CA2068295A1 - Corrosion inhibition process - Google Patents

Corrosion inhibition process

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Publication number
CA2068295A1
CA2068295A1 CA002068295A CA2068295A CA2068295A1 CA 2068295 A1 CA2068295 A1 CA 2068295A1 CA 002068295 A CA002068295 A CA 002068295A CA 2068295 A CA2068295 A CA 2068295A CA 2068295 A1 CA2068295 A1 CA 2068295A1
Authority
CA
Canada
Prior art keywords
water
calcium bicarbonate
concentration
ozone
predetermined level
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
CA002068295A
Other languages
French (fr)
Inventor
Clement Hinchliffe
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Aquazon Pty Ltd
Original Assignee
Aquazon Pty Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Aquazon Pty Ltd filed Critical Aquazon Pty Ltd
Priority to CA002068295A priority Critical patent/CA2068295A1/en
Publication of CA2068295A1 publication Critical patent/CA2068295A1/en
Abandoned legal-status Critical Current

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  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)

Abstract

ABSTRACT

The invention provides a method and apparatus for reducing corrosion in a water recirculation system. The method involves ozonating the water and adjusting the level of the calcium bicarbonate in the ozonated water to a predetermined level. The predetermined level is a level above that which would cause a scaling water but will not cause such scaling in the ozone solution.

Description

20~8~9~

The presPnt invention rQlates to a method and apparatu~ for ~educing corrosion in a tank cont~ining water. The present invention is particularly applicable to water cooling towexs.
There are many manufacturing plants, power generating systems and air conditioning installation~ which ra~uire efficient cooling. This cooling is generally achieved by using recirculating water systems to obtain the most efficient utilisation of water.
The ~ypical system consists of a basin or sump from which a pump circulates water through pipes to other components, which are normally one or more heat e~changers and a cooling tower, in which the warmed water is sprayed into an air stream. Cooling is achieved by the evaporation of the circulating water. The cooled water falls into the basin to complete the circuit. Any make up water needed, to replace water evaporated or bled from the system, is added into the basin. As water e~aporates from the system the concentration of natural salts is increased.
Scale formation and/or silt accumulation reduces the efficiency and performance of the cooling system due to rastricted heat transfer and interference with water flow.
The e~aporation of water from the cooling tower increases the concentration of natural salts in the circulating water. As this process continues, the natural calcium alkaline hardness in the water will pass its solubility limit and scale formation will take place. The higher temperatures at the heat transfer surfaces increases the rate of scale formation on these surfaces, thereby reducing the efficiency and operating capacity of the unit.
Often scale formation is accompanied by the ~rapping of airborne debris, removed from the cooling air by the scrubbing action of the water which is sprayed through the tower. This inclusion of corrosion product debris or a 20~2~

combination of these materials is often held more tightly together by organic growths.
The accumulation of debris in the absence of scaling results in silt creation.
Generally it is necessar~ to bleed off some of the concentrated water to limit ~ale formation and silting problems. In many cases the volumes of water which have to be bled off ~o prevent scaling are excessive and very precise control is required to achiev~ satisfactory results. This generally results in the method being impractical .
An extension of this method is the addition of acids to the circulating water. Very precise addition, mixing and control is needed to prevent severe damage to the system when acids are added. There are also problems of safety arising from the need to store, handle and apply these acids.
Target concentration for the addition of acid or bleed off of water may be calculated using the Langelier Index, however, this technique is far from satisfactory as the allowable margins of error are extremely limited.
These margins are greatly exceeded if there are any variations in the water composition. These methods also impose severe control re~uirements, especially in high output, smaller water capacity systems which have come into use in recent times, and which make such control extremely difficult.
Most waters are corrosive and this problem may be aggravated by absorption of acidic gases and other impurities from the cooling air. In addition, many of the salts in solution in the water enhance corrosion, particularly chlorides. Corrosive attack on the metal surfaces reduces the life of the plant necessitating repairs or complete replacement of the plant.
Corrosion product build up also interferes with heat 2~82~

transfer and water distribution, and this may be amplified by the inclusion of ~cale, sil~, airborn material or organic matter.
The control of corrosion by achieving desirable calcium bicarbonate concentrations in circulating water using the Langelier Index is an excellent method in theory, howe~er, in prac~ice it has b~en found to ba very difficult to apply given, the very precise cont~ol requirements needed to give ~h~ desired protection without scale formationO At~empts to widen the control parameters using scale modifiers have only been partially successful.
The use of various corrosion inhibitors such as chromatas, zlnc etc. ha~ m~t with some success, how~ver, increasingly tighter controls on the discharge of toxic wastes has led to severe limitations on the use of these chemicals. In addition, the emission of water droplets or aerosols from the air exhausts of water cooling towers containing toxic chemicals have caused concern to health authori~ies, and pollution control regulations are now increasingly preventing the use of these inhibitors.
The presence of organic contamination of the water in the recirculating water system provides the basis for very rapid growth of various forms of biological contaminants, such as slime, alsae and bacteria. The condi-tions of temperature and aeration present in these systems also helps to promote the growth of biological contaminants, as does exposure to sunlight.
Algae and slimes themselves reduce heat transfer.
They also increase the mass of scale and silt and bind it more firmly to internal surfaces of the cooling system further aggravating heat transfer problems. Corrosion is frequently accelerated by the presence of organic matter, which can also interfere with water distribution through the cooling tower, reducing the cooling effect. Bacterial contamination of the water circulating systems is also of : ! :.' .: .:. ' ' ' 20~8~

great concern. Many bacterla are highly darlgerous and in recen~ years special attention has been drawn to the pathogenicity of some strains of Legionnella, particularly for the elderly and others whose resistance to dise~se is di~inished. It is now generally felt that many deaths caused by Legionnella had been previously attributed to other causes.
Bacteria pass into the exhaust air from a tower a~
aerosols. These can be sucked in ~y fresh air intakes of air conditioning systems or can drift into the stre~t and can then be inhaled by people possibly causing infection.
Bacteria may also escape from the system in the bleed off water and in aerosols created when the system is washed out or maintenance is taking place.
A wide range of chemicals such as chlorine, ha~e been used to control biological growth with reasonable success in relation to algae and slime but with varying effect in relation to hacterial contamination.
Due to greater public awareness of the dangers of microbial contamination of cooling systems water in air conditioning systems, attention has been focussed on other methods of disinfecting the water present in these systems. One method of disinfection involves of the use of ozone.
Apart from being a very effective biocide ozone pro~ides a number of other benefits. Ozone has been found to passivate metal surfaces with an oxidised film or layer, and has ~een shown to have scale inhibiting properties. Algae, slime and other impurities in the water additionally act as a glue for solids such as calcium and other particulate matter to form layers of scale. By oxidising all slime and algae, ozone prevents such solids from being glued into scale layers on the walls of cooling towers and condensed water piping. The same properties also de-scale old cooling water systems.

- 206~29~

Another benefit achieved in th~ u~e of ozone is that ozone has a microfloculating effect on the cooling water which causes particulate matter to coagulate and settle to the bottom of the cooling tower or strainer as a fluidized powder or slurry.
It is known ~hat the presence o~ calcium bicarbonate will inhibit corrosion of metal surfaces. However, the use of an excess of calcium bicarbonate typically leads to the formation of scale.
The present inventor has surprisingly found that a combination of the use of oæone and adjustment of the concentration of calcium bicarbonate in the water leads to an ~nhancement of the corrosion inhibitory effect in comparison to ei~her alone.
Accordingly, in a first aspect the present invention consists in a method ~or reducing corrosion in a water recirculation system, the method comprising ozonating the water and monitoring and adjusting the concentration of calcium bicarbonate in the ozonated water to a predetermined level, the predetermined level being a level above that which would cause scaling in water but which will not cause such scaling in the ozone solution.
In general terms the concentration of calcium bicarbonate is ad~usted to give a positive Langelier index. Typically water with a negative ~angelier index i8 corrosive whilst water with a positive Langelier index is scale-forming. The present inventors have made the surprising finding that in combination with ozonation calcium salta plus bicarbonate salts can be added to the water to form calcium bicarbonate to give levels resulting in a positive Langelier index without forming scale. This ability to operate with a positive Langelier index results in a reduction in corrosion.
In a preferred embodiment of the present invention the calcium bicarbonate concentration is adjusted to the .. . . . . . . . . . . - , .

.

2~682~

predetermined level by dosing the ozonated water with solubie ~alts which will orm calcium bicarbonat~ in tha water.
The concentration of calcium bicarbonate can be monitored by any known means, howe~er, at present it is prefexred that the level of calcium bicarbonate is monitored by measurement of the conductivity of the ozonated water. The conductivity of the water is proportional to the level of total dissolved solids. By lG knowledge of the proportion of the total dissol~ed solids due to ~alcium bicarbonate, the conductivity m~asurement provides a slmple and ef~icient measurement of the concentration of calcium bicarbonate.
In a second aspect the present invention consists in an apparatus for reducing corrosion in a water recirculation system, the apparatus comprising an ozone generator connected to the system in a manner such that ozone produced by the ozone generator i5 released into the water, sensor means which measures the calcium bicarbonate concentration in the water or another characteristic of the water, said other characteristic being proportional to the calcium bicarbona~e concentra~lon, and control means connected to the system for main~aining the calcium bicarbonate concentration of the water at a predetermined level, the predetermined level being a level above that which would cause scaling in water under the operating conditions of the system but which will not cause such scaling in the ozone solution under the same conditions, said control means being responsive to output from said sensor means.
It is preferred that the sensor means monitors the total dissolved solids ~oncentrati.on in the water. This concentration will be a function of the concentration of calcium bicarbonate in the water. The total dissolved solids concentration is preferably monitored u~ing a 2~2~

conductivity monitor.
Tha control means pre~erably consists of a valve means ~hich enables the removal o~ concentrated water from the system and i~s replacement with ~resh water. For example, when ~he calcium bicarbonate concentration exceeds the desired le~el as determined by the sensor means, th~ control means enabl~s the removal of a proportion of the water from the system and replacement of this water with watsr having a lower concentration of calcium bicarbonate.
In a preferred embodiment of the present invention the con~rol means includes dosing means for the addition of soluble salts which will form calcium bicarbonate in the water.
In a further preferred embodiment of the present in~ention the system is also provided with a second sensor maans which measures the residual oxidation capacity of the water. The residual oxidation capacity of the water is a function of the ozone treatment. It is preferred that this sensor is connected to an alarm system which is activated when the residual oxidation capacity of the water drops below a predetermined level. The residual oxidation capacity of the water can be sensed by an appropriate electrode and mea~ured by a Redox monitor in millivolts. It is preferred that the Redo~ potential is maintained in the range of 700 to 900 millivolts.
The present invention by utilising the combined effects of ozonisation and increased calcium bicarbonate concentration results in a surprisingly effective reduction in the le~el of corrosion with no scale formation.
In order that the nature of the present invention may be more clearly understood, a preferred form thereof will now be described with reference to the following example and accompanying drawing.

2 ~
- ~ -The water recircula~ion system lO includes a cooling tower 12, sump 14/ hea~ exchanger~ 16 and first and second pump means 18 and 20 respectively. Water i~ drawn from sump 14 through line 22 by fi.rst pump means 18 from where it is kransferred to heat exchanger 16 via line 24.
The water passes through heat exchanger 16 and flows via line 26 to cooling tower 12. The water passes through the cooling tower 12 into sump 14.
Nater is also withdrawn from sump 14 by second pump means 20 via line 28. Water then passes from the second pump means 20 to a filter 32 via line 30. Typically filter 32 would only be required in situations where the water contains heavy insoluble pollutants. Water may then flow from the filter to tho drain via line 34 or to an ozone contact region 38 via line 36. Water reaching tha ozone contact region 38 is contacted with ozone produced by oz.one generator 40 which passes to the ozone contact region 38 via line 42. Water contacted with ozone in the ozone contact region 38 then flows to the sump 14 via line 44.
The level of total dissolved solids in the water in line 44 i8 sensed by means of conductivity element 46 which is connected to line 44. Information from the conductivity element 46 is passed to the conductivity controller 48 by line 47. If the level of total dissolved solids is too high as determined by the conductivity controller 48 a signal is passed via conductivity alarm 50 to valve 52 via line 54. This signal causes valve 52 to open allowing water to pass from the system via line 34 to the drain.
When water is allowed to pass from the system via line 34 and valve 52, make up water is provided via line 58. Provided on line 58 is calcium bicarbonate dosing means 56. The make up water dosed with calcium bicarbona~e passes from the calcium bicarbonate dosing .. . . . . . .

~6~29~
g means 56 into ~ump 14 via line 60.
When the level of total dissolved solids is sensed to be too low by conductivity controller 48, a signal is sent from the conductivity controller 48 to the calcium bicarbonate dosing means 56 via line 57. This results in calcium bicarbonate being dosed into the system. The amount of make up water added to the system is also regulated by the conductivity control means 48 by controlling the arnount of water passing through the calcium bicarbonate do~ing maans S6 by signals passed through line 57.
The level of ozone in the water in line 44 is sensed by ~edox sensing means 62 which is connected to line 44.
Signals from R~dox sensing means 62 is passed to control means 64 by line 63. If the level of ozone is sensed as being too low by control means 64 alarm means 66 is activated.
EXAMPLE
In order to demonstrate the applicability of the present invention tests were carried out in the Wollongong area, which has a water supply which is very low in dissolved solids, calcium hardness and total alkalinity.
When this water is used in cooling water systems, it is impossible to achieve sufficient concentration of the mineral content in the water to reach positive Langelier index values, therefore the water is always corrosive unless corrosion inhibitors are used.
To demonstrate the application of our claim, we evaluated the corrosion rates on two systems, each subject to ozone treatment.
System A. The cooling water system at a large department store, operating shopping centre hours, approxima~ely 60 hours per week, 52 weeks per year.
System B. The cooling system at an industrial plant ,~ , . . . .. ~ . ... .. .. . .. . . .. . . . . . .. .. .

2~2~

operating 24 hrs/day, 365 days per year.
In one s~ries of month long tests, the watex in System A
was modified by the addikion of calcium salts and bicarbona~e, to give Langelier index values which averaged -~ 0.6. The water in System B was not modified and had average Langelier index values of ~1.1.
~QLLosion ~ates Scale formatLon 1~ llil~ÇQl System A 0.03 m.p.y. 2.10 m.p.y. Nil System B 0.44 m.p.y. 16.06 m.p.y. Nil To check the reproducability of these results, a second series of test were carried out and the results were as follows.
~ _lan;ç~L~ CorrosiQn ~a~es Scale In~ Copper Mild Ste~L Formation System A -0.5 0.50 12.80 Nil System B ~1.2 0.02 1.94 Nil By reversing the test, it is clear that the decrease in corrosion rate observed is not due to differences in the system but due to the method of the present invention. The test coupons from the Ozone treated systems which had positive index values were black and had a similar appearance to phosphate treated steel.
It will be appreciated by persons skilled in the art that numerous variations and/or modi~ications may be made to the invention as shown in the specific embodiments without departing from the spirit or scope of the invention as broadly described. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive.

Claims (6)

1. A method for reducing corrosion in a water recirculation system, the method comprising ozonating the water and monitoring and adjusting the concentration of calcium bicarbonate in the ozonated water to a predetermined level, the predetermined level being a level above that which would cause a scaling water but will not cause such scaling in the ozone solution.
2. A method as claimed in claim 1 in which the calcium bicarbonate concentration is adjusted to the predetermined level by dosing the ozonated water with soluble salts which will form calcium bicarbonate in the water.
3. A method as claimed in claim 1 or claim 2 in which the level of calcium bicarbonate is monitored by measurement of the conductivity of the ozonated water.
4. An apparatus for reducing corrosion in a water recirculation system, the apparatus comprising an ozone generator connected to the system in a manner such that ozone produced by the ozone generator is released into the water, sensor means which measures the calcium bicarbonate concentration in the water or another characteristic of the water, said other characteristic being proportional to the calcium bicarbonate concentration, and a control means connected to the system for maintaining the calcium bicarbonate concentration of the water at a predetermined level, the predetermined level being a level above that which would cause scaling in water under the operating conditions of the system but which will not cause such scaling in the ozone solution under the same conditions, said control means being responsive to output from said sensor means.
5. An apparatus as claimed in claim 5 in which the sensor means monitors the total dissolved solids concentration in the water.
6. An apparatus as claimed in claim 5 or 6 in which the control means includes dosing means for the addition of soluble salts which will form calcium bicarbonate in the water.
CA002068295A 1989-11-01 1992-05-08 Corrosion inhibition process Abandoned CA2068295A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CA002068295A CA2068295A1 (en) 1989-11-01 1992-05-08 Corrosion inhibition process

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AUPJ717989 1989-11-01
CA002068295A CA2068295A1 (en) 1989-11-01 1992-05-08 Corrosion inhibition process

Publications (1)

Publication Number Publication Date
CA2068295A1 true CA2068295A1 (en) 1993-11-09

Family

ID=25643773

Family Applications (1)

Application Number Title Priority Date Filing Date
CA002068295A Abandoned CA2068295A1 (en) 1989-11-01 1992-05-08 Corrosion inhibition process

Country Status (1)

Country Link
CA (1) CA2068295A1 (en)

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Legal Events

Date Code Title Description
EEER Examination request
FZDE Discontinued