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Sunday, February 20, 2011

Iron & Manganese Removal Methods

Next to hardness, the presence of iron is probably the most common water problem faced by consumers and water treatment professionals. The secondary (aesthetic) maximum contaminant levels (MCL) for iron and manganese are 0.3 milligrams per liter (mg/l) and 0.05 mg/l, respectively. Iron and manganese in excess of the suggested maximum contaminant levels (MCL) usually results in discolored water, laundry, and plumbing fixtures.

Small amounts of iron are often found in water because of the large amount of iron present in the soil and because corrosive water will pick up iron from pipes. Clothing washed in water containing excessive iron may become stained a brownish color. The taste of beverages, such as tea and coffee, may also be affected by iron. Manganese produces a brownish color in laundered clothing, leaves black particles on fixtures and as with iron, affects the taste of beverages, including coffee and tea.

Well water from the faucet or tap is usually clear and colorless. However, when water containing colorless, dissolved iron is allowed to stand in a cooking container or comes in contact with a sink or bathtub, the iron combines with oxygen from the air to form reddish-brown particles (commonly called rust). Manganese forms brownish-black particles. These impurities can give a metallic taste to water or to food.

The rusty or brown stains on plumbing fixtures, fabrics, dishes, and utensils cannot be removed by soaps or detergents. Bleaches and alkaline builders (often sodium phosphate) can make the stains worse. Over time, iron deposits can build up in pressure tanks, water heaters, and pipelines, reducing the quantity and pressure of the water supply.

Unluckily, iron and manganese can often be quite difficult to treat. This is due primarily to the fact that iron can be present in several forms, and each form can potentially require a different method of removal..

Types of Iron

There are three main forms of iron and manganese. Other types are much rarer:

  1. Ferrous - This type of iron is often called "clear water iron" since it is not visible in poured water. It is found in water which contains no oxygen, such as water from deep wells or groundwater. Carbon dioxide reacts with iron in the ground to form water-soluble ferrous bicarbonate, which, in the water, produces ferrous ions (Fe++).
  2. Ferric - Ferric iron is also known as "red water iron". This type of iron is basically ferrous iron which has been exposed to oxygen (oxidized), usually from the air. As carbon dioxide leave the water, oxygen combines with the iron to form ferric ions (Fe+++). These oxidized particles are generally visible in poured water.
  3. Bacterial Iron - Slime depositing in toilet tanks or fouling water filters and softeners is a good indication of the presence of bacterial iron. Better described as iron bio-fouling, the iron bacteria problem is both complex and widespread. It attacks wells and water systems around the world in all sorts of aquifer environments, both contaminated and pristine. In some places, it causes great damage; in others, it is considered a minor nuisance

Treatment Methods

Iron Bacteria
Iron bacteria can be controlled by periodic well chlorination or it can be treated in the building. The treatment involves the following: Chlorination, retention, filtration. Activated carbon is usually used as the filter material so the excess chlorine can also be removed.

Ferric Iron
In theory, the elimination of ferric iron is simple - use a properly sized media filter to filter it from the water. In practice, however, there may be other issues:

  1. Some iron may be present in colloidal form. Unlike ferric iron, which will generally stick together to form large flakes, the tiny particles of colloidal iron do the opposite. Their large surface area and charge relative to their mass causes the individual particles to repel one another. As a result they will not coagulate. Their small size, then, makes them difficult to filter, and a coagulating agent is often required to obtain adequate filtration.
  2. Most water containing ferric iron also contains ferrous iron. This can add complexity to the process, since some of the methods for removing ferrous iron will also remove ferric iron.

Ferrous Iron
There are a variety of ways for removing ferrous iron, each with its own strengths and limitations. These methods fall into two categories: Ion exchange and Oxidation / filtration

Ion Exchange (Water Softener)

Ion exchange should be considered only for the removal of small quantities of iron and manganese. For practical purposes in an everyday working softener, the upper limit is about 5 to 7 parts per million. Ion exchange involves the use of synthetic resins where a presaturant ion on the solid phase (the "adsorbent," usually sodium) is exchanged for the unwanted ions in the water. One of the major difficulties in using this method for controlling iron and manganese is that if any oxidation occurs during the process, the resulting precipitate can coat and foul the media. Cleaning would then be required using acid or sodium bisulfate

Where the concentration of iron is above 5 or 6 parts per million, or when there is both dissolved and precipitated iron or manganese in the water, a different approach is needed.

Oxidation / Filtration

Oxidation followed by filtration is a relatively simple process. The oxidant chemically oxidizes the iron or manganese (forming a particle), and kills iron bacteria and any other disease-causing bacteria that may be present. The filter then removes the iron or manganese particles.

  1. Oxidation - Before iron and manganese can be filtered, they need to be oxidized to a state in which they can form insoluble complexes. Oxidation involves the transfer of electrons from the iron, manganese, or other chemicals being treated to the oxidizing agent. Oxidation methods fall into two groups: those using additives like chlorine, ozone or air; or those using an oxidizing filter media.
  2. Ozonation - An ozone generator is used to make ozone that is then fed by pump or by an air injector into the water stream to convert ferrous iron into ferric iron. Ozone has the greatest oxidizing potential of the common oxidizers. This is followed by a contact time tank and then by a catalytic medium or an inert multilayered filter for removal of the ferric iron.
  3. Chlorination - Chlorine can be introduced into water in one of several forms: a gas; as calcium hypochlorite; or commonly, as sodium hypochlorite. The treated water is then held in a retention tank where the iron precipitates out and is then removed by filtering with manganese greensand, anthracite/greensand or activated carbon. If applied this way, a dosage of one part of chlorine to each part of iron is used and 0.2 parts of potassium permanganate per part of iron is fed into the water downstream of the chlorine. The potassium permanganate and any chlorine residual serve to continuously regenerate the greensand.
  4. Aeration - Air is also used to convert dissolved iron into a form that can be filtered. This approach mimics what happens when untreated dissolved iron comes into contact with the air after leaving a faucet. Aeration methods can be of a two-tank or a single-tank variety. In a two-tank system, air is introduced into the first tank using a pump or other injection device. The dissolved iron precipitates in the first tank and is carried into the second tank where it is filtered in a Birm or multi-media filter. One drawback to this system is that water bearing the precipitated iron goes through the head of the first unit and the piping between the units. Particularly at lower flow rates, the sticky ferrous hydroxide tends to foul the valve on the first unit and may require cleaning every 6-24 months. A single-tank system essentially combines the two tanks of a single tank system into one. The iron is oxidized at the top of the tank before falling into the filter medium at the bottom. There is no potential fouling of the head. The iron is filtered before it goes through the outlet port of the valve. For very high levels of iron, chlorination with continuous regeneration is the only practical approach.
Oxidizing Filtration Media
  1. Manganese Greensand - the most common chemical oxidant used, it has a relatively high capacity for iron removal and can operate at high flow rates with moderate backwash requirements. Greensand is a processed material consisting of nodular grains of the zeolite mineral glauconite. The material is coated with manganese oxide. The ion exchange properties of the glauconite facilitates the bonding of the coating. This treatment gives the media a catalytic effect in the chemical oxidation reduction reactions necessary for iron and manganese removal. This coating is maintained through regeneration with potassium permanganate – about 1.5 to 2 oz. per cubic foot of greensand.
  2. Birm - acts as a catalyst to promote the reaction between the oxygen and iron dissolved in the water. It requires no regeneration but needs a relatively high level of dissolved oxygen and works best at a pH above 6.8.
  3. Pyrolox - a natural ore that oxidizes and then filters the resulting insoluble iron. It does not need to regenerate, therefore, it doesn’t need other chemicals. However, it needs, ideally, to backwash at 25 to 30 gallons per sq. ft.

Iron - Removal P&ID

Iron Removal from Water

Iron is one of the most abundant metals of the Earth's crust. It occurs naturally in water in soluble form as the ferrous iron (bivalent iron in dissolved form Fe2+ or Fe(OH)+) or complexed form like the ferric iron (trivalent iron: Fe3+ or precipitated as Fe(OH)3). The occurrence of iron in water can also have an industrial origin ; mining, iron and steel industry, metals corrosion, etc.

In general, iron does not present a danger to human health or the environment, but it brings unpleasantness of an aesthetic and organoleptic nature. Indeed, iron gives a rust color to the water, which can stain linen, sanitary facilities or even food industry products. Iron also gives a metallic taste to water, making it unpleasant for consumption. It can also be at the origin of corrosion in drains sewers, due to the development of microorganisms, the ferrobacteries.

In aerated water, the redox potential of the water is such as it allows an oxidation of the ferrous iron in ferric iron which precipitates then in iron hydroxide, Fe(OH)3, thus allowing a natural removal of dissolved iron.

4 Fe2+ 3 O2 --> 2 Fe2O3

Fe2O3 + 3 H2O --> 2Fe(OH)3

The form of iron in water depends on the water pH and redox potential, as shown in the Pourbaix diagram of Iron below. Usually groundwater has a low oxygen content, thus a low redox potential and low pH (5.5- 6.5)

However ground waters are naturally anaerobic: so iron remains in solution and therefore it is important to remove it for a water use.

The elimination of the ferrous iron, by physical-chemical way, is obtained by raising the water redox potential by oxidation thanks to oxygen of the air and this by simple ventilation. In the case of acid water, the treatment could be supplemented by a correction of the pH. Thus, the ferrous iron is oxidized in ferric iron, which precipitates in iron hydroxide, Fe(OH)3. The precipitate is then separated from water by filtration on sand or decantation. The stage of precipitation by chemical oxidation can also be carried out with the stronger oxidants such as the chlorine dioxide (ClO2), ozone (O3) or the potassium permanganate (KMnO4).
This elimination can be carried out by cascade or spraying open-air systems (for an acceptable maximum content of Fe2+ of 7mg.L-1) known as gravitating systems. Those systems require a significant place on the ground, but, in addition to an easy and a cheap exploitation cost, they also make possible aggressive CO2 and hydrogen sulfide (H2S) removal. There are also pressure systems, which in addition to their compactness, make possible to treat water whose Fe2+ concentrations between 7 and 10mg.L-1.

Iron is often found in water in complexed forms. In order to be eliminated, iron complexed requests a coagulation stage, which comes in between oxidation and filtration.

Remark : Thanks to microorganisms, it is possible to remove iron from water by biological way. Indeed, there are many bacteria, whose metabolism and thus their survival, are related to the oxidation of iron. However this biological removal requires conditions specific for the pH, the temperature, the redox potential, etc

Membrane Bio-Reactor - Oman

Oman's Haya Water plans next week to officially open the Al Ansab water treatment plant, which has a large membrane bioreactor (MBR) at its heart and is the main part of the Bausher Water Reuse Project.

Commenting on the forthcoming event on 19 February 2011, Haya's CEO, Omar Al-Wahaibi, said that the current stage was the cornerstone of the water-reuse project, adding that the company was currently working on the completion of the main trunk line to connect areas from Al-Hamria Roundabout to the complete line near Al Ghubra Power & Desalination Plant.

The production capacity of the plant is about 55,000 m³/d of treated water in the first stage, which will be followed by other stages with the production capacity increasing according to requirements. Once commissioned, it will be one of the largest of its kind worldwide using MBR technology.