FR2536678A1 - - Google Patents

Abstract

THIS PROCESS CONSISTS OF UNDERTAKING THE BACKWASHING OPERATIONS OF ION EXCHANGE RESINS IN THE PRESENCE OF A REVITALIZING AGENT WHICH IS PRESENT IN THE BACKWASHING CYCLE FOR AT LEAST THE FIRST 50 OF THE BACKWASHING OPERATION. PREFERABLY, THIS PROCESS IS IMPLEMENTED DURING Virtually EACH BACKWASH CYCLE. THE REVITALIZING AGENT IS CONSTITUTED IN PARTICULAR BY A NON-IONIC SURFACTANT AGENT AND BY A BIODISPERSANT, THE LATTER IN PARTICULAR A BIODISPERSANT CAPABLE OF PRODUCING AT LEAST A CHANGE OF BIOMASS OF 20.0 EVALUATED WITH A BIOMETER AT A TREATMENT RATE OF 10 PPM FOR AN HOUR AT ABOUT 37.8C. A BIOCIDE CAN ALSO BE USED WITH THE NON-IONIC SURFACTANT AND THE BIODISPERSANT.

Description

PERFEC Ti ONNE CONTRALAING PROCESS OF EXCHANGE RESINS Dt: ONS. The

  water softeners and demineralizers filter materials by: feed water icons These particles and the resins themselves also absorb natural and synthetic organic substances such as lignins, tannins, humates, oils, fats, soluble polymers or dispersible in water and others, which can be excellent food for bacteria

  or who may themselves be direct agents of fouling-

  As bacteria multiply, bacterial sludge from microorganisms and their wastes

  may accumulate These factors may influence consider-

  the performance of an ion exchange unit by the obligation to adopt shorter operating periods before regeneration, or because of lower capacities of the resin and poorer qualities of

  water effluent In addition, treated water containing micro-

  organisms and their wastes can cause health problems,

according to the use of water.

  It has been found that the combined use of a surfactant

  non-ionic and a biodispersant could remove micro-

  organisms and their wastes, as well as organic fouling agents and oily and greasy fouling agents,

  outside ion exchange resins and other processing solids

  temnent de l'eau Tests indicate that one obtains a: or: tion sensitive to the quality of water and the capacity of the ion exchange resin for softening resins and demineralization of water by cleaning the resins with an effective amount of a nonionic surfactant and

  of a biodispersant as will be described below A combination

  These nonionic surfactants and these biodispersants can also be used to maintain

  water treatment resins under operating conditions-

  Advanced processing by treating the resins on a continuous and cyclic basis during the backwashing cycle used in the regeneration process The combined treatment agent also allows stable removal of organic anions which severely foul strongly basic anion exchange resins. It has also been found that these combined agent products

  surfactant / biodispersant could also be improved

  res by the addition of certain microbiocides.

  Ion exchange resins softening and demineralizing

  reading the water can remove a wide variety of insoluble substances present in the feed water requiring treatment with these resins These insoluble substances can contain iron salts, inorganic precipitates, silt, semicollordinal lignins, tannins, humates, insoluble natural and synthetic polymers and others, plus oils or fats These resins

  ion exchangers and accumulated particles can also

  Mostly adsorb soluble organic substances Most

  organic substances adsorbed on influencing resins

  ultimately the capacity of the resin and the leak rate

  of an ion exchange unit due to reduced rates of diff

  ion fusion in and out of contaminated resin beads.

  In addition, organic substances either adsorbed by the resin, or filtered from water, can form excellent food for microorganisms. Since these microorganisms multiply, there is a

  microbiological fouling of ion exchange units.

  The resin beads, which are already coated with organic substances, are coated with a bacterial silt and other microorganism waste, further reducing the performance of the ion exchange units. Usually shorter periods are observed before regeneration and poor qualities of the water effluent The removal of these contaminating mixtures by inorganic regenerating agents alone or with

  salt or caustic solutions, does not succeed.

  Since organic fouling agents, bacteria, bacteria silt and waste continue to accumulate, there is the formation of large clumps enveloping large parts of the resin in the ion exchange units Ces clusters further reduce the efficiency of ion exchange units due to bed compaction and the formation of channels which can cause early ion leakage, i.e. can lead to early loss of capacity of these resin units Reports indicating reduced usage capacities down to 20-50% of

  original abilities are not unusual.

  Microorganisms are found in almost all water treatment resins and their presence is not limited to a specific type of resin They include water softening resins as well as cation and anion exchange resins used for demineralization of water bacteria are also found in domestic water softeners, which are used on chlorinated water, in industrial and commercial water softeners as well as in demineralization resins that we use to treat surface water or rainwater Even samples of resin seem relatively clean, which we

  takes place, show varying amounts of bacteria.

  In addition, it is obvious that one wishes to avoid excessive growth of bacteria if one considers that toxins

  causing fevers, such as waste bacteria (pyro-

  genes), can possibly pass from these units into

the treated water supply.

  There are two types of contamination problems. The first is the surface fouling of the beads or particles. The contaminating agent is absorbed on the surface of the ion exchange material and it forms continuous layers of contamination. The second is the fouling of particles

  ionic: the contaminating agents diffuse in the particles

  cules, and are linked to the internal exchange site in the resin.

  Given the problems indicated, it is desirable that the operator of the ion exchange units remove the contaminating agents from the resin. There is another reason for this,

  which of course is the additional function price

  Contaminated ion exchange units, for example, a unit that operates at 25% of its original capacity requires four times more chemical regeneration, which increases the price of chemicals and service. The total price for labor additional work required, for the costs of regenerating chemicals, for the costs of draining water and the like, can be extremely high,

  depending on the extent of organic contamination.

  If one could maintain ion exchange units in a clean state to guarantee a continually optimal performance of the units, one would reach a major advance in

the technique.

  The following United States patents are cited and incorporated here for reference and also for information regarding past attempts to resolve the problems described above: US Patent No. 3,442,798, issued on May 6, 1969, describes the concentration of organic fuels in waste water on a carbon adsorbent surface such as lignin charcoal, bone charcoal, pulverized coke, pulverized charcoal, activated charcoal , activated carbon and the like and then the oxidation of an aqueous dispersion of the adsorbent containing the adsorbed fuels. U.S. Patent No. 3,444,078, issued May 13, 1969, describes the use of granular activated carbon in a water purification filter, an underground gravel bed conduit, and the recovery of activated carbon from water

processed for human consumption.

  Patent US Pat. No. 3,373,085, issued March 12, 1968, describes the recovery of phenol from waste water from coke plants by adsorption of phenol into waste water on

coking coal.

  US Pat. No. 3,578,589, issued May 11, 1971, describes the removal, outside of water cooling systems, of accumulated deposits of slag, mud, silt, slime and other fouling agents by incorporation in water flowing through water cooling systems, a nonionic surfactant and an acid polymer

  acrylic or methacrylic or its water soluble salt.

  U.S. Patent No. 3,748,285, Wiltsey et al., Issued July 24, 1973, proposes treating ion exchange resins with sulfonated detergents to produce beads

clean of resin.

  U S N O 4 102 707, issued July 25, 1978,

  and U.S. Patent No. 4,045,244 issued August 30, 1977 in

  indicate the detachment and dispersion of micro-

  biological materials on support materials in contact with aqueous systems by adding to the aqueous phase a chemical having hydrogen bonding characteristics and comprising water-soluble acrylamide polymers and epoxy compounds, Le USNO patent 3,996,131, issued December 7, 1976, describes the prevention of fouling of reverse osmosis and ultrafiltration membranes by coating the membranes with a

  adsorbing agent, with or without activated carbon.

  Patent US Pat. No. 4,260,504, issued April 7, 1981, relates to the prevention of the formation of deposits on

  walls of heat exchangers, where there is circulation of ethyl-

  lene glycol / water, mixing with ethylene glycol / water, approx.

  ron 0.3-5% w / w of a surfactant, which is the addition product of ethylene oxide and 1,2-propylene oxide or of a monohydric alcohol, of water, a diol or a triol, 60-90% of the fixed oxides being oxyethylene groups. The present invention relates to a new method for improving, restoring and maintaining the performance of water treatment solids which are fouled or tend to become fouled with organic substances, microorganisms and their waste. This new method comprises the treatment cyclic of these water treatment solids with a quantity

  effective of a non-ionic surfactant and a biodispersing agent.

  The process of the invention can be improved by using a biocide in conjunction with the non-ionic surfactant and with the biodispersant. The biocide to be used with the surfactant / biodispersant can be chosen from the group formed by

  biocides ammonium salt = n quaternary fatty, bromoni- biocides

  trilo-substituted, isothiazoline and oxidizing biocides

  fatty quaternary ammonium ammonium biocides are best represented

  smelled by biocidal compounds of alkyl dimethyl chloride

  benzyl ammonium Bromonitrilo-substituted biocides are best represented by dibromonitrilo-propionamide Isothiazoline biocides are marketed biocides manufactured by Rohm & Haas Co and they are sold under the name ATHON 886, described in the product bulletin of Rohm & Haas,

  DIC-76-3, May 1977, which has been incorporated here for reference.

  Oxidizing biocides are best represented by materials such as chlorine, bromine, their hypochlorite salts or their acids, and hypobromous salts or their acids The use of these oxidizing biocides also has the possible advantage of using the power oxidizing chemicals such as chlorine or sodium hypochlorite to decrease, by

  oxidation mechanisms, molecular weight of hydro-

  phobes as biological degradation products and biological waste, so as to make these products more

  hydrophilic or dispersible in water.

  The process of the invention can be applied to water treatment solids such as ion exchange resins, carbon adsorption linings, gravel and sand bed filters, ion exchange membranes. , reverse osmosis membranes and the like Each of the classes

  above water treatment solids can be fouled

  organic substances, soluble or insoluble iron, microorganisms and their wastes, as well as substances

  natural organic derived from water used for food

  lie the water treatment solids according to the invention The preferred water treatment solids which are most subject to improvement, restoration and maintenance of performance

  are the ion exchange resins that we use for

  extract ionic species from contaminated feed water before this water is used for steam production and other uses These ion exchange resins can be chosen from cationic resins of the

  bel, anionic resins of the gel type, catio-

  macroporous nics and macroporous anionic resins.

  These methods can be used to improve, restore and maintain the performance of these ion exchange resins

  by one of the two methods or a combination thereof.

  In addition, the present invention provides a per-

  prepared washing in return of these ion exchange resins which consists in undertaking these washing operations in return in the presence of a revitalizing agent which is present in the return cycle during the first 50% of the operation of

  washing The present invention comprises a counter treatment

  washing, in the operating zone of the resin and, if

  wishes it, separately, that is to say the treatment of against.

  washing can be accomplished during normal washing operations

  resin or can be accomplished in se-

  trimmed o resins will not be immediately returned to

operating mode.

  The process which improves, restores and maintains the perfor-

  Mating ion exchange resins and other water treatment solids can initially be a process where a

  effective amount of a combination of a non-surfactant

  ionic with a biodispersant is added to the resin which has been fouled with organic, micro-organic substances

  and their waste, in a cleaning process of the type

  continuous This discontinuous process involves the addition of 50 to about 2,500 ppm (based on 2 bed volumes) of the active formula, in this fouled resin bed, preferably at elevated temperatures and for at least minus 24 hours These concentrations are based on a double volume of the resin bed or the ion exchange resin bed which is treated. A preferred range is between 200 and

  approximately 1000 ppm of the active ingredients and the pre-

  fermented takes place at temperatures between 38 and 82 C for times of about 20-24 hours with spraying or rapid circulation of the water used for mixing purposes

and contact.

  When this batch system is used to treat water treatment solids in order to remove fouling contaminants, one can add, simultaneously and simultaneously,

  a fatty quaternary amine biocide such as an alkyl dimethyl salt

  benzyl ammonium This quaternary amine biocide is used with the surfactant and the dispersing agent and it may be present in an amount of 50 to 50% by weight relative to the combined surfactant / dispersant formula. The biocide is preferably , used at a rate of 10 to 30% by weight based on the weight

  the total mixture of the three biocidal / surfactantlbio- ingredients

  dispersant The biocide, IATHON 886, described above, can also be used as an effective biocide with the surfactant / dispersant formulation. As previously explained, the addition of an oxidizing biocide to the treatment mixture is often useful for reducing the molecular weight of hydrophobic contaminants and residues of L 2 microorganisms. The oxidizing action of these biocides may tend to hydrophilic hydrophobic contaminants by helping to dissolve them or

  suspension This action tends to make these

  materials easier to remove during a wash cycle and

rinse.

  Before the resins are returned to service, the resin bed is completely washed with water to remove the last remnants of the conditioning agent formed by the combination of surfactant, biodispersant and possibly biocide. This is normally accomplished during the remaining

  of the backwash cycle and during the regeneration sequences

  neration. The second method, which is the preferred method, is a continuous cyclic treatment using the chemicals described above and below in the following manner Each

  ion exchange resin goes through a typical Initia-

  The new fresh resin is also introduced into the resin bed, wetted and regenerated with regeneration chemicals. These chemicals are rinsed out of the bed with washing water and the ion exchange bed is then put into operation in order to remove unwanted ionic species from feed waters that require

  treatment before use of these treated waters in the pro-

  steam generation and other applications After a prescribed time these ion exchange resins lose their ability to remove the required amounts of contaminating ionic species.

  moment, the resins are backwashed by water which rises

  try through the resin bed to increase the volume of the bed by about 50% by volume, in order to discharge, out of the bed, all the contaminating and insoluble species dispersed

  lighter in density than the resin beads themselves.

  This backwashing cycle is normally obtained at a water flow rate of approximately 135 to 676 liters / min, for 0.028 m 3

  of resin contained in the resin bed.

  Following this backwash cycle, the resin beds are allowed to settle and regeneration chemicals are added, flood the resin bed and are subsequently rinsed from the bed before it is returned to operation. The preferred method of the present invention is the addition of the cleaning chemicals described above, and which will be described more fully below, to the backwash cycle before addition of the regenerating chemicals. The preferred method includes the addition of these treatment chemicals at least in the first part of 10% but not more than a first part of 50% of the volumes used for the backwashing of the resins We called this "preventive maintenance mode" of this process Preferably, these treatment chemicals and cleaning solutions are added during the first 25 to 40% of this backwashing rinse cycle In practice this means dosing in backwashing water during the first 10 to 50% of the time allocated to the backwashing of the resin at a relatively constant backwashing rate, of a relatively constant metered flow of the treatment chemicals using

  the nonionic surfactant and the biodispersant, and optionally-

  biocides During the last 50 to 90% of backwashing, the supply of chemical products is no longer added and the rest of the backwashing water is used

  to rinse the processing chemicals and

system contamination sidus.

  After adding the processing chemicals

  and having rinsed them out of the resin bed,

  only the resins thus treated using products

  chemical and standard regeneration techniques.

  When treating resins according to this maintenance method

  preventive, the use of chemicals can be reduced

  cloud compared to the above mentioned batch processing concentrations The combined products comprising the

  non-ionic surfactants and biodispersants, even

  Tuellemient with or without addition of the biocides previously mentioned, can be added to the backwashing cycle at a concentration between about 10 ppm and about ppm of the active ingredient based on the volume of backwashing water If this concentration range is maintained at each subsequent backwash cycle, there is obtained

  the advantages of the present invention, The addition complemen-

  about 5 to about 200 ppm of the biocides mentioned above, preferably about 10 to about 100 ppm of a

  or more of these biocidal materials, can improve the effi-

  of the surfactant / biodispersing treatment agent in

many cases.

  The nonionic surfactant surfactants of the invention preferably have an HLB value between 6 and 14 HLS indicates the hydrophilic / lipophilic balance and is used

  as described in the publication i'Cutcheon- "Deter-

  gents and emulsifiers, North American Edition and International Edition, 1974 Annuals "published by McCutcheon's Division, Allured Publishing Corporation, 45 N Broad St, Ridgewood, New-Jersey, USA These nonionic surfactants are preferably chosen from the group formed by the nonionic adducts of ethylene oxide on phenols

  alkylated, nonionic ethylene oxide adducts

  lene on fatty alkyl alcohols, sorbitan esters

  nonionic and alkylaryl polyethylene glycol ethers non

  ionics The preferred nonionic surfactant is formed from ethylene oxide adducts on

  alkylated phenols which have an HLB value between 6 and 14.

  The most preferred nonionic surfactant is an ethoxylated nonylphenol containing about 9 moles of oxide.

ethylene.

  The biodispersants of the invention are preferably

  chosen from the group formed by ethylene oxide condensates

  lene with propylene oxide adducts on propylene glycol having an HLB value between 4 and 10 and a molecular weight between 1,000 and 5,000, polyethoxylated straight chain nonionic alcohols, tris cocodiamines cyanoethylated, polyoxyethylenated sorbitan esters / acids, non-ionic N, N-dimethlyl-stearamides, non-ionic polyglycolamine condensates and non-ionic ethoxylated alcohols Table I shows the types of chemicals that turned out 6 -vei 6 S have biod- 'spe-rsantes properties T r \ LEAU I Evaluation of the biodispersion capacity of plm compounds with 1 heul-e contact Data collected using a biometer Type of chemical dispersant% change in biomass Non-ionic condensate (polyol ) 66.4% of ethylene oxide with hydrophobic bases (propylene oxide with propylene glycol) Non-ionic polyethoxylated alcohol * 58.5% with straight chain Tris-cyanoethyl cocodiamine 47.3% Polyoxyethylenated sorbitan ester 45, 8% d fatty acids and resin and alkyl-aryl sulfonate mixture (non-ionic) Cationic products of conden 35.8% sation of ethylene oxide and Duomeen T * N, N-dimethyl stearamide 34.7% no - ionic Monoamine (cationic) 31.3% (cocomononitrile) Low weight polyacrylate 31.1%

molecular (molecular weight

  1000 to 10,000) Polyglycol-amine condensate 30.0% non-ionic Cationic cocodiamine 25.6% Non-ionic ethoxylated alcohol 21.2% Non-ionic ethoxylated alcohol 21.2%

  ______________________________________________________________ L

  * Duomeen T = N-tallow-trimethylene diamine

  The percentage change in biomass at Ta-

  bleau I was measured by ex: placing a mass of silt, which we had previously grown and attached to a surface,

  to clear recirculating water at around 380 Co The water contains

  10 ppm of each of the indicated biodispersants is born and it is allowed to recirculate at temperature for one hour. At the end of this time, a determination of the biomass of the water collected in a usual basin was carried out using a

  Dupont 760 lumiinescence biometer, described in-the publica-

  tion, "Dupont 760 Luminescence Biometer", published in December 1970 and described in US Patent 3,359,973, which is incorporated

here for reference.

  This table shows the filling of the accumulated biomass, which

  was dispersed by treatment with 10 ppm of the dispersing agent

  sant indicated Although other dispersants have been tried, which had less than 20% effectiveness, these results are not presented because any dispersant having an efficiency of less than 20% in these tests appears to not work

  appropriately in the invention.

  The weight of the surfactant relative to the dispersing agent in the pet treatment mixture will vary between about 0.1: 10 and about 10: 1 and it is preferably from 1: 2 to 2: 1. 1: 1 weight was found

8 be particularly effective.

  When a quaternary amine biocide is used with the slurfactant and the dispersing agent, it can be

  present in an amount of 1 to 50% by weight and, preferably

  from 10 to 30% by weight based on the weight of the mixture

  total age These cationic biocides are preferably not

  used when cleaning cationic exchange resins.

  The biocides of the invention are chosen from the * group formed by fatty alkyl quaternary salt biocides, non-ionic bromonitrilosubstituted propionamides, isothiazolines and oxidizing biocides The fatty alkyl quaternary salt biocides are represented by, and are preferably a biocide quaternary ammonium salt alyl dimr chloride thyl-b enzyl amoniun The nonionic biocide may preferably be dibromo-nitrilo-propionamide, although this material is not stable under condition of basic pI, so its effective use is limited to

  neutral or slightly acidic conditions Isothiazo-

  lines are best described as "KATHON E 886" and

  are mainly manufactured by Rohm & H Iaas Co These bioci-

  are described in a product bulletin previously

referenced, with N being part.

  Oxidizing biocides are materials such as chlorine, bromine, hypochlorous acid, hypobromous acid and the alkali metal salts of hypochlorous and hypobromous acids. Here, the alkali metal salts mean the salts containing sodium cations, potassium, ammonium and rubidium. Having described the discontinuous process and the continuous cyclic preventive maintenance process, having described the agents

  nonionic surfactants and the biodispersants of the invention

  tion, and having described the preferred biocides which can be used in combination with non-surfactants

  ioniaues and the biodispersants of the invention, it is now possible to

  nant describe, by way of example, the application of these products

  chemicals in processes to improve, restore and maintain

  hold the performance of water treatment solids which are clogged with organic substances, microorganics

and their waste.

E'TLUDS EXPERI> ENT'LES

  1 Effect of the invention on the performance of

  Contaminated cation exchangers The effect of the present invention on the capacities

  operating and leakage of heat exchangers

  contaminated with various organic substances, bacteria and bacterial residues, was observed in these tests Two

  resins had very large amounts of a gelatin mass

  sticky and covering the particles, under the form

  me of flakes from a ris-verd-tree and a resin contained a lesser amount of a fouling agent The first two resins had a foul odor while the third had only an annoying odorless odor The materials used for cleaning these resins were a surfactant,

  namely an ethooxylated nonyl-pheno I (9 moles) and a biodisper-

  health, ': to know a condensate of polyox-ypropyl-ne-polyoxyéthy-

  lene (cloud point 32 C); and a quaternary amine, to

  know an alkyl-dimdthyl-benzyl-amoniur chlorate In par-

  tie, the quaternary amine can serve as a solubilizer of the over-factant In order to determine the removal efficiency of the products

  organic, bacteria and bacterial residues of resins.

  by this process, the quantities of chemicals and

  the reaction times chosen were greater than those actually

also necessary.

  Test No. 1: Strong Acid Cationic Resin This resin contained substantial quantities of gray-greenish flakes of large and medium dimensions, and the beads were almost regularly covered with a mass of

  gelatinous type resembling the touch of a silt.

  Test conditions A quantity of 300 ml of the resin was added slowly to a 25 mm Lucite tube, with a minimum quantity of water between the additions of each portion of the sample.

  guaranteed that the silt-like flakes were melan-

  managed regularly throughout the resin column The height

  total of the bed was 57.15 cm We then left the resin.

  rest for 4 days After this time, the resin has been lifted by backwashing A solid mass of cylindrical shape has risen like a piston, and there have been only about 30-40% of the total beads of the resin which have separated from this solid mass After 15 minutes, the attempt to backwash the resin was stopped The amount of water removed by backwashing was $ 00 ml This water had an account

  total bacterial between 106 and 107 per ml, the determination

  nation being made by immersion sticks "Orion Easicult.

Test water.

  Test water with a total hardness of 7.93 gpl (US grains per liter), or 0.51 grams / l, was prepared using 62.6 g of anhydrous Ca C 12, 70.2 g of Mg SO 407 H 20 and 2 g, 35 g Na'-ICO 3 at 189 liters of deionized water The final water then contained 526 ppm of total hardness, with a ratio of two thirds of calcium to one third of magnesium, plus 150 ppm

of Na HC 03.

  This test water was passed through the unit at a rate of 30 ml per minute, the equivalent of 7.56 / mm for 0.0288 m 3 of resin, until the we obtain a leakage hardness of 0.264 US grains per liter (gpl), i.e.

0.017 gram / l.

  Test 1-A: Resin only backwashed The resin was then regenerated with the equivalent of 2.72 kg of Na Cl for O 0.028 n, or 270 ml of a 10% salt solution per 300 ml of resin The resin then was rinsed with a volume of a bed of deionized water at a rate equivalent to the regenerating flow At this point, the hard water passed to

ml / min.

  The pressure drop and hardness leak data are shown in Figure 1 The average pressure drop

  through the resin unit was dg 0.31 bar.

  Test 1-B: Resin loosened with an air lance and backwashed The water above the resin used in test 1-A was drained to the level of the bed and compressed in air for about three minutes with compressed air at a fair rate

  ** the 57.15 cm of resin in the 140 cm long tube.

  The resin was then backwashed with deionized water at a rate sufficient to obtain an "ultimate" expansion of the resin by 50%, until the effluents were free of all

  debris This required approximately 35 minutes of backwashing.

253 û 673

  During this time, a considerable quantity of a fluffy material, of brown and vertical color, was rinsed. The particles were comprised, in dimensions, between approximately 0.5 and 2 mm, The backwashed quantity was approximately 50 mlo The particles were quite sticky A microscopic examination showed main

  mainly translucent particles.

  We then passed the test water through the unit

as in test 1-A.

  The results are shown in Figure 1 o The fall in

  average pressure in the unit was 0.1 bar.

  Test 1-C: Resin treated with an agent which activates a biodis-

persistant and biocide

* The resin used in tests 1-A and 1-B was contraindicated

  washed for 10 minutes, then slowly passed through the resin, at a temperature of 43-54 Cs for one hour, one liter of a mixture of 1000 mg of nonyl-phenol

  ethoxylated (9 moles), 1000 mg of a polyoxypro- condensate

  pylene-polyoxyethylene (cloud point 32 C), and 500 mg of alkyl dimethyl benzyl-ammonium chloride (in the form of a 50% solution of the quaternary amine) The solution was reheated and was passed again for one hour The last part of the solution was left in the resin unit for 48 hours Then the resin was backwashed with deionized water for 48 minutes, i.e. until '' that the effluents are clear

  debris removed during this time had a dimension of par-

  very small and were light enough to require

  approximately 2 hours to deposit in the recovery tank

  ration A microscopic examination of these particles, a

  leurmarronclair, showed translucent gelatinous particles

  cides of various shapes and thicknesses The resin was then regenerated and rinsed as described in tests 1-A and 1-B The capacity and leakage properties of the treated resin were determined in identical procedures to those used for

  experience with backwash or air launch and counter

  wash Y N could not detect any pressure drop with the

pressure gauge used.

  The results for leaks and capacity are indi-

shown in Figure 1.

  As can be seen from the curves in Figure 1, a significant improvement in capacity and hardness leakage was obtained by treatment with the surfactant, the biodispersant and the biocide When backwashing the

  resin, we found that it was loose and without any heap.

  The pearls are separated by Eaita-zent The effluents from counter

  washing showed a moderate amount (about 3 ml) of small

  brown colored flakes that separated very easily.

  Some flakes (1 ml) remained at the top of the resin,

  with fibers originally from this sample.

  The supernatant liquid from this sample showed zero bacteria, when tested with brion Easiculte immersion sticks Test No. 2: Water softening resin

  This resin has been contaminated in unusual quantities-

  large flakes of large size, and the resin beads were coated with a gelatinous coating which gave the feel of the silt to the touch.

  was a gray-greenish color.

  Test conditions A quantity of 300 ml of this resin plus the free contaminants was placed in a 25 mm tube with a minimum

  of water between the addition of each portion of This agar resin.

  that the silt-like flakes were regularly

  mixed with resin The resin was left in the unit for

  for 4 days After this time, an attempt has been made to backwash the resin. It is reassembled in the tube in one piece, without coming off when the water is opened and closed.

alternately.

  Test 2-A: loosened with an air lance and backwashed The water was dredged at the level of the bed and the bed was loosened

  in the air for about 5 minutes while the plastic tube

  that thin used to introduce the air was moved so

  repeated from top to bottom The resin was then backwashed for

  for about 45 minutes until the effluents are clear The first 500 ml portion of the counter water

  washing showed a total bacteria count of 107, in

  using the "Orion Easi-

  cult The total amount of backwashed solids was approximately

  mi This material settled about 25 ml in two weeks

  The volume of resin reduced by approximately 5 ml to 325 ml in total. A microscopic examination of the gray-greenish flakes removed by backwashing showed translucent and gelatinous particles of irregular shape and size. The resin was regenerated with 29 C ml of 10% Na Ci or 2.72 kg of Na Cl for 0.028 m 3 of resin The resin was then rinsed and

  the test water was passed as described in the example:

rience of test 1.

  The capacity and the leaks are shown on the

figure 2.

  The average pressure drop across the unit was

0.036 bar.

  Test 2-B: Resin treated with a surfactant, a biodis-

  persant and a biocide The resin used in test 2-A was treated with 500 ml of a solution containing 500 mg of nonyl-phenol-ethoxylate

  (9 moles of EO), 500 mg of a polyoxypropylene condensate-

  polyoxyethylene (cloud point 32 C) and 250 mg of Xcyldimnthyl-benzyl-ammonium chloride (in the form of a 50% solution of quaternary amine), at 43-54 C for 3 hours while heating

  repeatedly and passing the solution,

  down, through the resin One bed volume of this solution was left in the unit overnight The resin was then backwashed to 50% expansion

  for 45 minutes until the effluents are clear.

  About 20 to 25 ml of a light brown substance was removed in the form of fine flakes The flakes had less

1 mm in diameter.

  The resin supernatant showed zero bacteria when tested with the "Orion Easicult" immersion stick.

  The resin was then regenerated as in test 2-A.

  The regenerant used was collected and showed a color

  ranging from weak yellow to brown We also noted the forma-

  tion of foam in regenerating effluents The resin has

  then been rinsed with 330 ml of deionized water at the flow rate of the reg-

  nering then quickly rinsed with the test water We then

  passes the test water through the resin under conditions

  identical to those used in test 2-A (7.56 / min

for 0.028 m 3) -

  The capacity and leakage results are shown

tees in Figure 2.

  No pressure drop could be measured with the

pressure gauge used.

  Effluent foaming was noted until 10 1/2 bed volumes were passed,

  i.e. 3.5 liters of test water, through the resin.

  At this point, no odor was noted either.

  tests, the resin was backwashed by raising and depositing it

  alternately the resin still showed some

  cluster formation, although much weaker than originally.

  But this essay indicates that, although a

  sensitive cleaning, not all contaminants have been removed

  res This resin was obviously so contaminated that a

  more cleaning or repeated cleaning is necessary.

  Microscopic examination showed considerable differences

  the appearance of the resin, that is, the cleaning has

  re a large portion of the original contaminants This is also indicated by the improvement in the capacity and the hardness leakage of the resin, as shown in Figure 20 Test N O 3: Water-softening resin

Z 536678

  This resin was only slightly contaminated with

  free cons and light brown, with some coating on

pearls.

  Test conditions 250 ml of resin plus small quantities were placed

  contaminant flocculating in a 25 mm tube with the result-

  tat a bed height of 52 mm This resin was left in the unit for 4 days The resin was then raised by a short backwash We observed several small clumps which did not break while the resin is slowly

  dropped through the water to the bottom of the tube.

  Test 3-A: loosens with an air lance and backwashed The water has been drained to the level of the bed and the resin

  was d 6 packed in the air for 5 minutes by moving simultaneously

  the thin air tube up and down in the resin bed The resin was then backwashed for minutes, i.e. until the effluents were clear The amount of fluffy material d very small size was around 7 ml when freshly collected This amount settled to 4-5 ml after a week The first 500 ml of backwashing water showed a total count of bacteria from 105 to 106 by measuring with the Easiculit immersion stick. The resin was regenerated with 225 ml of a 10% Na Cl solution, ie 2.72 kg of Na Cl for 0.028 m 3 of dresin La resin was then rinsed and exhausted with the test water in conditions identical to those used in all the previous experiments. The capacity and the leaks obtained are shown on the

figure 3.

  There was not enough pressure drop to

  measure it with the pressure gauge used.

  Test 3-B: Resins treated with a surfactant, a bio-

  dispersant and a quaternary amine The resin which had been used in test 3-A was

  treated with 500 ml of a solution containing 500 mg of nonyl-

  phenolethoxyl (9 moles), 500 mg of a polyoxypro- condensate

  pylene polyoxyethylene (cloud point 32 C) and 250 mg of alkyl dimethyl benzyl ammonium chloride (in the form of a 50% solution of the quaternary amine), at 43-54 C for 3 hours while reheating, repeatedly , the solution and enla

  passing downwardly through the resin.

  As in test 2-C, a volume of one bed of the solution was left in the unit overnight The resin was then backwashed until the backwashing water was clear, which required about 45 minutes The total amount of fluffy, fluffy, pale-colored material removed was approximately 3 ml Microscopic examination showed gelatinous and translucent particles of small size and various shapes and thicknesses The liquid supernatant of the resin was

  free of bacteria, by measuring by immersion stick test

  sion'Orion EasiculÈl The resin was then regenerated, rinsed and exhausted with water in the conditions identical to all the previous tests. The used regenerating agent exhibited a

light yellow color.

  The capacity and the leakage obtained are represented on.

figure 3.

  The foaming of the effluents stopped at approximately 2.5 liters of the test water having passed through, i.e.

the equivalent of 11 bed volumes.

  The capacity of the resin, which had only been air-stripped and backwashed, was close to the available capacity of this sample of particulate resin, that is to say that about 23.0 liters of softened had been softened. test water with 225 ml of resin The chemical treatment - with the surfactant, the biodispersant and the quaternary amine, resulted, therefore, only little improvement in terms of capacity (we treated in addition about a liter of water quality improvement was important however On average there is a reduction from 6 ppm of total hardness leakage obtained with the resin as received to 4 ppm with the resin

  chemically treated, as can be seen in Figure 3.

  The results obtained with this resin are particularly interesting if we consider that this resin was fairly new (10 months) and contained only a relatively small amount of bacteria and various organic debris coating the resin and in the form of free substances. in

the supernatant liquid.

  Test No. 4 In this test, according to the present invention, a marketed demineralizing system was treated having rapid losses in capacity for use. The reduction in capacity

  had required frequent replacement of the resin, shown

  both a major operating cost The cationic resin had to be replaced every three years; weak resin, every 11 months; and the strongly basic resin, every 18 months The reduced lifetime of the resin was due to rapid fouling by natural organic materials, bacteria, algae and synthetic polymers The harmful effect of surface fouling agents on cationic and weakly basic resin units was particularly evident. The purpose of the test was to determine whether a combination

  a biodispersant and a nonionic surfactant for

  will remove enough fouling agents to restore the system to a usable capacity. In this test, Na O Cl was added as an oxidizing agent, a solubilizing agent and a

inorganic oxidizing biocide.

  In the test, water was pumped from a collected lagoon

  on natural surface runoff to a water treatment facility where 1 to ppm of synthetic polymeric coagulant has been added. Water is passed through a filtration unit to remove material particulate then it was passed through a demineralizing system comprising, four lines of mineralizing, each

  line containing 11.2 m 3 of cationic resin, 6.3 m 3 of resin

  only weakly basic and 4.2 m 3 of strongly basic resin.

  The resin replacement of two of the four lines had been planned because of the lowered capacities. These two lines were treated according to the present invention in the following manner: Netto Sage of demineralizing lines 1 and 2 Each unit of the two demineralizing lines was

cleaned separately.

  1 Cation unit of line n 1 (11.2 m 3) Dosage: 1) '2500 ppm of a mixture of a surfactant and

  of a biodispersant The surfactant was a nonylphenoxy-

  nonionic liquid polyethoxyethanol having an HLB value

  of 13.3 The biodispersant was a non-block block copolymer

  ionic liquid propylene oxide and ethylene oxide

having an HLB value of 7.0.

  2) 250 ppm of C 12 added as a bleach, or

  well 9.46 liters of 18% Na O Cl per unit.

  The unit was agitated in air by the counter line

  wash every hour for 4 hours, then leave to stand overnight No foaming has occurred, possibly due to the unusually large amount of particulate matter released during cleaning The next morning, the unit was backwashed at 1,135 1 / min for 2 hours At this point, the water evacuated was clear We could observe the formation of foam after

  minutes A small particulate matter is still left

  large quantity output The surface coating of the parts

  resin cules accepted an Alcian blue dye until about 1/4 of most of the particles were coated with the colored substances This indicated the presence

  of poly-saccharides, that is to say of biological residues.

  2 Weakly basic unit of line N O 1 (6 3 m 3) Dosage: 1) 2,500 ppm of the mixture described above, 2 volumes

of bed or 15.14 1 per unit.

  2) 250 ppm of C 12 added as bleach, or else 3 1 of 18 O% Na O Cl per unit. Again, the unit was stirred in the air every hour for 4 hours. There was moderate foaming, and the stirring in the air was stopped when

  the foam has reached the top of the unit The unit has been left

  seated overnight, then backwashed for 1 3/4 hours until no more particles are noticed

  or foam in the effluent The backwash water has become

  crystal clear much faster than for the cationi A unit

  than, that is, there were fewer particles removed.

  3 Strongly basic unit of line no 1 (452 m A Dosage: Same concentration of the solution The total amount added was 9.46 liters of the mixture described above and

3.6 liters of 18% Na O Cl.

  This unit contained almost no loose particles

  and formed foam during air stirring and

  during backwashing Addition of an anti-chemical agent

  foam in the residual water was very effective in preventing

  foaming in the sewer lines.

  4 Resin units of line 2 The conditions described for line n 1 were used for the treatment of line 2 and the same was used

quantities of chemicals.

  The reaction time for the scrubber was however kept at 4 hours L, the cation unit was more seriously

  fouled as that of lalignen l Thus, a counter rinse

  2 1/2 hour wash was required compared to 2 hours

  for the cationic unit of line n 1.

EXAMPLE 1

  Preventive maintenance treatment of the demineralization line No. 1 A preventive maintenance dose of 20 ppm of the mixture of surfactant and dispersing agent used in the above tests was brought into the backwashing water of the units. cationic, weakly basic and strongly basic The product seemed to be rinsed out of the units during the remaining backwash, i.e. 20 minutes of

  the more, the more the normal regeneration and the flushing of the regener-

  rant The "final" rinse water taken during the last 2 minutes of rinsing showed equal surface tension

to the raw water supplied.

  After several backwash cycles, using this

  preventive maintenance program, cleaning treatment

  has restored the lines to their maximum possible operating condition The operating time of line 1 has been increased from 1,835,725 liters to 4,049,950 liters and an increase has been obtained from 3,292,950 to 3,974 250 liters for line 2 An analysis of the resin showed that only about 81% of the original capacity remained, that is to say

  that all the available capacity of this resin was restored

rée.

  The data collected after 5 months of operation.

  have established that the preventive maintenance treatment in line 1 reduced the decrease in operating times to around 12 to 15%, while line 2 showed a rapid decrease in operating times by 45%. i.e. relative quantities

treated water.

  This test shows that the preventive maintenance program

  is very effective The demineralizing line in 1 was initiated

  Cleaned and treated with a 1: 1 weight ratio of surfactant and biodispersant, plus chlorine. It was then treated continuously and cyclically with the same mixture of the nonionic surfactant and

  biodispersing to give it the optimal functional

  operation and excellent low leakage characteristics, typical of clean demineralization resins On the contrary, the demineralizing line n 2, which has been effectively discontinuously cleaned, but which has not been more fully treated

  with a cyclical prevention and maintenance program,

  very a decrease in its operating characteristics.

  The success in removing surface contaminants was probably due in part to the combination of the surfactant, dispersant and chlorine as the oxidizing biocide. It is also believed that chlorine can act on all contaminating polymer chains at branching sites causing a chain break, resulting in lower molecular weight and the formation of a more water-soluble polymer residue The alkalinity produced by the use of bleach may also be beneficial for the conversion of

  polymer in its sodium salt form more soluble in water.

EXAMPLE 2

  2 Improvement of the performance of a highly basic contaminated anion exchange resin The following tests were carried out to study whether it is possible to improve the performance characteristics of dirty anionic resins by using a surfactant and a bio-dispersant as an additive to the commonly used cleaning solution, i.e. a mixture of Finalenent salt and caustic base, it is believed to provide sufficient evidence of the usefulness of such components to help maintain anionic resins * in good condition. state-of-the-art operation, that is, to prevent the accumulation of organic matter instead of letting the resin get dirty and waiting until the unit's operating price is so high and the quality water produced so bad that the user

  of the installation has to face a serious problem.

  The resin chosen was a sample

  recently received from a client Leclient had suffered both

  water quality and a high p H with this resin Cet

  sample contained a moderate amount of flo-

  brown-colored connoisseurs of various shapes and sizes, and the resin itself was coated with moderate amounts of a silty substance The sample smelled foul

  which is not characteristic of new anion exchange resins The water surrounding the resin particles had a count

  total batteries of about 107 by measuring by the "Orion Easicult" test, which indicates that the environment of the resin was microbiologically fouled and contaminated. The sample had only 79% of its original total capacity and 67% of its original salt separation capacity It contained 10% broken pearls, was contaminated with

  429 g of Fe and 928 g of Si per m 3 of resin, and was also

  fouled large amounts of organic substances

dark in color.

  A Capacity and leakage test before chemical treatment Two 40 ml samples of this resin were placed in a 50 ml burette, and were exhausted with water containing 585 ppm of hydrochloric acid, calculating as Ca C 03, until a leak of 50 M 5 (micro Siemens) The resin was then regenerated with 81 kg of Na OH per m 3 of resin, rinsed and exhausted with test water at 585 ppm of hydrochloric acid at

total as Ca CO 3.

  A sample (column A) showed an effluent having a conductivity of 10 to 21 micro Siemens The other sample (column B) gave a water having a conductivity of about -30 / PS but at the end of the cycle, we noted that this sample

  contained slightly more debris than the first sample.

  B Capacity and leakage test after chemical treatment.

  Column A was treated with the normally recommended treatment of 167 kg of Na Cl and 16.7 kg of Na OH per m 3 of resin,

  applied as a 10% solution at 60 C for 3 hours.

  The actual amount used was 60 ml of the solution for

ml of the resin.

  Column B was treated with a mixture of 60 ml of

  the above solution, diluted to 110 ml in total with a solution

  aqueous 50 mg of ethoxylated nonylphenol (9 moles), 50 mg of a polyoxypropylene-polyoxyethylene condensate (cloud point 32 C) and 25 mg of chloride of 1 yldimethy 1 berlr ammonium (quaternary amine biocide), La treatment time was 3 hours at 6 00 C. The two columns were left without heating overnight, with enough of each treatment solution surrounding the resin beads, The resin samples were then rinsed with Hl I at 092 N and then with water, then regenerated, rinsed and exhausted as in A The accumulated effluents from the treatment were both of a very dark red-brown color The quality of the water obtained was however quite different The resin

  treated with surfactant, biodispersant and bio-

  cide in admixture with salt and caustic, gave water having a conductance of about 5 to 10 t 15 less than the column treated with the surfactant and the like, and gave water quality d '' about 6 / day for about

  2/3 of the test, while the resin treated without these additives

  tifs gave a water quality of around 15 to 20 / f S on

  most of the trial, with approximately 5% of the es

  sai giving a water quality of 8/4 s.

  The initial 1/3 of the water treated with the two resins showed a clear color, more color, was noted with the resin treated with the surfactants, etc. This seems to justify the assertion that a strongly basic resin in which allowed to accumulate organic matter can most likely never be completely cleaned, due to the low mobility of organic matter - high molecular weight In other words, one can not expect that a resin o have accumulated these substances over a long period of time can be completely cleaned during the relatively short period of time provided for cleaning. The positive improvement noted here, however, provides proof of the validity of the concept of the use of surfactants and biodispersants to help remove organic matter from otherwise anionic resins

  difficult to move resins In addition, these results indicate

  also that the components used are candidates

  excellent for preventing the accumulation of organic matter

  on anion exchange resins.

EXAMPLE 3

3 Product preparation

  A total of four products have been prepared.

  were taking a biodispersant (polyoxypropylene condensate-

  polyoxyethylene prepared as described in US Patent No. 2,674,619, incorporated by reference) and a surfactant (nonylphenol ethoxylated to 9 moles of ethylene oxide>

  with or without quaternary amine (alkyl dimethyl chloride-

benzyl ammonium) as a biocide.

  All the products are 6 t formulated in the form of a 50% solution in water. The individual components were mixed at -65 C, without any difficulty. At the lower temperatures, the mixing was somewhat more difficult; the viscosities of the solutions during mixing were such that a time

  considerable effort was required to achieve a uni-

  formally mixed The preferred order of mixing was as follows, water, surfactant followed by dispersing agent and finally

quaternary amine as a biocide.

  Product components and mixing order Product Water Surfac Dis Der Disper Amine NÈ quaternary health A

CX-29 50% 20% 20% 10%

CX-30 50% 25% 25%

CX-31 50% 18.2% 18.2% 13.6%

CX-32 50% 25% 25% -

  Dispersant B is of the same type as dispersant A except

  except that it has a cloud point (32 C) which is 8 higher than that of dispersant A All the products prepared are colorless solutions,

  limpid and somewhat viscous O They dissolve easily

  in water at all concentrations and at all temperatures.

  erasures. These CX products were subjected to stability tests at 49: C, 24 C, O C and -18 Co After 2 weeks, no change was observed except that the products

  are frozen at -180 C During thawing, a recovery was observed

  complete ration in the freeze-thaw cycle.

  The following surfactants have been successfully used in the process:

* kakon 10 alkylphenoxy-polyoxyethylene-non-liquid ethanol

ionic

  Surfonic N-85 nonylphenoxy-polyethoxy-ethanol, non-liquid

ionic.

EXAMPLE 4

  The effectiveness of the combined non-surfactant program

  ionic and biodispersing to maintain the capacities of

  nes ion exchanger has been tested in an installation with

  Southern United States One cationic unit and two anionic units

  demineralization was clogged with water

  organic substances from natural sources and also

  possibly upstream sewage treatment plant Cation exchange resins

  showed a surface coating with organic materials

  undefined, bacterial silts, with detection of microorganisms The anion exchange resins were severely fouled with dark brown substances, which are believed to be lignins and tannins Likewise, substances of an oily or greasy nature were detected on the

  anion exchange resins, causing a cluster of parti-

  resin cules The three units were treated with a

  combination of the nonionic surfactant and the biodis-

  persant preferred in combination with sodium hypochlorite both as an oxidizing agent and as a biocide

  The temperature of the water passing through the demi-

  were between 29.5 and about 35 C

  during the test The water contained significant amounts of

  natural organic matter plus the evacuation of an installation

  Sewage treatment upstream, although no analytical attempt has been made to identify each of the organic contaminants, a reasonable estimate of these contaminants may include the presence of tannins, lignins, fatty acids, organisms microbiological and their waste. The cation exchange unit had been charged with tbermutit QB and it was tested as having a total exchange capacity equal to 1.55 milliequivalents per milliliter, which is about 77% of the original capacity of the resin ion exchanger The No. 1 anion exchange unit was responsible for Dowex having a capacity for separating salt equal to 0.44 milliequivalents per milliliter, or approximately 34% of the original capacity; it has been tested as having 0.45 milliequivalents per milliliter of weak groups

  basic when no weakly basic group is detected

  table on new frank resin; she had a capa-

  total exchange city of 0.89 milliequivalents per milliliter,

  corresponding to around 68% of the original capacity.

  The No. 2 anion exchange resin unit was charged with "IRA-402" from Rohm & Haas and it was tested as having 0.38 milliequivalents per milliliter of separation capacity

  of salt, which is about 29% of the original capacity.

  The weakly basic capacity of this resin was tested as being 0.71 milliequivalents per milliliter although it is not possible to detect a weakly basic capacity on a new fresh resin. The total exchange capacity of this anionic resin was 1 .09 milliequivalents per milliliter, which turns out to be 84% compared to the

  capacity of the original new fresh resin.

  Treatment of cation exchange resins with

  Alcian blue dye indicated the presence of polysacchari-

  such as bacterial silt, wood sugars and

silt-forming bacteria.

  As noted above, the anionic resins were dark in color, formed small clumps and had a white coating which dissolved only with a con-

  prolonged tact with a hot caustic product Again.

  although no analyzes have been done, this hot caustic dissolution would be typical of silicate deposits which would tend to form when soluble silicates pass over an acidic resin, for example a resin having

  high percentages of weakly basic groups.

  Each of the 3 units was initially treated with a batch treatment containing 2500 ppm of a combined product, which contained the nonionic surfactant and the biodispersant preferred according to the invention. In addition, 250 ppm of chlorine was added (under form of sodium hypochloride} based on 2 volumes of water bed The treatment of the anionic resin units also included the addition of

  l O Oppm of a quaternary amine biocide.

  The units were opened, the water drained up to approx.

  15 cm above the resin, and the chemicals listed above were added Water temperatures were

  between 29.5 and 320 C during the addition of these pro-

  chemical duits The units were soaked with an air lance immediately then every hour for 4 hours The foaming inside the units was excessive and the air purging was stopped when the foam was

  appeared at the top of each of the resin bed units.

  Each of the units was then backwashed to cébar-

  until the effluents no longer contain particulate matter and little or no foam is observed. This required approximately 45 minutes for the cationic resin bed units and approximately 75 minutes for each.

  anionic units O The three units were then regenerated

rees in a normal way.

  The preventive maintenance treatment started immediately-

  following the discontinuous cleaning of the cation unit n 1 and also of the anion unit n 1 The anion unit n 2 was left without any other treatment in order to be able to compare the performance of this unit with the anion unit nl to thus compare two identical units while having the possibility of observing the effect of the periodic maintenance treatment as a function of the performance of the unit only exposed to a

discontinuous cleaning treatment.

  The preventive maintenance or maintenance program includes

  was taking 80 ppm of a 25% aqueous solution of the combined product formed of a non-ionic surfactant and a biodispersant for the first 10 minutes of

  each backwash with continuation, for 20 minutes

  tes, backwashing with standard cleaning water and subsequently normal regeneration Table 2 presents data comparing the results obtained with these field tests.

TABLE II-

  CAPACITIES OF F Oi CTIOMNEDOENT BEFORE AND AFTER TREATMENT Days Cationic unit Anionic unit Anionic unit N 1, cleaned, N 2, cleaned N 3, cleaned, more maintenance only more preventive preventive maintenance Cleaned unit Cleaned unit more maintenance no more

preventive start full treatment

  cement 211 960 1 to 140 045 1 of 68 130 1 above the less than *% less than * 2 pre quantity (leakage of (sight leakage to the silica screen) silica) measurement profile, l, ", ,, 4,158,970 1 Cleaning plus

less than "start of hand-

your preventive

113 5501 -

  Regeneration 75,700 1 left 6 before leaking to the device of 113,550 1 of measurement (leak less than silica) 8401 68 130 1 left 7 to the measuring device (leak of silica) $ above the quantity provided at the measuring device * W the quantity provided at the measuring device j I - Careful observation of the results in the table shows the effects of cleaning and the effects of the preventive maintenance program The personnel using the installation were asked to monitor these units up to the actual end point, i.e. silica leaks for anionic units and a decrease in free mineral acidity

  for cationic units, Normally, in this installation

  lation, the demineralization units operated as an automatic stop device with a water meter When a predetermined number of liters of water had passed through the units, the units were automatically backwashed,

  regenerated and rinsed before being exposed to the necessary water

  both this treatment In the case of anionic units, the normal operating times went far beyond

  of silica leakage Our tests indicated that the uni-

  Anionic tees no longer lost capacity, but that cleaning according to the discontinuous system of the invention did not increase operating capacity This is not very surprising because the results relating to the original resins indicate that these resins have dramatically deteriorated

  to the point that the continuation of this trial was questionable.

  However, the preventive maintenance program indicated that the extent of fouling was reduced beyond the reductions obtained using the cleaning process

discontinuous.

  The results of this evaluation also indicated that the surface coating fouling the cationic resin was removed and that the flow rate for this resin was increased by 908,400 liters per operating time to 1,021,950

  liters per operating time A subsequent application

  quente of the preventive maintenance dose according to the invention a

  helped maintain this significant increase in volume processed.

  Ionically fouled anionic resins have no

  initially no change in volume treated Cepenr-

  dmimim with these relatively short tests, where these ionically fouled anionic resins have not shown further decreases in operating capabilities and characteristics. The preventive maintenance program continued for approximately 14 months. During this period, the service life-

  on strongly basic and severe anionic resins

  fouled have improved by about 643,450 to 860,000 liters and have been maintained at this level for the last four months of this 14 month period Water quality

  total demineralization line was also considered

significantly improved.

  The observation that the chemical capacity, that is to say the

  salt separation capacity, no longer decreased but has at the

  milking slightly increased is also remarkable In spring

  cipe, the tests shown in Figure 4 indicate that 1 Uap-

  implementation of the preventive maintenance program has increased the life of the resin by at least 19 months and has successfully decomposed anionic resin beds considered to be irreversibly fouled It is interesting that

  the total exchange capacities of the resins treated according to the

  vention by a preventive maintenance program remained

  unchanged throughout the length of this test This indicates

  that the invention completely inhibits and prevents further degradation of the resins and inhibits and prevents losses

  additional exchange capacities for this type of resin.

  In summary, this comparison of the field tests, in particular of the two lines of anionic units, indicates that

  the demineralization lines had a capacity which increased

  dually decreased over a period of approximately 2 or 3 years.

  This gradual decrease in efficiency was attributed to a degradation of the resin plus an excessive accumulation of natural organic fouling agents and microorganisms as well as their waste, originating from natural waters as well

  that a sewage treatment plant discharges

  giant, upstream, in the waters brought to these demining lines

  This field test compared both a net-

  discontinuous toy using the chemicals of the

  vention and the preventive maintenance program using these chemical products when applied to anionic and cationic units forming the demineralization lines.

  tion in this production location The disconti-

  cleaning or cleaning showed no appreciable measurable effect, although the total durations of use

  showed a gradual increase.

  After the discontinuous treatment, a feed pump was connected to the backwashing line of the anionic unit and the chemicals of the invention were brought to backwashing water during the first third of the

  total backwash cycle 30 minutes before each regeneration

  The chemical supply was 80 ppm in

  based on the total volume of treated water

  There were no other chemical treatments on these units. At the time when the preventive maintenance program was started, the total capacity of the unit to which this backwash system was connected was 567,750 liters. This operating time slowly and gradually improved over the following 14 months until total duration

of 859,200 liters.

  It is also extremely remarkable that the resin

  of this ignionion has only 29% of its separation capacity

  original salt ration and 84% of its total ori

  gine, when this test was started A rechecking of the capacities of this resin about 13 months later indicated

  that the resin had 30% of its original capacity to separate

  tion of salt, indicating a gain of approximately 10% of the total chemically available exchange capacity. This indicates that the continued use in preventive maintenance of the chemicals of the invention reduces further chemical degradation of these anionic resins. The products chemicals used throughout this test were a 1: 1 mixture of an ethoxylated nonylphenol containing 9 moles of ethylene oxide and a biodispersant that had been synthesized by condensing ethylene oxide with a product of addition of propylene oxide on propylene glycol, to give a product having a molecular weight of about 1500-5000 and a value

of HLB between 4 and 10.

EXAMPLE 5

  An oil refinery on the Gulf Coast had 7 demineralizing lines with a problem of loss of ion exchange capacity and requiring long rinsing with water and long regenerations Resin fouling due to

  various types of natural and synthetic organic matter

  as well as an accumulation of microorganisms and their wastes, was considered to be the major cause of these

  operating problems cationic and anionic resins

  that weakly basic of two lines of this demining system

  have been cleaned intermittently with the pro-

  chemical products of the invention followed by treatment of

  preventive maintenance of a line only Treatment available

  continuous cleaning slightly improved the performance of these lines The demineralizing line receiving no other preventive maintenance treatment remained at a bad level

  The demineralizing line, which has received the

  preventive maintenance using the chemicals of the invention, has shown appreciable improvement and

stable.

  Field tests at this C 6 te Gulf refinery were established to compare the results obtained.

  on a demineralizing line N O 1 compared to a half line

  néralisante n 2 Line n 1 was maintained according to the pra-

  standard ticks from this refinery, during long

time periods of this test.

  The demineralizing line No. 2 was placed in pro-

  grammedb preventive maintenance, requiring the addition of pro-

  chemical products of the invention in the first 10%, but not more than the first 50%, of the backwash cycle with

  then a standard regeneration and rinsing technique.

  The chemicals were added to each backwash over a period of about 9 months. The two demineralizing lines were initially backwashed and cleaned using the batch treatment described above and using the chemicals of the invention. cleaning, installation personnel had cleaned the resins throughout the demineralizer system with caustic and regeneration chemicals, approximately 2 to 3 months

  before starting the on-site test.

  The results of the batch cleaning which followed very closely the full cleaning of the resins indicated only slight improvements in the regeneration of the resin capacity as well as the use of chemicals and the use of water, in addition to water quality However, this slight improvement was observed on the line

  having received the treatment according to the invention.

  However, the line receiving the maintenance treatment

  preventive, recovery and restoration according to the invention

  tion has slowly noticeably improved the performance of the resin, as well for the high-pressure resin as for the anionic resin, in this demineralizing line until the

  resin has almost recovered all of its original capacity

  tial to treat waters containing an ionic species.

  This installation has remained under the restoration program.

  preventive rationing and maintenance until now The results

  states continue to indicate that resins, as well-

  both ionic and anionic, contained in this demineral-

  have kept their maximum resin capacity and their maximum salt separation capacity; Also reveal that no further degradation of the resin has occurred during the last 7 months of this particular test.

  on site Continuous improvement in the duration of use

  tion of this demineralization sequence was recorded by the personnel of this refinery on the Gulf Coast Tables III, IV, V, VI and Figures 5, 6, 70 8, 9, 10, 11, and 12 show the results obtained by monitoring the resin system during the preventive maintenance program used to recover, improve and maintain the performance of these water treatment exchange resins

TABLE Ill

  _________ RESINS CHAGEUSES OF ION DA "NS DE'S LINES OF D 12 14 INIERA'LISATION

  te Replaced blume TE b tolibSSCC C / CiSscd / or & lx perl es Fouling mfle c'1 I (previous) _ (m 3) (mqil CE Cb (çjk 3 SSCC 3 / sccd IRC assees org anique C 120-î: 0 / 00, (7/76) 9,971.69 89 53.0 3 N Nf WB 68/8 (W 378 M 8-) 8.57 714 71 O grand SB 402 11/78 r 10/8913 1.03 76 O , 77 57 5 grand c10 + 110 f 8/76) 9.97 1.59 82 54.7 5 d 68 1 l / 80 (5/780) 8.57 896 89 rn SB 402 8 d / 76 9.13 0.93 68 0.58 42 5 large c 120 e-, 1 l / 8 (674 '9971.69 89 52.9 3 i B 68 1/1 (/) 57 911 77 O moderate SB 402 11/81 ( 6 / la) 9,131.18 87 1.15 85 2 moderate 4 C 120 11/81 (1/79) 9,971.8 99 5,292 T-ô Niit 4M 94 11/81 (1/79) 3.57 578 70 2 moderate SB 3 402 1/79 (1/64) 9, 131.02 76 0, 84 62 5 moderate c 120 5/70 1279) 9.97 177 I * 90 T OB 94 5/81 (5/78) 83 , 57 57 820 2 3 gr Nd SI 3 402 7/76 9.13 0.99 73 0.70 52 5 large ic 120 2 / 999.46 77 N 1 WB68 12/80 8.57 N Nf 685mdr 1 SB 40210 / 77 9.13 03.99 83 0, 70 58 1 e1 rn

2 C 120 1/79 9.97 1.47 77 5 220 5 N

  2 WB68 24/80 8.7 96 852 moderate 2 SB 402 47 9.13 13.00 83 1.00 66 35 large a Analyzes by Ionsd's Echanae Laboratory SCO Capct nptt oon b, TEC = total exchange capacity e WR capacity den reentitcoon dea c SSCI = salt separation capacity f NN = not particularly noted in the analysis report w OI Co

TABLE IV

PERFORMANCE

  Operating data for final S i O 2 (ppn) 0.011 0.014 0.014

0, O 11

0.011 0.011

_ 0.017

0.014 0.014 0.014 0.014

0.0147

  0.017 0.014 0.011 0.014 0.017 0.028 0.014 0.014 0.020

Conduc -

  final activity (pt 3 4. p F ondtr-t. base- weak 4 - '28 _ -41 demineralizing line N 02 S j Re gener a

tion tota-

840,000

899,000

883,000

891,400

-928,000.

915,600

819,500

211,200 '

832,700

883,800

767,200

981,400

813,400

811,900

794,800

-757,000

853,100

835,300

957,600

964,000

I. Total operation in liters

3,659,700

4.760 or 000-

4.261 600-

4,062,800

3,820,600

3.3-08 800

3.266 500

4,792,200

4,049,900

4,290,300

3,533,300

4,315,000

4,209,700

3,577,600.

3,537,500

3,525,300

3,611,300

4.123 800

3,890,600

4,591,200

4,542,400

4.000000

4,736,900

q Day i il 16- I M -, k -j

TABLE V

PERFORMANCE

  Operating data of the final i Sj O 2 (pm

0.001 -

0.017 0.014 0.014 0.014 0.014 0.017

0.014, '0.014 0.017 0.014 0.014

0.0 014

  0.011 0.017 0.017 0.014 0.014 0.017 0.019 0.011

I Conduc-

  final activity (-4 Condurt. ase- a ible-j -18 mined irnne Re genera

tion tota-

the in itres

832,700

846,700

958,700.

801,700

885,300

825,900

8-55,400

912,200

921,300

988,000

977,300

837,000

969,300

* 889,000

014,000

500

944,300

922,400

964,400

500

_ 097 600

999,200 o

.0140400

Realizing N 02 Fonc tiornnement

total-

in liters

4,715,200

5,028,000

4,696,400

4,731,200

4,846,300

3,982,600

4,887,600

5,969,300

* 5,677,500

5,043,500

* 4.372 400

, 352,400

4,357,700

* 3 976 100 '

* 4.478 400

4,153,300

3,799,800

5,236,900

4,215,700

3.245 300

5,166,100

i 30 p v 1.r "KY T, i s

0011009, P

009,999, ú

00 EIL 9 LIE

00 LIVE 119

001 IL 9 to 19

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OOEIVEZIP

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07,0,10

im, o o ', o

L -10 "W

900 O ilo, O t'10 O LTO O t Io 'Io

TIO ', O

  1-ro ', OT Io ,, O c Io' O 1-ro ', O ilo', O -rio, OL 9 t'9 ú 9 Z 9 LS 9 s ss s ES Es is M 6 9 C nor 9 oz la S 'i 19 là 9 la z 1 -laz 1 Il z 1 I 18 1 i 19 al, 9 go 8 ass si 6 las ce 8 la 8- as 9 las le 9 ta Il E: sui E: 009' -LTL't, OOL 1 M 1 t,

OOZ'6910 P

  0 o 91 o Zc 1 006, 090, t, 000, loi, 9

OOL'ZLP'S

00 ú 1 M 1-9

00 CIT 9015

006 '69 Z'S

0061 úúLIP

009, OOZIS

OOLIESSIS

OOP'SG 6 'P

001.99119

   T 8; 92 z-îl ue E eq 01 (1) G-rru-tj G: Yr A: 1 -On PUOD (mdd luuîg z O '; s pp au 3-'j VI ap luatuauuo-tlouoj ep saauuo (j M fi sui 91.-1

EXAMPLE 6

  Finally, a test was carried out in a chemical installation.

  that in a 4 state of the% ddle of the United States of America This installation used two water softeners for its low pressure boiler system, using a standard ion exchange technology The durations of use of this installation were only around 193,000 liters, although the capacity of the resin was greater than 80% of the initial capacity but less than 90% of this This on-site test was intended to demonstrate that the program preventive maintenance itself was able to

  restore, improve and maintain the performance of these solids

  water treatment and these ion exchange resins which were fouled with iron, organic substances,

  microorganisms, and microorganism waste.

  The operating processes have not been changed during the

  during this test No discontinuous cleaning of this resin was carried out, but simply a preventive maintenance program was started, consisting in treating cyclically,

  ion exchange resins in softening units

  water from this installation, with an effective quantity

  of a non-ionic surfactant and a biodisper

  health according to the invention This treatment was increased by

  the addition, with the non-ionic surfactant and the bio-

  dispersant described above, of an ammonium quater biocide-

  nary. The nonionic surfactant chosen was again

  the product -addition of ethylene oxide on an alkyl phenol-

  with an HLB value of approximately 13-14 The biodispersant chosen to carry out these tests was a condensate of ethylene oxide on adducts of propylene oxide on propylene glycol This biodispersant had a molecular weight between 1500 and 3000 and an HLB value

between 7 and 8.

  The resin beds were treated by adding approximately ppm of a product comprising a 1: 1 weight ratio of the nonionic surfactant to the biodispersant, to the resins

  anionic contained in this water softening unit.

  The addition was made during the first third of the backwash cycle and was followed by a bed rinse during the

  Next 2/3 of the backwash cycle, followed by techniques

  ques regeneration standards The cationic resin beds

  which have been backwashed using 20 ppm of the above formula and, in addition, an effective amount of a biocidal compound quaternary ammonium salt Again, the cleaning solution containing the nonionic surfactant and the, biodispersant as well as the biocide, was added during the

  first third of the backwash cycle, followed by a rinse

  cleaning chemicals during the last two-thirds of the backwash cycle; then standard regeneration chemicals and techniques were used

standard rinse.

  Results indicated that total usage times increased from an initial value of 193,000 liters to approximately 261,000 liters in a two-week period After the first month, usage times

  had stabilized at around 261,000 liters and were reduced

  carried out at a constant value of 238,000 liters to put

  this automatic control system for ease of operation

  rators of this chemical plant This plant has operated successfully and continuously at this value of 238,000 liters, without any indicated loss of capacity

  resin or ion separation capacity,

for about 6 months.

  This last on-site test indicates the successful use of the

  preventive maintenance program alone without requiring an operation

  Previous discontinuous cleaning ration Such a program avoids downtime of the demineralization line, thus avoiding downtime in the production of steam and downtime in the operation of

chemical treatment.

EXAMPLE 7

  It can be expected that, if a system is started up with a newly charged free ion exchange resin, and if this system is treated as described above with the preventive maintenance program using the chemicals of the invention, this system can be maintained at an optimal capacity of the resin, an optimal capacity for separating salt and optimal useful lives for a greatly improved period of time.

  system operating with the advantages of the invention allows

  relates to considerable savings to the user on costs normally incurred in the use of water, the use of regenerating chemicals, operating outages, costs

  resin replacement and labor costs.

EXAMPLE 8

  A domestic water softening unit was

  severely fouled by accumulated debris, agents

  organic taminants, micro-biological growth and their residues The domestic water softening unit did not have a backwashing cycle before regeneration but instead went directly from operation to regeneration,

  then to a rinse cycle, and back into operation.

  The formula from Example 1 was added directly to

  concentrated Na Cl brine, which was used to regenerate

  rer this water softening unit Concentrations were around 2000 ppm and normal regeneration

  with brine including the chemical formulation of the example

  ple 1 was followed by the normal rinse cycle which removed the

  excess brine and any residual chemicals

  significant amounts of accumulated organic, inorganic and biological debris have been removed from the resin used in this domestic water softener Continuous treatment during each regeneration and rinse cycle using 10 to 200 ppm of agent-containing formulations

25366? 8

  nonionic surfactant, a nonionic biodispersant and a fatty quaternary amine salt biocide almost maintained the

  resin in this unit to its original effectiveness.

EXAMPLE 9

  The formulas of Example 8 were found to be only slightly soluble in the concentrated brine used for

  regenerate domestic water softening units.

  To improve the contact of the resin bed with the formulations according to the invention, various coupling agents were used. These agents included materials with high HIB having an HLB value between approximately 12 and approximately 30. More particularly, the addition, up to in equal amounts, the following compounds appear to improve the solubility of the formulation of

Example 1:

  Coupling agents 1 Triton DF-20 'Rohm & Haas, modified ethoxylated alcohol;

  2 Triton X-114 "Rohm & Haas, octyl phenoxy-polyethoxy-

ethanol;

  3. "Diacid 1550 'Westvaco, dimeric acid.

  Addition of formulations can be expected

  according to the invention, coupled with semi-coupling agents

  blable or identical to those given above, operates in a process to improve and maintain the performance of water treatment solids which are or tend to be fouled with organic substances, microbiological growth and their residues The process must include the cyclic addition of these formulations, with the coupling agent as described above, to each regenerating cycle or backwashing cycle, if separated, followed by a rinse cycle to remove chemicals

  regenerants as well as the formulations according to the invention,

  taking coupling agents, if their use is necessary to maintain solubility or dispersibility

  complete in regenerating brine solutions.

  In summary, it can be said that treating contaminated resins with surfactants and biodispersants will significantly improve performance characteristics

  resins If we compare to the treatments commonly available

  differences in industry, the differences in restoring the performance of exchangeable resins

  ion geuses are quite sensitive In addition, the new

  strongly decrease the bacterial growth on the resin and reduce the probability of a discharge of large quantities of bacteria in the treated water supply. The physical rupture of the resins is reduced when the particles and the bacterial waste no longer accumulate and cause more

  excessive pressure drop in the unit.

  The current mode of operation of an ion exchange unit is to let the unit operate until it

  is contaminated and until functional difficulties-

  are too important to continue using

  unit If cleaning the resin does not show the results

  desired states, resin is replaced This is commonly accepted practice because the user of the units

  ion exchange has no other choice.

  The present invention provides (1) A means of preventing the accumulation of organic and microbiological fouling agents by treatment of

  resins frankly loaded before or during each counter

  washing and regeneration cycle with surfactant

  non-ionic and the biodispersant according to the invention, -

  (2) A means to improve and maintain performance

  of these resins using the above cyclic treatments

  above described; and (3) The recovery of the lost capacity of the resin due to, the fouling of these resins by materials

  organic, microorganisms and their wastes.

  The benefits of such treatment programs include

  the following (1) Resins can be kept in good condition

  tion and can be used at a reasonable price

  soundly low for regeneration and operation, and (2) the buildup of contaminants in a resin unit will be kept to a minimum, reducing the amount of broken resin beads For these reasons, the savings can expect from the present invention may be sensitive Likewise, the resin bed will no longer provide excessive amounts of food to bacteria, and the treated water will be less contaminated with bacteria, which is a

  important consideration in cases where treated water is used

  used in the food industry for beverage or

  drinking water or for pharmaceutical uses.

  The use of activated carbon and other adsorptive agents

  bants for the pretreatment of ion exchange units is an accepted practice They are used to remove water, 1 dilore, organic matter, iron and various particles, before the ion exchange treatment The use of the present invention s has been shown to expand the use of these

  adsorbents over a longer period of time and

ter the growth of bacteria.

  The possibilities of application of the agents and of the process of the present invention are not limited to ion exchange resins or adsorbent agents. Other products accumulating organic matter, bacteria and bacterial waste, such as, for example, membranes. osmosis

  reverse, ultrafiltration or dialysis can be net-.

  Used and maintained by the techniques described.

Claims (7)

  1 Improved backwashing process of ion exchange resins, characterized in that it consists in undertaking said backwashing operations in the presence of a revitalizing agent which is present in the backwashing cycle, during at most the first 50 % of operation backwash.   2 Method according to claim 1, characterized in that it is implemented during practically each backwash cycle.   3 Method according to one of claims 1 and 2,   characterized by the fact that the conditioning agent is   killed by a nonionic surfactant and a bio-dispersant   health. 4 Method according to claim 3, characterized   by the fact that a biocide is used with the surfactant   non-ionic active and bio-dispersant.   Method according to one of claims 3 and 4,   characterized in that the nonionic surfactant has a hydrophilic / lipophilic balance value (HLB) included between 6 and 14.   6 Method according to one of claims 3 and 4,   characterized by the fact that a biodispersant capa-   ble to produce at least a 20.0% biomass change evaluated with a biometer at a treatment rate of 10 ppm   for one hour at around 37.8 C.   7 Method according to claim 6, characterized in that the biodispersant is chosen from the group formed by ethylene oxide condensates with adducts of propylene oxide on propylene glycol having a hydrophilic balance value / lipophilic (HLB) between 4 and 10 and having a molecular weight between 1500 and 5000, non-ionic polyethoxylated straight chain alcohols, tris-cyanoethylated cocodiamines, polyoxyethylene sorbitan-ester acids, N, Ndimethyl-stearamide   non-ionic and non-ionic polyglycol-amine condensates.   8 Method according to claim 4, characterized in that the biocide is chosen from the group formed by biocides of fatty quaternary ammonium salt, substituted bromonitrilo biocides, isothiazolines and oxidative inorganic biocides.   9 Method according to one of claims 1 to 8,   characterized in that the ion exchange resin is selected from the group consisting of cationic gel-type resins, anionic gel-type resins, cationic macroporous resins and anionic macroporous resins.