Dealkalization and Softening with Lewatit CNP 80 / S 8528 S 1467 / S 1468 MonoPlus S 100 H MonoPlus M600

Data for part demineralization with Coflow, Stratabed and Split Stream processes

Table of contents
TABLE OF CONTENTS.....................................................................................................................................................2 1 DEALKALIZATION AND SOFTENING WITH COFLOW SYSTEM ................................................................3 1.1 GENERAL INFORMATION .........................................................................................................................................3 1.2 ION EXCHANGE SYSTEMS ........................................................................................................................................3 1.3 RECOMMENDED LEWATIT RESINS ......................................................................................................................4 1.4 OPERATING CAPACITY LEWATIT CNP 80/S 8528...............................................................................................5 1.5 REGENERANT ..........................................................................................................................................................7 1.6 OPERATING CAPACITY LEWATIT S 1467 / S1468................................................................................................7 1.6.1 Operating capacity: standard conditions.......................................................................................................7 2 DEALKALIZATION AND SOFTENING WITH SPLIT STREAM PROCESS...................................................9 2.1 2.2 3 GENERAL DESCRIPTION ...........................................................................................................................................9 OPERATING CAPACITY LEWATIT MONOPLUS S100 H.....................................................................................10

DEALKALIZATION AND SOFTENING WITH STRATA BED SYSTEM.......................................................11 3.1 3.2 3.3 3.4 GENERAL DESCRIPTION .........................................................................................................................................11 OPERATING CAPACITY ..........................................................................................................................................12 START UP ..............................................................................................................................................................12 REGENERANTS AND REGENERATION SEQUENCES ..................................................................................................13

SOFTENING AND DEALKALIZATION WITH LEWATIT S 1467 AND MONOPLUS M 600....................13 4.1 4.2 4.3 GENERAL DESCRIPTION .........................................................................................................................................13 OPERATING CAPACITY ..........................................................................................................................................15 REGENERATION AND SERVICE CONDITIONS FOR LEWATIT MONOPLUS M600.....................................................15

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1
1.1

Dealkalization and Softening with Coflow System

General information

When the feed water is both high in hardness and alkalinity and has hardness to alkalinity ratios of 1or more, dealkalization using a weakly dissociated cation exchange resin becomes extremely efficient and cost effective. The aim of dealkalization and softening is to remove the HCO3- ions and the alkaline earth ions from the water to be treated. To remove the carbon dioxide released from the bicarbonate alkalinity, use is made of degassers, which are either located between the filter units filled with LEWATIT CNP 80 and LEWATIT S 1467 (Fig. 1) or downstream the last filter unit (Fig. 2). The overall salt content is reduced by the amount of the bicarbonate alkalinity. A very small amount of caustic soda may have to be fed to raise the final effluent pH to the required levels.

1.2

Filter arrangements

The most common form of dealkalization and softening is an arrangement in which the weakly acidic cation exchange resin LEWATIT CNP 80 (H-form) is followed by a softener filter unit filled with a strongly acidic cation exchange resin (LEWATIT S 1467) in Na-form. The placement of the degasser between both filter units allows to neutralize the effluent after degassing with caustic (NaOH) before going into the softener column. With this set-up the softener column does not have to be rubber-lined. The economy of that process is also improved, since the used LEWATIT S 1467 can be used at full capacity. Other processes like split stream systems (Fig. 3), stratabed process (Fig. 4) or the use of a type II resin for salt splitting dealkalization are explained in chapters 2-4.

Dealkalization and Softening Degasser placed between the filter units

Figure 1 Page 3 of 15

Where the degasser is installed downstream the filter units the LEWATIT S 1467 assumes two functions: Adsorption of the non-carbonate hardness Partial buffering of the carbon dioxide released from the bicarbonate alkalinity

Since the adsorbed H+ ions are displaced by the Ca2+ and Mg2+ ions which are also adsorbed, it is difficult to calculate their occurrence in the effluent of the LEWATIT S 1467 indicated by a drop in the pH to the mineral acid range particularly as the content of bicarbonate alkalinity in the raw water differs from case to case. Experience has shown that, in this case, the operating capacity can only be estimated at 0.5 till max. 0.7 eq/l. For this case, a regenerant level of 200-220 g NaCl 100% per l LEWATIT S 1467 will be needed.

Dealkalization and Softening Degasser placed downstream the filter units

FEED

Figure 2

1.3

Recommended LEWATIT resins

In case of drinking water applications we recommend to use the food grade qualies: LEWATIT S 8528 and LEWATIT S 1468. For normal industrial water applications we recommend to use LEWATIT S 1467 and LEWATIT CNP 80. For the Split Stream process we recommend to use LEWATIT CNP 80 and LEWATIT MonoPlusS100 H.

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Operating capacity LEWATIT CNP 80/S 8528

The Lewatit CNP 80 WS is used almost exclusively in dealkalisation (by the cocurrent process!) and in demineralisation using the compound fluidised bed system. The chemical demand in the dealkalisation application is approx. 103-105% of the theoretical value depending on the bicarbonate concentration of the water to be treated. The capacities shown in Diagram 1 apply to waters which besides the carbonate hardness also contain noncarbonate hardness whose proportion in the total hardness is at least 10%. This is normally so in most raw waters. If the proportion of non-carbonate hardness is lower than 10% of the total hardness or if the total hardness of the raw water is lower than the concentration of the bicarbonate ions ( so called alkaline water ), the operating capacity should be read from Diagram 2. For these so called alkaline waters the operating capacities decreases considerably as the quotient of total hardness/bicarbonate ions becomes smaller. The correction factor for the operating capacity as a function of the temperature of the feed is shown in Diagram 3

Operating capacity of Lewatit CNP 80 WS as a function of operating time

2,7 2,5

Operating capacity [ eq/l ]

2,3 2,1 1,9 1,7 1,5 1,3 1,1 0,9 0,7 0,5 4 9 14 19 24 29 34 39 44 49 54

Chemical demand

- 103 - 105% of theory - 120 % of theory

Operating time [ h ]

Operating Capacity CNP80, B. Brings, ION

Diagram 1

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Correction factor Lewatit CNP 80 WS as a function of the hardness/alkalinity ratio and total salt concentration
1,05 1 0,95 0,9 0,85 0,8 0,75 0,7 0,65 0,6 0,55 0,5 0,45 0,4 0,35 0,3 0,25 0,2 2 4 6 8 10 12 14 16
1,2

Correction factor operating capacity

1,0

0,2 Hardness/Alkalinity ratio 0,4 Hardness/Alkalinity ratio 0,6 Hardness/Alkalinity rartio 0,8 Hardness/Alkalinity ratio 0,8 1,0 Hardness/Alkalinity ratio 1,2 Hardness/Alkalinity ratio

0,6

0,4

0,2

18

20

Total salt concentration [ meq/l ]

Operating Capacity CNP80, B. Brings, ION

Diagram 2

Correction factor for Lewatit CNP 80 WS as a function of water temperature

1,15 1,1 Correction factor for operating capacity 1,05 1 0,95 0,9 0,85 0,8 0,75 0,7 0,65 0,6 5 7 9 11 13 15 17 19 21 23 25 27

Temperature [ C ]
Operating Capacity CNP80, B. Brings, ION

Diagram 3

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1.4

Regenerant

Hydrochloric acid is usually used for regeneration. Sulphuric acid is also possible, but only at very low concentrations, otherwise precipitation of calcium sulphate in the resin bed may occur. The concentration for hydrochloric acid should be 3%. Higher concentrations (up to 6%) do not involve any disadvantages. The concentration for sulphuric acid should be in the range from 0,7% till max. 1%. Mineral acid in the treated water with a pH of < 4,3 is always the result of over-regeneration. This overregeneration can also occur if the preceding cycle was interrupted prematurely and regeneration was still carried out with the usual amount of acid. This can be corrected by short, intensive backwashing aimed at bringing about a restratification of the weakly acidic cation exchange resin.

1.5

Operating capacity LEWATIT S 1467 / S1468

Diagram 4 shows the operating capacities of LEWATIT S 1467/1468 as a function of regenerant dosage and process mode. The operating capacities apply to the Na supply form of the resins and an endpoint of 0.5 meq/l hardness. The operating capacity illustrated here is gross capacity excluding sodium leakage (Diagram 5). For more detail information please refer to the Engineering Information Softening with Lewatit.

1.5.1 Operating capacity: standard conditions

Standard conditions - Resin as delivered ( Na form ) - Water temperature 15 C - Endpoint 0,5 meq/l hardness - Brine concentration 10 % - Resin bed depth min. 800 mm - Resin bed depth max. 3000 mm - Brine injection time min. 20 minutes - Linear flow up to 40 m/h - Specific flow rate 20 BV/h - Regenerant: NaCl, 10 %

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Operating capacity Lewatit S 1467/S 1468 as a function of regenerant level in coflow and counter-flow operation
1,8

1,6

Operating capacity [ eq/l ]

1,4

1,2

Counter flow

Coflow

0,8

0,6

0,4

0,2

0 0 50 100 150 200 250 300 350

NaCl [ g/l ]
Operating capacity S1467/S1468, B. Brings

Diagram 4

Hardness leakage of Lewatit S 1467 / S 1468 as a function of regenerant level

0,25

0,2

Hardness leakage [ meq/l ]

0,036 meq/l hardness = 0,1 d

0,15 Co-flow regeneration Counter-flow regeneration

0,1

0,05

0 50 100 150 200 250 300

NaCl [ g/l ]

Nr. 2 Operating capacity S 1467/S1468 , B. Brings

Diagram 5

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Dealkalization and Softening with Split Stream Process

2.1 General description

In cases where the bicarbonate concentration of the water to be treated is subject to strong fluctuations or its quantity is close to the value for the total hardness or even exceeds it, it is advisable to use the so called split stream process, consisting of two parallel operated units operated with LEWATIT S 1467 ( Na-form ) and LEWATIT MonoPlus S 100 ( H-form ). The split stream process is particularly recommended as the composition of the feed water is, for a weakly acidic ion exchange resin, likely to result in an operating capacity below that of LEWATIT MonoPlus S 100 H (alkaline water). The split streams from the two filter units are adjusted with the support of a pH control so that the mineral acid formed from the neutral salts of the feed water reacts completely with bicarbonate ions of the softened water to achieve neutrality in the blended water (Fig. 3). Finally, the CO2 that is created by the FMA of the acidified water source and the alkalinity from the softened water source, get removed via degasser. Controlling the percentage of each flow in the blended water controls the amount of alkalinity in the treated water.

Dealkalization and Softening Split Stream Process

FEED Treated water FEED

HCl + NaHCO3 NaCl + H2CO3

Figure 3

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The split stream dealkalization process has the following advantages: Alkalinity in the final blend can be controlled to the required level TDS is removed to the extent that the alkalinity is removed The operating capacity of the SAC resins are higher than those of the Type II anion resin used in the salt-splitting process

The disadvantages include: The use of hazardous acid in the regeneration process is required The capital and operating cost are increased du to the need of a degasser The feed of small amounts of caustic may be required to raise the pH of the final effluent to acceptable levels

2.2 Operating capacity LEWATIT MonoPlus S100 H

The operating capacity is mainly determined by regenerant requirements. Other factors are the ratio of mono and bivalent cations and the proportion of hydrogen carbonate ions in the water to be treated. Diagram 6 shows the operating capacities of LEWATIT MonoPlus S100 for water where the sodium and bicarbonate content is 35 % of the total salt content. The operating capacities apply to the Na supply form of the resins and an endpoint of 10 S/cm (measured after the downstream strongly basic anion exchange resin). The correction factors for operating capacity as a function of the sodium and bicarbonate concentrations in the feedwater are shown in Diagram 7.

Operating capacity of LEWATIT MonoPlus S 100 as a function of regenerant dosage with coflow regeneration
1,70 1,60

Operating capacity [ meq/l ]

1,50 1,40 1,30 1,20 1,10 1,00 0,90 40 60 80 100 120 140 160 180 200

HCl [ g/l ]

Diagram 6 Page 10 of 15

Correction factor for LEWATIT MonoPlus S 100 as a function of ionic loading rate
Correction factor for operating capacity
1,1

1,08

1,06

1,04

1,02

0,98

0,96 0 10 20 30 40 50 60 70 80 90 100

Monovalent Cations and Bicarbonate [ % of total salt content ]

Factor Na+/ K+/ NH4+ percentile

Factor HCO3- percentile

Diagram 7

3 Dealkalization and Softening with Strata Bed System

3.1 General description

Stratified beds (Fig.4)can be used for treating raw waters where the equivalent ratio of hardness/bicarbonate is in the range of 0.4-0.9. The used LEWATIT CNP 80 is in the hydrogen form whereas the LEWATIT S 1467 operates in the sodium form. The treated water has an average alkalinity of 0.2 meq/l and a residual hardness of approx. 0.03 meq/. The free carbonic acid can be removed by a downstream degasser. The same water quality can be achieved in modern counter-current demineralization plants (e.g. VWS-System) using a double compartment for deacationization consisting of LEWATIT CNP 80 and LEWATIT MonoPlus S 100.

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Dealkalization and softening with strata bed system (quotient from hardness and alkalinity in the range of 0,4-0,9)

Figure 4

3.2 Operating capacity

The operating capacity of used LEWATIT CNP 80 is dependent on the cycle operating time ( Diagram 1 ). In the case of LEWATIT S 1467, an operating capacity of approx. 0,7 eq/l resin , referred only to the concentration of alkaline earth chlorides and sulphates, must be used. This prevents treated water effluent containing mineral acidity.

3.3 Start up
After backwash ( 5-7 m/h linear velocity ), 200 g/l NaCl per l LEWATIT S 1467 are passed through the entire filter unit as a 10% solution. Regeneration of the weakly acidic ion exchange resin is not necessary as filled in H-form.

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3.4 Regenerants and regeneration sequences

The stratified bed is initially regenerated with hydrochloric acid and subsequently with common salt solution. The quantity of HCl is calculated in equivalence to the operating capacity of the l LEWATIT CNP 80 and increased by the following regenerant factors: Bicarbonate concentration in the feeded water of Up to 2 meq/l by 1.01 2-5 meq/l by 1.03 5-10 meq/l by1.05 > 10 meq/l by1.08

These additions compensate for acid consumption when diluting the regenerant solution with raw water. The regenerant solution should contain 2-3 % HCl. If desired, an equivalent quantity and concentration for nitric acid can be used. 200 g NaCl/l are required as an 8-10% solution to regenerate LEWATIT S 1467.

The influent water can always be used for making up the regenerant solution, for displacement, backwash and rinsing. The system is regenerated downflow and is started without previous backwash in accordance with the following steps: Sequence Acid injection Acid displacement Backwash NaCl injection NaCl displacement Backwash Rinsing Time [ minutes ] 30 30 15-20 30 30 5 to the desired resiual hardness Flow rate [ m/h ) 5 5 10-12 5 5 10-12 at service flow rate

4 Softening and Salt Splitting Dealkalization with Lewatit S 1467 and Lewatit MonoPlus M 600
4.1 General description
The salt splitting dealkalization process (see Figure 5) probably is the most prevalent in commercial and light industrial applications and where low-pressure boiler systems are involved. The characteristic arrangement is the use of a softener (anion resin would foul if any hardness like calcium and magnesium found its way onto the resin) followed by a type II anion exchange resin (Lewatit MonoPlus M600) regenerated with common

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salt (NaCl) or more often common salt with a small amount of caustic soda (NaOH) added (e.g. by using a static mixer). Used in its chloride-form and regenerated with common salt solution LEWATIT MonoPlus M 600 removes bicarbonate ions to a large extend from the water to be treated and the anion exchange resin releases the corresponding quantity of chloride ions. At the same time, the sulphate and nitrate ions are also exchanged, which means that the treated water practically contains only chloride whereas the total dissolved solids remain unchanged. Therefore, levels of CO2 in a boilers condensate would decrease, resulting in lower amine usage. However, there may be no ability to increase the boilers cycles because the TDS in the make up water has not changed. In fact, the conductivity of the make up water actually may increase slightly. Salt splitting dealkalization has the following advantages:

Common salt is a non-hazardous material and can be used to regenerate both resin types Often, excess softener capacity can be converted to use as a dealkalizer

However, this process also has the following disadvantages:

The process does not remove any TDS (neutral exchange only) Anion resins are susceptible to fouling from organics and hardness passing the first softener unit Relatively low dealkalizer operating capacities (810 Kg/ft3 or 0,37-0,45 eq/l are achieved)

Salt splitting dealkalization with Lewatit MonoPlus M600 (used as single filter or downstresm a softener unit)

Figure 5 Page 14 of 15

4.2 Operating capacity

Diagram 8 shows the operating capacities of LEWATIT MonoPlus M 600 for HCO3- ions depending on the bicarbonate ion proportion of the total anion content of the feed water. The bicarbonate alkalinity leakage depends on the regeneration efficiency. If the resin is not optimized regenerated, some bicarbonates remain in the bottom of the resin bed. These ions are first to come off as leakage during next service cycle.

Operating capacity of Lewatit MonoPlus M600 as a function of ionic composition

0,4

0,35

Operating capacity for HCO 3 [ eq/l ]

0,3

0,25

0,2

0,15

0,1

0,05

0 0,1 0,2 0,3 0,4

-

0,5

0,6

0,7

0,8

0,9

Proportion of HCO3 in total anions including free CO2

Diagram 8

4.3 Regeneration and service conditions for Lewatit MonoPlus M600

Regenerant level for MonoPlus M600: 100 g/l NaCl, 100% as 10% solution 5 g/l NaOH, 100%

The addition of a small amount of caustic to the common salt regenerant solution will enhance the removal of alkalinity (plus silica) and increase the capacity for CO2 because bicarbonate ions exchange more efficiently with hydroxide ions than with chloride ions. This also results in a higher effluent pH. If possible both chemicals are injected after get mixed together. Service flow rate: 5-20 m/h. The endpoint is defined by the m-value (alkalinity) of 0,5-1 meq/l. Regenerant level for Lewatit S 1467 please see chapter 1.6.

This information and our technical advice - whether verbal, in writing or by the way of trials - are given in good faith but without warranty, and this also applies where proprietary rights of third parties are involved. Our advice does not release you from the obligation to check its validity and to test our products as to their suitability for the intended processes and uses. The application, use and processing of our products manufactured by you on the basis of our technical advice are beyond our control and, therefore, entirely your own responsibility. Our products are sold in accordance with the current version of our General Conditions of Sale and Delivery.

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