, it makes little sense to use citric acid in place of specialty cleaning chemicals which are more effective over a broader spectrum and are of a similar cost7:08 Challe If silica is not removed by ion exchange, does that mean it is colloidal silica? It is not possible to have colloidal silica in your feedwater unless your silica concentration is above the solubility limit under those conditions, resulting in polymerization and hence colloidal silica formation. The difference between results from ICP-AA vs molybdate reactive silica is often mistakenly attributed to the presence of colloidal silica - but 99% of the time, the difference is due to calibration issues. Silica leaks through demineralizers because it only partially deprotonates at neutral pH and is not fully charged unless the pH is very high. That has no relevance to its existence in colloidal or silicic acid form. Surface groups on colloidal silica will also deprotonate and become anionic at high pH, and can be removed no differently than silicic acid by ion exchange.¢ H4SiO4 6 H3Si0, +H* + H3Si04 « H2Si04” +H At neutral pH, the calculations show that no measurable amount of silica is charged. Even at pH 10, about 40% of the silica remains unionized, and therefore cannot be removed by ion exchange resin As an example, here are some calculations from a water analysis where reactive silica was 33 ppm as SiO, (52.793 ppm as H»Si04) pH 7.3, Temp 25 deg C, lonic Strength 0.0554, reactive silica 52.793 as silicic acid mols/L mg/L [H)Si0,2] 8.80E-11 0.000 [H3Si0,-] 1.53E-06 0.146 [H,SiO,] 5.48E-04 52.646 pH 10, Temp 25 deg ©, lonic Strength 0.0918 (increased due to caustic addition), reactive silica 52.793 as silicic acid oe13 One) hours. My research also tells me that while | may have cleaned off all the rust, | have also potentially opened up my items to suffering a complete secondary rust action. This is because there is probably not going to be an oxide covering the metal surface (an oxide layer can prevent rust from occurring) | suspect some of the higher quality components were a bit more impervious to the acid. So without doing any real research, | cleaned the bits with a towel and then sprayed them with CRC! That's definitely a short-term solution. It sounds like what | should have done is used a different acid instead of HCL, such as phosphoric acid (found in Coca Cola!) Phosphoric acid is readily available from your hardware store (or try Amazon) and is apparently a proven rust remover. Well, kinda it seems. It will turn the rust (iron oxide) into iron phosphate which can be a black substance that forms on the items you are removing the rust from. This then needs to be scrubbed off, often with a wire brush.CAN | USE HYDROCHLORIC ACID TO REMOVE RUST FROM METAL? Rust never sleeps but hydrochloric acid sure can put it to bed! Sometimes it happens because your tools get wet or + Re) .oe Sometimes it happens because your tools get wet or rust slowly creeps along like the Star Wars crawl and then bam! Rust attack! It's suddenly covered all your drill bits, Allen keys, and screwdrivers. | was tidying the shed one morning and | found two things. A massive jar of rusting drill bits and screwdriver heads and also some hydrochloric acid (also known as muriatic acid) which | had stored for 8 years since | moved into our house and never used It seemed like the time had arrived.foe | placed all the bits and items in a plastic container, put on my safety glasses and added some of the hydrochloric acid to it. | then added the same amount of water. Immediately small bubbles began to rise from the bits, the reaction was obvious. | then placed the stuff high on a shelf in the shed so the kids couldn't get at it. | went and had a look about 6 hours later and could some pretty shiny items in the container! Well, | then promptly forgot all about my experimentar e fea) Well, | then promptly forgot all about my experiment until | got home from work the next day - so everything had 24 hours to soak in the solution! | carefully drained the solution and placed the nuts and pieces on some an old cloth As | did this, | was wearing long sleeves and protective eyewear. A more seasoned pro may have worn plastic gloves (but not your good chainsawing gloves!) | then sprayed a thick coat of CRC on the items to form a protective barrier for the short term and to dilute the acid. | don't know if this was the best move, just something that | did as I'd read acids can strip away protective layers on tools. So how did they come out? Black!Many of the drill bits came out coated black, some worse than others. They were originally coated silver! The acid also ate through this bit extender tool so the lesson is maybe don't buy cheap parts and don't leave the metal in the acid too long! The rusty screws came out silver, so all good there - so what is this black residue? I've done some research and there appears to be two chemical reactions at play here. The first is the HCL reacting with the rust, and the second is the HCL with the iron of the bits itself:cea) Fe (s) + 2 HCI (aq) —> FeCl2 (aq) + H2 (g) So the bubbles we see are hydrogen and the black seems to be iron chloride. So what | should have done is not used such a strong dilution (50:50) and not left it to react for 24 hours. My research also tells me that while | may have cleaned off all the rust, | have also potentially opened up my items to suffering a complete secondary rust action. This is because there is probably not going to be an oxide covering the metal surface (an oxide layer can prevent rust from occurring) | suspect some of the higher quality components were a bit more impervious to the acid. So without doing any real research, | cleaned the bits with a towel and then sprayed them with CRC! That's definitely a short-term solution It sounds like what | should have done is used a different acid instead of HCL, such as phosphoric acid (found in Coca Cola!) Phosphoric acid is readily available from your hardware store (or try Amazon) and is apparently16 Ones) Well, kinda it seems. It will turn the rust (iron oxide) into iron phosphate which can be a black substance that forms on the removing the rust from. This then needs to be scrubbed off, often with a wire brush. items you a If you are looking for a more commercial rust remover for your tools then there are many products that you can try which is Rust911 is a concentrated rust remover. When mixed with water (necessary) 16 oz makes 2-gallons which you can immerse your rusty item in.Foods, Materials, Technologies and Risks R Ryther, in Encyclopedia of Food Safety, 2014 Single versus Multiuse CIP Designs CIP circuits can be designed to be (1) single use with cleaning solution dumped directly to drain after completion of the CIP cycle or (2) reuse or multiuse systems. Multiuse CIP systems are often designed to recover final rinse water for use to make up subsequent cleaning solutions. Some or all of the cleaning solution itself can also be saved and reused to minimize chemical usage. In all CIP designs, any final rinse or sanitizing rinse would not be reused in that function but fresh final steps would generally be required by food processing regulations in most regions. Single use systems, where all cleaning, sanitizing, and rinse solutions are used once, are simple to design and result in the highest level of sanitation These single use systems would be required for food production equipment having very high soil loads or allergenic material. These single use systems avoid the potential for cross-contact of these soils types on equipment that would be possible with CIP solution reuse. Facilities with very limited space for additional equipment would also benefit from a single use CIP.Me Recovery of rinse water is a popular choice for CIP as there is little chance of soil redeposition. Multiuse systems in which the cleaning chemicals are reused require a fairly complicated CIP design and a high level of understanding of the CIP circuit to avoid soil redeposition. There are many of these systems in use and some where automated make up water and cleaning chemical additions are balanced to achieve equilibrium and can run for weeks or months without the need to dump the cleaning solution. PROCESS HYGIENE | Modern Systems of Plant Cleaning Y. Chisti, in Encyclopedia of Food Microbiology (Second Edition), 2014 CIP Chemicals CIP relies substantially on the action of chemicals on soil; hence, proper selection of cleaning agents is essential. Carbohydrate and protein-based soil is removed by alkalis. Fats and oils are insoluble in water and may protect other underlying soil. Fats1 water and may protect other underlying so S are melted by heat and effectively solubilized by alkalis. Polyphosphates emulsify fats and oils, thus, increasing the rate of alkaline digestion. Mineral deposits are produced when hardwater with or without alkali is heated. Similarly, calcium- containing deposits form when heating milk and spinach (calcium oxalate). Such deposits resist alkalis but are dissolved by acids. Alkaline cleaners are especially useful as they digest most organics. Sodium hydroxide is a commonly used alkaline cleaner. Typically, a 0.15- 0.5% (wt/wt) sodium hydroxide solution at 75- 80°C (15-30 min) is used, but heat exchange surfaces with burnt-on protein deposits require treatment with 1-5% sodium hydroxide. Because sodium hydroxide is corrosive and difficult to rinse, silicates and wetting agents are added to inhibit corrosion and improve rinsing. Alkali may be supplemented with sodium hypochlorite (30- 100 ppm) to significantly enhance protein and fat removal capability. The damage to stainless steel normally associated with chlorine is insignificant in alkaline environment at the noted hypochlorite concentrations; however, at alkaline pH, chlorine does not act as a biocide. The amount of various additives, for example, sodium metasilicate corrosion inhibitor, sodium tripolyphosphate sequestering or softening agent, wetting agents, and others, needed for a given volume of water is determined by the hardness of the water used in38 w cleaning. High-quality soft water (e.g., reverse osmosis water) is used in many biopharmaceutical cleaning operations, but the potable-quality water used to clean food-processing plants may be much harder. Generally, it is less expensive to use ion exchanger-softened water than to add large amounts of softening chemicals An acid wash generally follows an alkaline wash in food-processing facilities. Acid neutralizes any alkaline residue and removes mineral deposits, such as hardwater stone, milk stone, beer stone, and calcium oxalate. Acid cleaners contain about 0.5% (wt/wt) acid. Formulations may have phosphoric acid; however, because mineral acids are extremely corrosive to steel, the use of organic acid (e.g,, lactic, gluconic, and glycolic) cleaners is preferred. Routine acid washes of biopharmaceutical process equipment are not necessary if deionized water is used in production and cleaning, and the peculiarities of production (e.g., media high in Ca2* and Mg?*) do not contribute to the build up of acid-soluble deposits. An occasional acid wash - every 6 months — with S min recirculation of 0.5% (w/v) nitric acid at 60 °C is sufficient. Nitric acid should not be used for routine cleaning. Any wetting agents (surfactants) used in alkaline and acid CIP washes should be a nonfoaming type, or an antifoam agent may have to be included in the formulation. Typically, a cleaning formulation38 w has ~0.15% wetting agent. Depending on compatibilities, anionic, cationic, or nonionic wetting agents may be used. Nonionic agents (e.g., ethylene oxide-fatty acid condensates) are especially useful because they are poor foamers A sanitizing wash commonly follows acid treatment in food-processing facilities. A solution of QAS usually at <200 ppm is sometimes used. QATs are cationic wetting agents that have good bactericidal properties especially against Gram-positive microorganisms. QATs are less effective against Gram-negative microbes, such as Escherechia coli and Salmonella sp. QATs are incompatible with many minerals and soils; hence, they are used in the final treatment stages when all of the soil has been removed. QATs tend to foam. Other useful disinfecting agents include biguanides and peracetic acid. Peracetic acid should not be used in water containing excessive chloride, or corrosion could be promoted in stainless steel equipment. A sanitizing wash is essential in food processing, especially when equipment lines employ less sanitary devices, such as butterfly and ball valves, or other machines not intended for extended sterile processing. These guidelines for the selection of CIP chemicals are intended to provide only a general picture. Because the nature of soil varies tremendously, selection of suitable cleaning media requires consideration of relevant chemistry, microbiology,Cleaning agent Alkaline cleaners Acidic cleaners Enzymes Composition Mainly sodium hydroxide or potassium hydroxide with wetting agents (surfactants), emulsifiers, and corrosion inhibitors (e.g. sodium metasilicate). May contain phosphates to reduce water hardness. May contain chlorine to enhance efficacy in soil digestion Mainly phosphoric acid or nitric acid. May contain organic acids, e.g,, sulfamic acid, acetic acid, and citric acid. May contain surfactants and chelating agents. Proteases, lipases, and carbohydrases. Usually heat stable enzymes capable of functioning in an alkaline environment are used. Chu hes) Function Provide the main cleaning action on organic materials; digest proteins, fats, and other organic compounds Neutralize residual alkaline cleaners; remove mineral scale; remove rust Digest proteins, fats, and carbohydrates; used in special applications for which strong alkaline cleaners are unacceptableSanitizers Ozone; chlorine dioxide; Kill residual hydrogen peroxide; microorganisms quaternary ammonium salts. Others Various. Wetting agents (surfactants); water softeners; corrosion inhibitors Ameo Purchase book Water and Membrane Treatment Rajindar Singh, in Membrane Technology and Engineering for Water Purification (Second Edition), 2015 2.5.2 Membrane sanitisation Sanitisation means disinfection for reducing microbial contamination down to an acceptable level, whereas sterilisation implies the inactivation of all microorganisms. Cleaning always precedes sanitisation. When a membrane system (membrane elements, pressure vessels and piping)EL) FE) 2.5.2 Membrane sanitisation Sanitisation means disinfection for reducing microbial contamination down to an acceptable level, whereas sterilisation implies the inactivation of all microorganisms. Cleaning always precedes sanitisation. When a membrane system (membrane elements, pressure vessels and piping) has been infected by bacteria or mould, the system requires chemical sanitisation. Hot water sanitisation is used in pharmaceutical membrane systems. Chemical sanitisation The CIP system is used for chemical sanitising also. Disinfection was discussed in Section 2.2. The most common chemical disinfectants are chlorine, hydrogen peroxide and peracetic acid. + Chlorine is mostly used in the form of hypochlorites as discussed in Section 2.2. + Hydrogen peroxide is not compatible with PA membranes. It is relatively non-corrosive and slow acting, and decomposes into oxygen and water. + Per(oxy) acetic acid is a mixture of hydrogen peroxide and acetic acid. It is effective against bacteria, viruses, mould and spores. It releases oxygen that affects microorganisms. Oxygen release is an added benefit as it sanitises the membrane pores. It is fast acting at low temperatures, is non-corrosive toThe following safety precautions should be followed during chemical sanitisation: + Continuous exposure to per(oxy) acetic acid at high levels may eventually damage the membranes. Hence, it should be used only periodically. The biocide efficacy of peracetic acid is much higher than that of hydrogen peroxide, but as most peracetic acid solutions also contain hydrogen peroxide, care must be exercised not to exceed the 0.2% concentration total for both compounds. + When hydrogen peroxide is to be used, the pH of the solution must be < 4.0, and preferably equal to 3.0. This will ensure optimal biocide result and longer membrane life. If the pH is high, chemical attack on the membrane will be much faster. When a mixture with peracetic acid is used, pH adjustment is usually not required. + If an alkaline cleaning has preceded sanitisation, alkalinity must be carefully rinsed out of the membrane vessels, and the pH checked before hydrogen peroxide or hydrogen peroxide/peracetic acid solution is applied. The rinse must include the permeate side. If the alkalinity is not rinsed out, the membranes may get oxidised. + The sanitising solution temperature must not exceed 25°C. Several hours of sanitising at40 ec7) + The sanitising solution temperature must not exceed 25°C. Several hours of sanitising at higher temperatures results in a dramatic increase in the salt passage. + Iron or other transitional metals must not be present because they will catalyse membrane degradation in the presence of hydrogen peroxide due to oxidative degradation, resulting in an increase in salt passage. Hot water sanitisation (HWS) HWS is commonly used to kill microorganisms. RO membranes reject bacteria and other microbes. However, due to defects in the membrane surface, the rejection is not 100% or absolute so that microorganisms can pass through the membrane into the permeate side of the membrane where they can multiply. Hence, sanitisation of a membrane system is essential for the production of US Pharmacopeia (USP) water and water for injection to meet the very low bacterial limits [57- 59]. HWS of RO membrane (and EDI) systems is a relatively recent development made possible by the development of TFC membranes and membrane equipment capable of handling hot water at 85°C for a short time; membrane elements are manufactured with special adhesives, permeate tubes and connectors to withstand elevated temperatures. These membranes also make it possible to sanitise and protect the RO membranesaT Sea) The HWS equipment includes a CIP skid with a heat exchanger to heat and circulate hot water through the membrane system loop. Sometimes a heat exchanger is added to aid in cooling during the cool-down period. The HWS procedure recommended by membrane manufacturers involves separate steps: 1, Clean the membranes with a low-pH cleaner to remove mineral scale and foulants. 2. Heat the water to 80°C at 3-5°C per minute at low flow rate (< 10 m 9h) and pressure (< 3 bar g) 3. Circulate the water in the CIP-RO skid loop at 80°C for up to 1h. Maintain the cross-flow velocity so that the pressure drop is less than 0.15 bar per membrane element. 4. At the end of the re-circulating period, start cooling the membrane system down to 25°C at 3-5°C per min HWS is a superior process to chemical sanitisation, and does not require prolonged rinsing as in the case of biocide sanitisation. However, two points need to be noted. First, HWS is performed more frequently than chemical sanitisation. Second, high temperature reorients the polymer chains permanently [60]. At high temperatures, the membrane structure becomes tighter with increased rejection and decreased flux due to changes in the membrane morphology as aoa CT pc:3) HWS is a superior process to chemical sanitisation, and does not require prolonged rinsing as in the case of biocide sanitisation. However, two points need to be noted. First, HWS is performed more frequently than chemical sanitisation. Second, high temperature reorients the polymer chains permanently [60]. At high temperatures, the membrane structure becomes tighter with increased rejection and decreased flux due to changes in the membrane morphology as a result of changes in the glass transition temperature [60] because deformed polymers shrink when heated [61,62]. The first shrinkage results in almost a 50% reduction in flux according to the membrane manufacturers, but after the initial shrinkage subsequent HWS cycles are unaffected. To compensate for the anticipated loss, HWS systems are designed with more surface area then ambient temperature membrane elements [57]. Purchase book 21st European Symposium on Computer Aided Process Engineeringi Men) 2.1 Process Description A Biotechnology process has numerous clean-in- place (CIP) steps that require both the equipment to be cleaned and a shared equipment item known as a CIP skid. These processes also require the preparation of buffers or media. For this example there are 3 blends to be prepared, 2 blend tanks and a single CIP skid. Blending operations require 2 hours and cleaning requires 1 hour. Blend 1 requires Tank 1 while the remaining blends require Tank 2. The goal is to produce the blends and free the tanks as soon as possible. Water and membrane treatment Rajindar Singh, in Hybrid Membrane Systems for Water Purification, 2005 2.5.3 Hot water sanitisation Hot water sanitisation (HWS) or pasteurisation is commonly used to kill microorganisms. RO membranes reject bacteria and other microbes. However, due to defects in the membrane surface, the rejection is not 100% or absolute so thataT Sea) 2.5.3 Hot water sanitisation Hot water sanitisation (HWS) or pasteurisation is commonly used to kill microorganisms. RO membranes reject bacteria and other microbes. However, due to defects in the membrane surface, the rejection is not 100% or absolute so that microorganisms can pass through the membrane into the permeate side of the membrane where they can multiply. Hence, sanitisation of a membrane system is essential for the production of US Pharmacopeia (USP) water and water for injection to meet the very low bacterial limits. HWS of RO membrane systems is a relatively recent development made possible by the development of TFC membranes and membrane equipment capable of handling hot water as high as 85°C for brief period of time; membrane elements are manufactured with special adhesives, permeate tubes, and connectors to withstand elevated temperatures. These membranes also make it possible to sanitise and protect the RO membranes from biofouling especially when the use of biocides is not acceptable. Typical membrane manufacturers’ specifications of a hot water sanitisable TFC membranes are given in Table 2.15. 45-47 5. Hot water sanitisable TFC-SW Table operating membrane dataaT a The HWS equipment includes a CIP skid with a heat exchanger to heat water and a pump to circulate hot water through the membrane system loop. Sometimes a heat exchanger is added to aid in cooling during the cool down period. The HWS. procedure recommended by membrane manufacturers involves the following steps: 1, Clean the membranes with a low-pH cleaner to remove mineral scale and foulants. 2. Heat the water to 80° at of 3-5°C per minute at low flow rate (<10 m3/h) and pressure (<3 bar g) 3. Circulate the water in the CIP-RO skid loop at 80°C for up to 1 h. Maintain cross-flow velocity so that the pressure drop is less than 0.15 bar per membrane element 4, At the end of the re-circulating period, start cooling the membrane system down to 25°C. at 3-5°C per min HWS is considered a superior process to chemical sanitisation, and does not require prolonged rinsing as in the case of biocide sanitisation. However, two points need to be noted. First, HWS is performed more frequently than chemical sanitisation. Second, high temperature reorients the polymer chains permanently. 4° At high temperatures, the membrane structure becomes tighter with increased rejection and decreased flux due to changes in the membrane morphology as ara e HWS is considered a superior process to chemical sanitisation, and does not require prolonged rinsing as in the case of biocide sanitisation. However, two points need to be noted. First, HWS is performed more frequently than chemical sanitisation. Second, high temperature reorients the polymer chains permanently.“® At high temperatures, the membrane structure becomes tighter with increased rejection and decreased flux due to changes in the membrane morphology as a result of changes in the glass transition temperature*8 because polymers shrink when heated.49,59 The first shrinkage results in almost a 50% reduction in flux according to the membrane manufacturers, but after the initial shrinkage subsequent HWS cycles are unaffected. To compensate for the anticipated loss, HWS systems are designed with more surface area than ambient temperature membrane elements. “© cea) Mo coe Purchase book Facility Design and Process Utilities John Joseph, in Biopharmaceutical Processing, 20181 Cleaning equipment and associated transfer piping are inherently self-cleaning and their cycles should be validated, especially those systems that are centralised and shared between numerous unit operations or functional areas. The cleanability characteristics of the CIP system itself are therefore just as important as with process equipment. Cleaning regimens will be most critical for shared CIP systems serving multi-product operations. Increasing the number of equipment cleaning cycles may be necessary to provide assurance that all contaminants have been removed. Operations downtime from additional cleaning cycles may justify the use of segregated CIP systems. Biopharmaceutical Systems Stephen Hall, in Branan's Rules of Thumb for Chemical Engineers (Fifth Edition), 2012 Clean-in-Place (CIP) System Design ConsiderationsClean-in-Place (CIP) System Design Considerations An automated CIP system can successfully clean pipelines, tanks, and other process equipment. It is important that the CIP system be designed simultaneously with the process system to ensure they are tightly integrated. Dale Seiberling wrote that these factors influence the design, selection, and application of CIP equipment [12]. Also see Appendix B + Required Delivery Flowrate: The required pumping capacity will be determined by the size of the transfer lines and tanks to be cleaned. If a single CIP recirculating unit is applied to clean lines and tanks, the tank CIP requirement for the largest tanks will generally establish the maximum delivery rate + Delivery Pressure: The CIP supply pump discharge head must exceed the head loss through the longest piping circuit, and supply the sprays in the largest and most distant tank at the required pressure. Pressures at supply pump discharges are normally in the range of 350 to 550 kPa (50 to 80 psig), well within the capability of a sanitary centrifugal pump. + Required Sequence of Treatment: Nearly all CIP cleaning is accomplished with water- based solutions by a program consisting of;