CA2193494C

CA2193494C - Method of cleaning and maintaining potable water distribution pipe systems with a heated cleaning solution

Info

Publication number: CA2193494C
Application number: CA002193494A
Authority: CA
Inventors: Edward Charles Perry; Jerome H. Ludwig
Original assignee: HERC Products Inc
Current assignee: HERC Products Inc
Priority date: 1994-06-20
Filing date: 1995-06-14
Publication date: 1999-12-07
Anticipated expiration: 2015-06-14
Also published as: WO1995035419A1; MY115961A; BR9505483A; CA2193494A1; EP0766765A1; IL114194A0; AU2828395A

Abstract

A method of cleaning and maintaining potable water distribution systems which have reduced flow due to an increase of water scale deposits, sediment, and the like on the inside surface of the pipe is disclosed. An aqueous acidic cleaning solution (12) is heated and circulated through the pipe (25) to be treated for a sufficient time to dissolve and loosen the scale and sediment, and the spent solution containing dissolved or suspended scale and sediment is flushed from the pipe (25) to provide a cleaned pipe with improved water flow.
It is also desirable to flush the water distribution pipe system with high pressure water after the treatment to remove loosened scale and sediment that was not removed during the circulation and flushing of the treating solution (12).

Description

2?9349 ~-METHOD OF CLEANING AND MAINTAINING POTABLE WATER
DISTRIBUTION PIPE SYSTEMS WITH A HEATED CLEANING
SOLUTION
It is well known that hardness, microorganisms and suspended solids in water sources vary widely in composition depending on the source and will result: in scale deposition including microbial tuberculation and sedimentation on surfaces wherever water is a=_,ed. Scale deposition and sedimentation is particularly troublesome in water distribution pipe systems whi-ch service the residential and commercial .., SHEET

WO 95/35419 ~ , L~ ~ ~ ~ PCT/US95/07546 ,, , ~2~
customers of municipalities, private water companies and the like along with industrial process water distribution pipe systems as found in the mining, petroleum,, agriculture and the like industries. In these systems, the formation of scale, tuberculation and sediment can reduce the water flow through the pipe system which will limit the capacity of the pipe to service the requirements of the customers or to provide the required water necessary for an industrial process, to irrigation, etc. For instance, in municipal systems an increa:ae in the f ire risk would be obvious if the fire hydrant did not supply sufficient water to extinguish the fire due to scale, tuberculation and sediment .deposits in the feed pipe line. At some point, th~a water distribution pipe would have to be replaced clue to these restrictions at a high cost and with prolonged interruption of service.
Additionally, scale, tuberculation and sedimentation will increase the nossibilitv of 2o corrosion in the water distribution pipe along with promoting the growth of other organisms. The organisms also can he a health hazard, promoting corrosion and biomass which binds scale and sediment together and to the surfaces of the system. Corrosion can eventually lead to the leakage of the system and the necessity to replace the leaking section.
The microbiological tuberculation found in water distribution pipes and wells are typically due to WO 95/35419 ~ j 9 ~ ~ 9 4 PCT/US95/07546 iron and manganese bacteria that attach themselves to the walls of the pipe and live on the soluble iron or manganese in the water along with other nutrients.
Their spaghetti-like features also allow them to trap all particulate matter which is present in the water.
There are over 20 different iron bacteria that havEa been characterized. As part of their metabolism, they convert ferrous ion to ferric ion which results in iron oxide (rust) accumulation in the tuberculaition. Manganese bacteria convert manganous ion to manganic ion which results in manganese dioxide accumulation in the tuberculation in the water pipe.
After generations of bacteria, the iron oxide, manganese dioxide, particulate matter and biomass accumulation on the side of the pipe results in mounds of tuberculated "growth" annalogous to a coral reef.
As the tuberculation grows, flow becomes increasingly restricted and turbulant. This leads to red water and turbidity complaints by consumers.
Restricted flow results in low pressure complaints and poor hydrant performance. Tuberculation can also interfere with valve and hydrant performance and operation. There can also be corrosive sulfate reducing bacteria that live under the tuberculation and cause pipe. corrosion.
Strong acids have been used to clean water wells, however, submersible pumps are removed prior to treatment to prevent corrosion by the acids employed.

Also, organic acids, mixtures of mineral acids and organic acids or inhibited acid compositions have been found to clean water wells without the necessity of removing the pumps or other equipment. These methods for cleaning water wells have involved static and surging treatment.
A proper cleaning and maintenance program for water distribution systems will prevent decreased water flow capacity, corrosion and the necessity to replace the system or portions thereof. A simple and effective method for cleaning and maintaining these systems is needed.
French Patent 2571571 describes a mobile all-purpose descaling apparatus with a reservoir, a pump and a moveable chassis. The apparatus may include means for preheating a cleaning solution to be pumped from the reservoir through a pipe system.
French Patent 2602571 describes a method for cleaning the pipes of a potable water distribution system in which a pulsed air jei_ is directed into water in a pipe section.
The method replaces mechanical scraping with air/water scraping.
U.S. F~atent 4025359 describes a pipe cleaning composition mhich has a reduced tendency to attack galvanised or steel pipe, the solution being an aqueous acidic solution.
A~,?~~Y'G'tD SHEET

._. 2193494 . ,.~ , . v ., ~, - 4a -Intern,~tional Patent Application W092/20629 describes a soap composition for the removal of water scale comprising a 1:1 stoichiometric equivalent of a carboxylic acid and an amine base.
SUMMARY OF THIS INVENTION
Thia invention is directed to a method of cleaning and maintaining water distribution systems by employing cleaning solutions at elevated temperatures.
Water systems having interior scale and sediment deposits are cleaned by introducing and circulating an effective amount of an aqueous treatment solution for a sufficient period of time at an elevated temperature which results in the solution, loosening and suspension of the undesired scale and sediment. The scale is associated with sulfate-reducing and iron bacteria consisting primarily of iron oxide, biomass and sediment. As developed above and hereinafter, other bacteria such as manganese bacteria may be involved in the microbial tuberculation found in water distribution pipes. Thus, "scale", as the term is used herein, is AMErde L ~ ~" ,,-.-, L:. fu ,f intended to include microbial tuberculation associated with such bacteria or other bacteria. Thereafter, the spent treating solution containing the dissolved or suspended scale and sediment is flushed from the water distribution system to provide a clean system with improved water flow and operation. Additionally, further f7~.ushing with high pressure water will also remove additional scale that had been loosened by the treating solution.
l0 It has been found that potable water distribution systems may be cleaned and maintained by employing cleaning or treating solutions at elevated temperatures. In general, temperatures on the order of about 40° to about 80°C have been employed and, more particularly, from about 40° to about 50°C. By employing elevated temperatures, water distribution pipes may be cleaned of tuberculation more rapidly, for example, tuberculated pipes cleaned at ambient temperature over a period of about twelve hours may be cleaned in a matter of about 1-2 hours where the cleaning solution has been elevated in temperature to about 75° to 80°C.
'.the cleaning solution may be acidic, neutral or basic. :Cn the most preferred form, in potable water pipe systems, mineral acids or organic acids, and mixtures thereof, are employed as acidic treatment solutions. The acidic treatment solution may contain further additives such as inhibitors, chelating agents, WO 95135419 , PCT/US95107546 'r:~' v ~~ 2193494 penetrating and/or dispersing agents to assist in the removal of scale and sediment and to minimize any adverse effects on the pipes, valves, or other system surfaces clue to the acids employed.
This invention provides a simple, low cost and effecaive method of removing water scale and sediment from water distribution systems in order to maintain proper water flow, operation and to prevent corrosion of the system which would require the high cost and :inconvenience of replacement.
Other advantages and objectives of this invention will be further understood with reference to the following detailed description and drawings.
DETAILED DESCRIPTION OF THE INVENTION
Among the acidic treatment solutions found to be useful in practicing the method of this invention are aqueous solutions of mineral acids such as hydrochloric, nitric, phosphoric, polyphosphoric, hydrofluoric, boric, sulfuric, sulfurous, and the like.
Aqueous solutions of mono-, di- and polybasic organic acids have also been found to be useful and include formic, acetic, propionic, citric, glycolic, lactic, tartaric, polyacrylic, succinic, p-toluenesulfonic, and the like. The useful treatment solutions may also be aqueous mixtures of the above mineral and organic acids.
Alkaline, acid, or neutral cleaning solutions may also be employed, as indicated above, depending _ 7 _ upon the type of scale that needs to be removed.
Sequestering or chelating agents such as EDTA
(ethylenediamine tetraacetic acid), NTA (nitrilotriacetic acid), and derivatives, i.e., basic alkali salts, and the like have also been found to be useful in the treatment solution in certain cases.
The acidic treatment solution may also contain acid inhibitors which substantially reduce the acidic action on metal surfaces of the water distribution system, particularly valves, fire hydrants, etc., and these various inhibitors fo=r acids have been well documented in the patent art. 'typical, but not necessarily all inclusive, examples of acid inhibitors are disclosed in the following U.S. Patents: 2,758,970; 2,807,585; 2,941,949; 3,077,454;
3,607,781; 3,668,137; 3,885,913; 4,089,795; 4,199,469;
4,310,435; 4,541,945; 4,554,090; 4,587,030; 4,614,600;
4,637,899; 4,670,186; 4,780,150 and 4,851,149.
The treatment solution may also contain dispersing, penetrating or emulsifying agents to assist in the removal of the scale and sediment. These surface active agents may be anionic, cationic, nonionic or am;photeric as defined in the art.
Compounds such as alkyl ether sulfates, alkyl or aryl sulfates, alka:nolamines, ethoxylated alkanolamides, amine oxides, ammonium and alkali soaps, betaines, hydrotropes such as sodium aryl sulfonates; ethoxylated _g_ and propoxylated fatty alcohols and sugars, ethoxylated and propoxylated alkylphenols, sulfonates, phosphate esters, quarternaries, sulfosuccinates, and mixtures thereof, have been found to be useful in admixture with the acid treating solution.

DRAWINGS AND OPERATING EXAMPLES

Fig. 1 is a schematic of a laboratory test system illustrating the method of this invention.

Fig. 2 is a diagram of a field system for cleaning a potable water distribution system.

With reference to Fig. 1, a laboratory test system is shown to evaluate the removal of scale and sediment by acidic treating solutions from a test pipe sample taken from a water distribution system. This system includes a 56.8 L (15 gallon) acidic treating solution reservoir 5, submersible ,acidic treating solution circulation pump 6 rated at 75.7 L/minute (1200 gallons per hour), 2.54 cm (1") inlet transfer line 7, drain valve 8, heavy rubber diaphragm seals 9 for the ends of the test pipe specimen 10, 2.54 cm (1") outlet transfer line 11 and the treating solution 12. The test pipe specimen 10 is mounted at about a 30 angle so that the test solution will contact essentially the entire inner pipe surface to be treated.

A laboratory test, for example, was run on a four foot section of 15.24 cm (6") diameter pipe which had been removed from a potable water distribution system that had been used for over 40 years. The scale on the inside of lcd:km the pipe consisted of tuberculated nodules of up to 2.54 to 3 . 81 cm ( 1 to 1~ inches ) in height covering 100 0 of the inside pipe surface which had substantially reduced the opening inside the pipe for water to flow. Analysis of the scale indicated it consisted of primarily iron with some calcium, magnesium and manganese in the form oxides, hydroxides and carbonates along with fine mineral acid insoluble solids and some "biomass". This is typical scale associated with manganese and iron bacteria along with the associated corrosion.

About 37.9 L (10 gallons) of a 12.50 aqueous inhibited hydrochloric/glycolic acid solution containing a penetrating agent was placed in the reservoir 5 and circulated through the test pipe 10 for a period of 24 hours at ambient temperature of about 25-30C. After 2 hours of circulation, particles of the scale were breaking loose and could be heard in the outlet transfer line 11 and observed entering the reservoir 5. The color of the treating solution also become increasingly. darker with circulation time. After 24 hours the circulation was stopped and the system was drained of the treating solution. The diaphragms 9 were removed and the inside of the test pipe was observed to be about 80$ cleaned of scale and sediment solids.

On treating the test pipe with a second identical treating solution for a period of 21.5 hours, about 800 of the interior surface of the test pipe was observed to still lcd:km be covered over with a scale and/or sediment that was a soft and paste-like semi-solid which contained some grit and could be easily removed with a probe. The remaining scale nodules had been substantially reduced in size since the end of the first treatment. It was concluded that the second treatment would probably not be necessary if a high pressure water flush was employed to remove the insoluble soft sediment which had coated the remaining scale nodules after the first treatment.
With reference to Fig. 2, a field equipment and system diagram is shown which may be employed in the cleaning of a potable water pipe distribution system. Two 1892.7 L
(500 gallon) treating solution reservoir tanks 20 and 21 along with a 378.5 L/minute (100 gallon per minute) circulation pump 22 and sight glass 23 are mounted on a flat bed truck (not shown). A heating means 22A is also shown. In this example, a 6.35 cm (2=~") inlet pipe 24 is secured to a 198 m (650 foot) section of 15-24 cm (6") water distribution pipe 25 after the main shut off valve 26. The fire hydrant 27 and fire hose 28 were employed for the acidic treating solution return to tanks 20 and 21.
The section of pipe 25 to be treated was isolated by closing off the two water main shut-off valves 26 and 29 along with all service line valves, typically 30 and 31.
With valves 32 and 33 closed, 3785 L (1000 gallons) of acidic treating solution was prepared in tanks 20 and 21.
With the coupling 34 open, the lcd:km treating aolution was allowed to enter the system by opening valves 33 and 35 and turning on the circulation pump 22. The pH of the water coming from the open coupling was then monitored until a decrease was noted which indicated the acid treating solution had displaced the water in the section to be treated. The circulation pump 22 was turned off and the coupling 34 connected. Valves 36 and 37 were then closed and valve 32 opened for circulation. The circulation pump 22 was then started again for the treatment period. Valve 37 was closedl to allow for loosened solids to accumulate in tank 20 while the treating solution could overflow at 38 to tank 21 which reduces the chances of plugging during treatment.
The treating solution was then circulated in the system of Fig. 2 for a period of 5 hours at about 20°C. Observation of the treating solution through the sight gl<iss 23 showed an increasingly darker discoloration with time. At the end of the treatment period, the circulation pump 22 was turned off, and valves 33 .and 35 were closed. The main shut-off valve 26 was slowly opened and fresh water allowed to enter the system until the treating solution was displaced as noted when the tanks 20 and 21 were full. Valve 32 was then closed. The fire hose 28 was then disconnected from the fire hydrant 27 and the main shut-off valve 26 opened full to allow high pressure flushing of the treated wai_er main 25. As the flush water emerged from the fire hydrant 27 it was dark in color with considerable tuberculation or scale and sediment solids. Flushing continued until the flush water was clean of solids for a period of time prior to putting the treated section of the water distribution system back into service.
The flow rate through the fire hydrant 27 prior to treatment had been determined by a Pitot Gauge to be 2226 L/minute (588 gallons per minute). After treatment, the flow rate was determined to be 2990 L/minute (790 gallons per minute). This was an increase of 34.50.
Also, improved mechanical operations of the hydrants and valves of the system were achieved. The flow of cleaning solution may also be reversed in the system to further improve cleaning efficiency. The above cleaning solutions met the requirements of the National Sanitation Foundation (NSF International, Ann Arbor, Michigan), Standard 60 for potable water distribution systems.
Other examples of cleaning solutions may be employed as follows:
Preblend Ingredients o by wt 31o Hydrochloric acid in water 87.14 +/- 2%
70o Glycolic acid in water 5.27 +/- 0.30 40o Sodium xylene sulfonate in water 2.06 +/- 0.20 Triethanolamine and diethanolamine 2.96 +/- 0.2$
mixture (850/15%) Water 2.57 +/- 0.2o In a preferred form of the invention, the above preblended cleaning solution is used in an amount of about 12.50 by weight with water in the field for lcd:km WO 95/35419 ~ i g 3 ~ 9 4 P(:T/US95/07546 cleaning an underground potable water distribution pipe system. However, more generally, the solution may be employed :Ln amounts of from about 5 to about 50% by weight wii=h water in the field, depending upon such variables as the amount of tuberculation or scale, pipe volume to be cleaned, circulation time and other faCtOrS. The amounts of anhvrlrnttc rthctni ral ~ i n n broader range of ingredients are about 1% to 27% HCl, 0.1% to 10% glycolic acid, 0.04% to 5% sodium xylene sulfonate and about 0.1% to 5% of the triethanolamine/diethanolomine mixture (hereinafter referred to as "TEA").
It should be understood that the above chemical ingredients may be blended for cleaning the underground pipes, for example, hydrochloric acid may be added to a concentrate of the glycolic acid, sodium xylene su7lfonate and TEA. In the potable water distribution systems, an underground section of the pipe to be cleaned is sealed off from the rest of the system. A:a illustrated above in Fig. 2, the cleaning solution is then introduced from a tank into the pipe section and, if water is in that section of pipe, it is removed upon the introduction of the cleaning solution.
After the cleaning solution has been introduced into the pipe section, circulation of the cleaning solution through the underground pipe is initiated for a sufficient period of time for solubilization, loosening and/or suspension of the scale, tuberculation and sediments.

In the above preblends, a soap having a 1:1 stoichiometric equivalent of the acid (HC1 and glycolic acid) and TEA base is formed with an excess of the acid.

This composition has been found to work effectively in the field for the removal of scale and tuberculation associated with iron bacteria consisting primarily of iron oxide, biomass and sediment. These 1:1 soaps have also been described in the above referred to International Application WO 92/20629. These soaps may be more generally categorized as soaps of mineral and/or organic acids and a base such as an amine and ammonia. Further examples of these soaps include 1:1 soaps of TEA and glycolic acid (also known as hydroxyacetic acid); TEA and acetic acid;

TEA and citric acid; TEA and benzoid acid; hydrochloric acid and ammonia; sulphuric acid and ammonia; nitric acid and ammonia; TEA and hydrochloric acid; TEA and sulfuric acid; TEA and nitric acid; ammonia and glycolic acid;

ammonia and benzoic acid; and ammonia and p-toluene sulfonic acid. Accordingly, it will be understood that other cleaning solutions of the acidic type employing 1:1 soaps may be employed to effectively solubilize, loosen and/or suspend the scale, tuberculation and sediment from the potable pipe in accordance with the principles of this invention.

The comparative effects of elevated and ambient lcd:km temperatures are illustrated by the following examples.
Example 1: CLEANING OF TUBERCULATION FROM POTABLE
WATER DISTRIBUTION PIPE AT AMBIENT AND
ELEVATED TEMPERATURES
A 10.2 cm (4") diameter potable water distribution pipe obtained from a town in Arizona having up to 2.54 cm (1") of tuberculation on the inside pipe wall was cut into two 0.61 m (2-foot) lengths for cleaning on the pipe testing station. The tuberculation consisted primarily of iron oxide, manganese oxide and biomass.
AMBIENT TEMPERATURE CLEANING
One section of the pipe was mounted in the pipe cleaning test station. A treating solution was prepared by mixing the "Preblend Ingredients" (by wt.) of 87o muriatic acid, 5o glycolic acid, 2% sodium xylene sulfonate, 3%
triethanolamine/diethanolamine mixture, and water in the test station mixing tank. The treating solution was then circulated through the pipe section at ambient temperature using an electric 416.4 L/minute (110 gallon/minute) swimming pool circulating pump.
The test was run for 5 hours and the pipe section was inspected. Considerable tuberculation was still present.
The test was continued for another 33~ hours and inspected again. Tuberculation persisted.
The test was continued for another 4~ hours and inspected. About 950 of the tuberculation had been removed from the interior surface of the pipe section.
lcd:km ELEVATED TEMPERATURE CLEANING
The second section of the pipe was mounted and cleaned in the same manner except that a gasoline engine driven pump was employed. The pump was mounted on the crank case of the engine which caused the pump and the circulating treating solution to be heated during the test. The pump was rated at 586.7 L/minute (155 gallons per minute).
The test was run for 1~ hours at which time the treating solution was hot to the touch and estimated to be about 75-80°C. Upon inspection of the pipe section, the interior wall of the pipe was essentially as clean as the pipe section cleaned at ambient temperature for 13 hours.
EXAMPLE 2: CLEANING OF TUBERCULATION FROM A HEAVILY
TUBERCULATED WATER DISTRIBUTION PIPE BY
AMBIENT TEMPERATURE CLEANING FOLLOWED BY
ELEVATED TEMPERATURE CLEANING
A 15.24 cm (6") diameter 0.92 m (3') length potable water distribution pipe obtained from a town in Massachusetts having heavy tuberculation of about 5.08 to 6.35 cm (2" to 2~") thickness (opening was about 3.81 to 5.08 cm (l~" to 2")) was mounted on the pipe cleaning test station. The tuberculation consisted essentially of iron and manganese oxides, biomass and sulfate-reducing bacteria. A treating solution was prepared as in Example 1 .
Circulation was begun using the electric 110 gallon per minute circulation pump at ambient temperature. The test lcd:km was run for 11 hours and the pipe section inspected. Heavy tuberculation remained, about 1.27 cm (~") of tuberculation had been removed.
Additional cleaning composition was added to the treating solution thus doubling the concentration of the treating solution. Circulation was continued at ambient temperature for an additional 7 hours and the pipe section inspected again. The tuberculation was still heavy and was about 2.54 to 3.81 cm (1 to l~") thick on the interior pipe wall .
At this point the electric pump was replaced by the gasoline engine pump which heated the treating solution.
The temperature of the treating solution was controlled by the circulation time. Circulation was continued for 30 minutes at which time the treating solution was 42°C.
Circulation was then discontinued and the pipe section drained of treating solution. After the treating solution cooled to room temperature, circulation was again started for a period of one hour at which time the treating solution was 50°C. Circulation was again discontinued and the pipe section drained of treating solution. The next day the circulation was again continued for a period of 3~
hours at which time the temperature of the treating solution was about 50°C. The circulation was then discontinued and the pipe section inspected. A small amount of soft residue was in the pipe which was removed with a water flush from a hose. The pipe was clean of lcd:km -18_ tuberculation.
In this example, about 25~ of the cross sectional area of tuberculation was removed after 18 hours of ambient temperature treating solution circulation and about 750 of the cross sectional area of tuberculation was removed by 2~
hours of periodic elevated temperature treating solution circulation as described above.
In view of the above detailed description, other method variations to clean domestic and industrial water distribution systems, like houses, hotels, plants, offices, etc., will be apparent to a person of ordinary skill in the art. The method is especially advantageous in cleaning underground potable water distribution systems having tuberculation or scale associated with iron and manganese bacteria consisting primarily of iron oxide and manganese oxides, biomass and sediment.
lcd:km

Claims

1. A method for cleaning a water distribution system having a scale comprising introducing an effective amount of a neutral cleaning solution heating the cleaning solution and circulating the heated cleaning solution through the system, characterised in that the system is water distribution system having a scale associated with sulfate-reducing manganese or iron bacteria, in that the cleaning solution is an aqueous solution for the removal of said scale associated with sulfate-reducing manganese or iron bacteria consisting primarily of iron or manganese oxide, biomass and sediment from inside surfaces of a water distribution system, the solution alternatively being acidic or basic, in that the cleaning solution is heated to an elevated temperature of 40°C to 80°C and in that the method includes sealing off a section of pipe (25) in the system for circulation of the cleaning solution therethrough, circulating the heated cleaning solution in the section of pipe (25) for a sufficient period of time for solubilisation, loosening and/or suspension of the scale and sediment, and flushing the cleaning solution containing solubilized, loosened or suspended scale and sediment from the pipe section (25) in the system.

2. A method for cleaning a water distribution system as claimed in Claim I comprising providing a reservoir (20, 21) for containing the cleaning solution, heating the cleaning solution in the reservoir and then circulating the heated cleaning solution from the reservoir (20, 21) through the pipe section (25) and returning the solution to the reservoir (20, 21).

3. A method as claimed in Claim 2, wherein the reservoir is truck mounted for makeup, storage and disposal of cleaning solution.

4. A method as claimed in either Claim 2 or Claim 3 , wherein the section (25) is sealed between two fire hydrants (27) and the cleaning solution is circulated by connecting one of the fire hydrants (27) to the reservoir (20, 21) for pumping the cleaning solution therethrough.

5. A method as claimed in any preceding claim, wherein the distribution system is a domestic or industrial water distribution system.

6. A method as claimed in any preceding claim, wherein the aqueous treatment solution meets the requirements of the National Sanitation Foundation Standard 60 for potable water distribution systems.

7. A method as claimed in any preceding claim, wherein the aqueous treatment solution is acidic and wherein the acid solution contains further additives selected from the group consisting of acid inhibitors, chelating agents, surfactants, penetrating agents and dispersing agents, and mixtures thereof to assist in the removal of the scale and sediment.

8. A method as claimed in any preceding claim, wherein the aqueous treatment solution is acidic and wherein the acid is selected from the group consisting of mineral and organic acids and mixtures thereof.

9. A method as claimed in any preceding claim, wherein the cleaning solution contains a soap having a 1:1 stoichiometric equivalent of an acid and a base wherein the acid is selected from the group consisting of a mineral acid and an organic acid and the base is selected from a group consisting of an amine and ammonia, and wherein an effective amount of free acid is present in the solution to react with the scale.

10. A method as claimed in either Claim 8 or Claim 9, wherein the acid is a mineral acid selected from a group consisting cf hydrochloric, nitric, phosphoric, polyphosphoric, hydrofluoric, boric, sulfuric and sulphurous, mixtures thereof, and/or the organic acid is selected from the group consisting of formic, acetic, propionic, citric, glycolic, lactic, tartaric, polyacrylic, succinic, poly-toluenesulfonic and mixtures thereof.

11. A method as claimed in any one of Claims 8 to 10, wherein the cleaning solution is a mixture of hydrochloric acid, glycolic acid, and alkanolamine and a surfactant.

12. A method as claimed in claim 11, wherein the mixture is employed in a preblend as the aqueous cleaning solution.

13. A method as claimed in any preceding Claim, wherein the temperature is 40°C to 50°C.

14. A method as claimed in any preceding Claim, comprising the further step of flushing the system with clean water after the removal of the spent cleaning solution.

15. A method as claimed in any preceding Claim, comprising the further step of flushing the system with high pressure water for the removal of any spent cleaning solution, scale and/or sediment.