Tech Manual Excerpt

FILMTEC Membranes Water Chemistry and Pretreatment: Calcium Carbonate Scale Prevention
Brackish Water For brackish waters with TDS < 10,000 mg/L in the concentrate stream, the Langelier Saturation Index (LSI) is used to express the scaling potential for calcium carbonate /6/. The following data are needed to calculate the LSI of the concentrate stream (LSIc): Caf = Calcium concentration in feed as CaCO3, mg/L TDSf = Concentration of total dissolved solids in the feed, mg/L Alkf = Alkalinity in feed as CaCO3, mg/L pHf = pH of the feed solution T = Temperature of the feed solution Y = Recovery of the reverse osmosis system, expressed as a decimal Calculations 1. Calculate the calcium concentration in the concentrate stream, Cac, as CaCO3 in mg/L:
1 Ca c = Ca f 1 Y

Eq. 6

2. Calculate the total dissolved solids in the concentrate stream, TDSc in mg/L: 1 TDS c = TDS f 1 Y 3. Calculate the alkalinity in the concentrate stream, Alkc, as CaCO3 in mg/L:
1 Alk c = Alk f 1 Y

Eq. 7

Eq. 8

4. Calculate the free carbon dioxide content (C) in the concentrate stream by assuming that the CO2 concentration in the concentrate is equal to the CO2 concentration in the feed: Cc = Cf. The concentration of free carbon dioxide in the feed solution is obtained from Figure 2.2 as a function of the alkalinity and the pH of the feed solution. 5. Calculate the pH of the concentrate stream (pHc) using the ratio of alkalinity Alkc to free CO2 in the concentrate, Figure 2.2. 6. From Figure 2.3 obtain: pCa as a function of Cac, pAlk as a function of Alkc, C as a function of TDSc and temperature (temperature of the concentrate is assumed equal to temperature of the feed solution). 7. Calculate pH at which the concentrate stream is saturated with CaCO3 (pHs) as follows: pHs = pCa + pAlk +" C" Eq. 9 8. Calculate the Langelier Saturation Index of the concentrate (LSIc) as follows:
LSIc = pHc pHs

Eq. 10

Adjustments of LSIc In most natural waters, LSIc would be positive without pretreatment. To control CaCO3 scaling, LSIc has to be adjusted to a negative value, except if adding a scale inhibitor (Section 2.3.3) or preventive cleaning (Section 2.3.7) is applied.
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Brackish Water
(cont.)

The conditions for CaCO3 scale control are: LSIc < 0 when no antiscalant is added LSIc 1 when 20 mg/L sodium hexametaphosphate is in the concentrate stream LSIc > 1 possible with polymeric organic scale inhibitors. For the maximum LSIc and required dosages, please refer to the scale inhibitor manufacturers literature. If LSIc is not within the above conditions, adjustments can be made by one of the following means. A new LSIc can then be calculated: The recovery, Y, can be lowered and LSIc can be calculated as above by substituting a new value for the recovery. Decreasing the calcium concentration in the feed solution by means of sodium cycle ion exchange. This will increase the pCa and will therefore decrease the LSIc. Softening will not change the alkalinity or pH of the feed solution and the slight change in TDSf may be considered negligible. After softening, the LSIc can be calculated as above using the lower value for calcium concentration. Adding acid (HCl, CO2, H2SO4, etc.) to the feed solution changes the Alkf, Cf, and pH. The slight change in TDSf can usually be neglected. Acid addition will decrease the LSIc; however, since many variables change with acidification, trial and error computations are required to determine the amount of acid needed to obtain the desired LSIc. The number of trial and error computations required to determine the amount of acid needed can be reduced greatly by using the pHs calculated in Eq. 9. Since pHc will usually be 0.5 units higher than the pHf, the first computation can be made with an acidified feed solution that is 0.5 units lower than the pHs. For an assumed pH (pHacid), obtained from addition of acid to the feed solution, obtain the ratio of Alkacid/Cacid from Figure 2.3. From this ratio, Alkf, and Cf, calculate the mg/L of acid used (x). For example, for H2SO4 addition (100%):

Alk acid Alk f 1.02 x = C acid C f + 0.90 x

Eq. 11

Calculate the total alkalinity of the acidified feed water (Alkacid) and the CO2 content in the acidified feed water (Cacid) as follows: Eq. 12 Alk acid = Alk f 1.02 x

C acid = C f + 0.90 x
Using Alkacid and Cacid for the new pH, calculate the LSIc. If HCl (100%) is used for acidification, Eq. 11 is:

Eq. 13

Alk acid Alk f 1.37 y = C acid C f + 1.21 y

Eq. 14

where: y = HCl (100%), mg/L Reverse Osmosis and Nanofiltration in Operation Once a reverse osmosis or nanofiltration system is operating, the Langelier Saturation Index can be directly calculated from the analysis of Alkc, Cac, TDSc, and pHc of the concentrate stream and compared with the projected LSIc. Use of Computers The LSIc and the acid dosage required to adjust a certain LSIc can be determined using a personal computer and the FILMTECTM Reverse Osmosis System Analysis (ROSA) computer program. The ROSA computer program can be downloaded here, www.dow.com/liquidseps/design/rosa.htm.
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Brackish Water (cont.)

Figure 2.2 pH versus methyl orange alkalinity/free CO2

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Form No. 609-02017-1004

Brackish Water
(cont.)

Figure 2.3 Langelier saturation index

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Form No. 609-02017-1004

Seawater

For high-salinity brackish waters with TDS > 10,000 mg/L in the concentrate stream and for seawaters, the Stiff & Davis Stability Index (S&DSI) is used to express the scaling potential for calcium carbonate. The data needed to calculate the S&DSI of the concentrate stream are the same as the data needed to calculate the LSI. Additionally, the molal concentrations of all ions in the feed solution are required, at least of all major ions (i.e., Ca2+, Mg2+, Na+, K+, HCO3, SO42, and Cl). Calculations /7/ 1. Calculate the calcium concentration in the concentrate stream, Cac, as CaCO3 in mg/L:
Ca c = Ca f 1 1 Y

Eq. 6

2. Calculate the alkalinity in the concentrate stream, Alkc, as CaCO3 in mg/L:

Alk c = Alk f 1 1 Y

Eq. 8

3. Calculate the ionic strength of the feed stream (If):

If = 1 2

m z
i

2 i

Eq. 3

4. Calculate the ionic strength of the concentrate stream (Ic):

1 Ic = I f 1 Y

Eq. 5

5. From Figure 2.4, obtain pCa as a function of Cac and pAlk as a function of Alkc. From Figure 2.5, obtain K as a function of concentrate ionic strength and feed temperature. 6. Calculate the pH at which the concentrate stream is saturated with CaCO3 (pHs) as follows:
pHs = pCa + pAlk +" K"

7. Calculate the free carbon dioxide content (C) in the concentrate stream by assuming that the CO2 concentration in the concentrate is equal to the CO2 concentration in the feed: Cc = Cf. The concentration of free carbon dioxide in the feed solution is obtained from Figure 2.2 as a function of the alkalinity and the pH of the feed solution. 8. Calculate the pH of the concentrate stream (pHc) using the ratio of alkalinity (from Eq. 8) to free CO2 in the concentrate (from Step 7), Figure 2.2. 9. Calculate the Stiff and Davis Stability Index of the concentrate (S&DSIc) as follows:
S & DSIc = pHc pHs

Adjustments of S&DSIc The S&DSIc in the concentrate stream will be positive with most natural high-salinity waters. In order to prevent CaCO3 precipitation and scaling, the S&DSIc has to be adjusted to a negative value by acid dosing. The S&DSIc can remain positive, however, if CaCO3 precipitation is prevented by the dosage of a scale inhibitor - see Scale Inhibitor Addition (Section 2.3.3). For the maximum allowed S&DSIc and the required dosage, please refer to the scale inhibitor manufacturers literature.

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Form No. 609-02017-1004

Seawater

(cont.)

If the S&DSIc is unacceptable based on the above recommendation, adjustments can be made by one of the following means. A new S&DSIc can then be calculated. The recovery can be lowered and the S&DSIc can be calculated as above by substituting a new value for the recovery. Decreasing the calcium and alkalinity concentrations in the feed solution by means of lime or lime-soda ash softening will increase the pCa and pAlk and will therefore decrease the pHs. Addition of acid (HCl, CO2, H2SO4, etc.) to the feed solution either with or without lime or lime-soda ash softening changes the Alkf, Cf, and pH. The slight change in If can usually be ignored. Acid addition will decrease the S&DSIc; however, since many variables change with acidification, trial and error computations are required to determine the amount of acid needed to obtain the desired S&DSIc. These computations have been described already in the previous section. For seawater systems, a dosage of typically 10 mg/L sulfuric acid is required to achieve a pHf of about 7 and a negative S&DSI in the concentrate. RO/NF in Operation Once an RO or NF system is operating, the S&DSIc can be directly calculated from the analysis of Alkc, Cac, pHc, and Ic of the concentrate stream and compared with the projected S&DSIc.

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Form No. 609-02017-1004

Seawater

(cont.)

Figure 2.4 Conversion of calcium and alkalinity to pCa and pAlk

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* Trademark of The Dow Chemical Company

Form No. 609-02017-1004

Seawater

(cont.)

Table 2.6 Standard procedures relevant to water analysis for RO/NF applications

FILMTEC Membranes
For more information about FILMTEC membranes, call the Dow Liquid Separations business: North America: 1-800-447-4369 Latin America: (+55) 11-5188-9222 Europe: (+32) 3-450-2240 Pacific (ex. China): +800-7776-7776 China: +10-800-600-0015 http://www.filmtec.com

Notice: The use of this product in and of itself does not necessarily guarantee the removal of cysts and pathogens from water. Effective cyst and pathogen reduction is dependent on the complete system design and on the operation and maintenance of the system. Notice: No freedom from any patent owned by Seller or others is to be inferred. Because use conditions and applicable laws may differ from one location to another and may change with time, Customer is responsible for determining whether products and the information in this document are appropriate for Customers use and for ensuring that Customers workplace and disposal practices are in compliance with applicable laws and other governmental enactments. Seller assumes no obligation or liability for the information in this document. NO WARRANTIES ARE GIVEN; ALL IMPLIED WARRANTIES OF MERCHANTABILITY OR FITNESS FOR A PARTICULAR PURPOSE ARE EXPRESSLY EXCLUDED.

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*Trademark of The Dow Chemical Company

Form No. 609-02017-1004