Silica antiscalant composition and method for silica scaling inhibition in membrane applications

Abstract

To provide a silica antiscalant composition in membrane applications and method for silica scaling inhibition in a membrane system.SOLUTION: An antiscalant composition has a silica inhibitor composition, and a dispersant composition. A method for inhibiting scale formation includes: providing an antiscalant composition, the antiscalant composition having a silica inhibitor and a dispersant; and adding the antiscalant composition to an aqueous stream of an aqueous system.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] (CROSS REFERENCE TO RELATED APPLICATIONS) This application is a continuation of U.S. Provisional Patent Application No. 62 / 896,939, filed September 6, 2019. No. 6,313,635, filed on Oct. 13, 2003, the disclosure of which is hereby incorporated by reference in its entirety.

[0002] (Technical field) The disclosed technology generally relates to compositions and methods for silica scale inhibition in membrane applications. More specifically, the present invention relates to a method for the prevention of silica scale in high silica water membrane applications. SUMMARY OF THE DISCLOSURE An anti-scalding agent and method are provided. [Background technology]

[0003] In the membrane desalination industry, practitioners generally pursue higher recovery rates to save on operational costs. Implementing membrane systems to reduce concentrate disposal. However, this goal is being met by increasing silica concentrations. It is very difficult to do this in elevated water. Using high concentrations of silica can result in silica scale or silica Accumulation of calcium deposits can result in lost productivity, poor product quality, unplanned downtime and In addition, silica scale forms on the membrane surface, which requires frequent membrane cleaning-in-place (CIP) operations. Once there, it is nearly impossible to remove.

[0004] Silica scaling in membrane systems is very complex and depends on many factors (e.g. silica level, The influence of the pH, temperature, other metal ions, system operating conditions, etc. The silica level and pH value are the two most important factors. Two to improve recovery and reduce concentrate disposal for high silica water treatment in membrane applications The first approach is to adjust the pH of the feed by adding acid. However, the addition of acid requires additional supply / metering pumps, body / skin contact with concentrated acid, handling (potential safety issues), inhalation of fumes, etc. The second approach is The key to success is to administer a highly effective silica scale inhibitor.

[0005] Therefore, what is needed in the art is a method for producing silica scale in high silica water membrane applications. Compositions and methods for suppressing leukemia. Summary of the Invention

[0006] The disclosed technology generally relates to compositions and methods for silica scale inhibition in membrane applications. More specifically, the present invention relates to a method for the prevention of silica scale in high silica water membrane applications. SUMMARY OF THE DISCLOSURE An anti-scalding agent and method are provided.

[0007] In one aspect of the disclosed technique, a scale inhibitor composition is provided. The article includes a silica inhibitor composition and a dispersant composition.

[0008] In some embodiments, the silica inhibitor composition comprises an organophosphate, phosphonate-based compound. In some embodiments, the organic phosphate is 1-hydroxyethylidene-1,1-diphosphonic acid. In some embodiments , the silica inhibitor is present in a concentration of about 5-40% active material.

[0009] In some embodiments, the dispersant composition comprises a sulfonated acrylic acid polymer. In some embodiments, the sulfonated acrylic acid polymer is characterized by the following formula: It contains repeating units that can be

[0010] [ka] (Chemical formula A)

[0011] where n ranges from about 1 to 100 and Z is H, Na, K, Ca, or NH4.

[0012] In some embodiments, n is about 1 to 20. In some embodiments, Z is c , d and e may be the same or different. The molar ratio of :d:e ranges from about 20:10:1 to 1:1:20.

[0013] In some embodiments, the molecular weight of the sulfonated acrylic acid polymer is about 10,000. In some embodiments, the silica to dispersant composition is in the range of about 30,000. The concentration ratio of the inhibitor composition is about 1:2. In some embodiments, the concentration ratio of the dispersant composition to the The concentration ratio of the silica inhibitor composition to the silica inhibitor composition is about 1:1.6. The refractory agent and the dispersant composition are mixed together.

[0014] In yet another aspect of the disclosed technique, a scale inhibitor composition is provided. The silica inhibitor composition includes (i) a silica inhibitor composition, the silica inhibitor composition being a 1-hydrogen (ii) a silica inhibitor composition comprising a sulfopropyl ether-1,1-diphosphonic acid; The invention includes mixtures of acrylated / sulfated acrylic acid polymers or terpolymers.

[0015] In some embodiments, the sulfonated acrylic acid polymer or terpolymer comprises It comprises repeating units characterized by a chemical formula.

[0016] [ka] (Chemical formula A)

[0017] where n ranges from about 1 to 100 and Z is H, Na, K, Ca, or NH4.

[0018] In some embodiments, the silica inhibitor and dispersant composition are mixed together at about 25° C. can be.

[0019] In yet another aspect of the disclosed technique, a method for inhibiting scale formation in a membrane system includes: The method includes providing a scale inhibitor composition, The scale inhibitor composition includes a silica inhibitor and a dispersant. and adding the scale inhibitor composition to an aqueous stream of the water system.

[0020] In some embodiments, the silica inhibitor is an organophosphate, phosphonate-based compound or In some embodiments, the dispersant comprises a sulfonated carboxylic acid copolymer. In some embodiments, the scale is a silyl acrylate polymer or terpolymer. The inhibitor composition is a mixture of a silica inhibitor and a dispersant.

[0021] In some embodiments, the silica inhibitor is 1-hydroxyethylidene-1,1-diphos. The dispersant comprises a sulfonated / sulfated acrylic acid polymer or terpolymer. In some embodiments, the sulfonated acrylic acid polymer or terpolymer is , comprising a repeating unit characterized by the following chemical formula:

[0022] [ka] (Chemical formula A)

[0023] where n ranges from about 1 to 100 and Z is H, Na, K, Ca, or NH4. do.

[0024] In some embodiments, the aqueous stream comprises a silica content of at least 300 ppm. In some embodiments, the aqueous stream has a silica content of about 300 ppm to about 350 ppm. In some embodiments, the aqueous stream comprises a pH of at least 7. In some embodiments, the aqueous stream comprises a pH of about 7.5. Has a pH of .5 and a silica content of at least 300 ppm.

[0025] In some embodiments, the aqueous system comprises a reverse osmosis membrane or a nanofiltration membrane. In one embodiment, the scale inhibitor composition is added to an aqueous stream in an amount of about 1 ppm to about 100 ppm. In some embodiments, the scale inhibitor composition comprises about 3 ppm to about 30 ppm is added to the aqueous stream in amounts

[0026] These and other features and advantages of the techniques of the present disclosure are described in the following detailed description, which include, by way of example only, the following: This is specifically shown in the embodiment to be described with reference to the schematic diagram of FIG. [Brief description of the drawings]

[0027] [Figure 1] 1 is a graph providing results of an exemplary embodiment of the techniques of this disclosure. [Diagram 2] 1 is a graph providing results of an exemplary embodiment of the techniques of this disclosure. [Diagram 3] 1 is a graph providing results of an exemplary embodiment of the techniques of this disclosure. [Figure 4] 1 is a graph providing results of an exemplary embodiment of the techniques of this disclosure. [Figure 5A] 1A-1D provide results of an exemplary embodiment of the techniques of this disclosure. [Figure 5B] 1A-1D provide results of an exemplary embodiment of the techniques of this disclosure. [Figure 5C] 1A-1D provide results of an exemplary embodiment of the techniques of this disclosure. [Figure 5D] 1A-1D provide results of an exemplary embodiment of the techniques of this disclosure. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0028] The disclosed technology generally relates to compositions and methods for silica scale inhibition in membrane applications. More specifically, the present invention relates to a method for the prevention of silica scale in high silica water membrane applications. SUMMARY OF THE DISCLOSURE An anti-scalding agent and method are provided.

[0029] As used herein, the term "scaling inhibitor" refers to the formation and and / or compositions / formulations that inhibit (reduce) the size and / or shape of solid silica particles. Refers to...

[0030] Surprisingly, the mixture of silica inhibitor and dispersant composition has been shown to be effective in controlling silica scale. It has been discovered that the membrane silica scale inhibitor composition described herein exhibits a synergistic effect when used in combination with other compositions. is the performance of a membrane, such as a reverse osmosis (RO) or nanofiltration (NF) system, under given process conditions. In applications, the membrane has been shown to be effective in treating feed streams containing high silica. The Rika scale inhibitor composition is intended to be used in plants operating at concentrated silica levels exceeding 300 ppm. This indicates a synergistic effect between threshold silica scale inhibition and particle dispersion, and allows the membrane system to Increase system recovery rates and reduce operational costs.

[0031] In one aspect of the disclosed technique, a scale inhibitor composition is provided. The article includes a silica inhibitor composition and a dispersant composition. The mixture of the inhibitor composition and the dispersant composition is used to handle high silica water treatment in membrane applications. It has been shown that the present invention provides an effective treatment for

[0032] Typically, silica dissolved in the feedwater is concentrated several times in an RO or NF system. This leads to polymerization of silica, which grows into larger molecules or colloidal silica. In this case, polymerization of such silica leads to the formation of silica levels and / or particles. and accelerates with increasing pH value. Surprisingly, the silica inhibitor and dispersant composition The silica scale inhibitor composition described herein is a mixture of It was found that this method makes it possible to prevent silica particles suspended in the flow from settling on the membrane surface. It was done.

[0033] In addition, the disclosed silica scale inhibitor composition is non-toxic to the environment (i.e. (i.e., "environmentally friendly"), and since high-silica water can be treated without adding acid, there is no need for acid treatment. The silica scale inhibitor composition described herein eliminates the problems caused by the addition of excess acid. This avoids an increase in the total dissolved solids (or TDS) of the water produced, thereby reducing the This reduces energy consumption and lowers operational costs.

[0034] In some embodiments, the silica inhibitor composition comprises an organophosphate, phosphonate-based compound. The specific anion of the silica inhibitor composition includes a carboxylic acid sulfonated copolymer. The groups can interact with cations in the feed solution to inhibit the precipitation of crystalline inorganic salts, and the silica colloids can be used to inhibit the precipitation of crystalline inorganic salts. This can reduce the chance of co-precipitation with ions or particles, thus reducing silica scale formation. It is believed that this may be helpful and may minimize any detrimental effects on membrane performance.

[0035] In some embodiments, the organophosphate is 1-hydroxyethylidene-1,1-diphos In some embodiments, the silica inhibitor of the present technology is silica dihydrogen phosphate (HEDP). Not only does it inhibit polymerization, but it also effectively prevents calcium carbonate precipitation. In the form, the silica inhibitor is present in a concentration of about 5-40% active material.

[0036] In some embodiments, the dispersant composition comprises a sulfonated acrylic acid polymer. In some embodiments, the sulfonated acrylic acid polymer is characterized by the following formula: It contains repeating units that can be

[0037] [ka] (Chemical formula A)

[0038] where n is in the range of about 1 to 100 and Z is H, Na, K, Ca, or NH4. .

[0039] In some embodiments, n is about 1 to 20. In other embodiments, n is about 10 In some embodiments, Z can be the same in c, d and e, In some embodiments, the molar ratio of c:d:e is about 20:10: The range is 1 to 1:1:20.

[0040] In some embodiments, the sulfonated acrylic acid copolymers, terpolymers or A sulfonated acrylic acid comprising a repeating unit characterized by the chemical formula A described in the specification. The polymer imparts a negative charge to the suspended silica particles present in the feed stream, which leads to enhanced electrostatic Aggregation due to electrical repulsion and steric hindrance are avoided.

[0041] In some embodiments, the molecular weight of the sulfonated acrylic acid polymer is about 10,000. to about 30,000. In another embodiment, the sulfonated acrylic acid polymer is The range is about 12,000 to about 25,000.

[0042] In some embodiments, the concentration ratio of the silica inhibitor composition to the dispersant composition is about 1. In some embodiments, the concentration of the silica inhibitor composition relative to the dispersant composition is 2. The ratio is approximately 1:1.6.

[0043] In some embodiments, the silica inhibitor composition is about 5-25% by weight of the dispersant composition. The composition is about 10 to 40% by weight of the total scale inhibitor composition.

[0044] In some embodiments, the silica inhibitor and the dispersant composition are mixed together. In some embodiments, the silica inhibitor and the dispersant composition are mixed together at room temperature. In an embodiment, the silica inhibitor and dispersant composition are mixed together at about 25° C. may be provided by any conventional mixing technique sufficient for the purposes described herein. It should be understood that, for example and without limitation, conventional mixing techniques include flat baffles, , pitched blade impeller and / or Rushton turbine.

[0045] In some embodiments, the disclosed silica scale inhibitor composition comprises a phosphonate-based For example, diethylenetriaminepenta(methylenephosphonic acid )(DTPMP), aminotris(methylenephosphonic acid)(ATMP), hexanediamine and the like, but are not limited to, tetra(methylene phosphonic acid) (HDTMP). Phosphonic Acids if or when the feedwater or aqueous stream contains a high potential for CaCO3 precipitation The presence of a base inhibitor may be necessary. In such cases, the disclosed scale inhibitor composition The composition may include the addition of a CaCO3 inhibitor.

[0046] In certain embodiments, the scale inhibitor composition comprises: (i) a silica inhibitor composition comprising: Here, the silica inhibitor composition is 1-hydroxyethylidene-1,1-diphosphonic acid (H (ii) a silica suppressor composition comprising a sulfonated / sulfated acrylic acid copolyester (EDP); A mer, terpolymer or sulfone containing repeating units characterized by chemical formula A and mixtures of methyl acrylic acid polymers.

[0047] In yet another aspect of the disclosed technique, a method for inhibiting scale formation in a membrane system includes: The methods described herein do not involve the addition of acid (i.e., the conventionally used (This process allows for the treatment of high silica waters without the need for added acid as has been conventionally done.) It has been shown to provide synergistic benefits in treating high silica containing streams in membrane applications. The method described herein allows, inter alia, the inhibition of silica scale on the membrane surface and is useful in RO or enables NF systems to operate at silica levels up to 350 ppm at pH 7.5 do.

[0048] The method includes providing a scale inhibitor composition including a silica inhibitor and a dispersant. and adding the scale inhibitor composition to an aqueous stream of the water system. The scale inhibitor composition of the disclosed method is a mixture of a silica inhibitor and a dispersant. As previously mentioned, the mixture may be provided by any conventional mixing technique as described herein. It can be done.

[0049] In some embodiments, the silica inhibitor of the disclosed method is an organophosphate, phosphonate, The base compound includes a carboxylic acid sulfonated copolymer.

[0050] In some embodiments, the dispersant of the disclosed method is a sulfonated acrylic acid copolymer. In some embodiments, the sulfonated acrylic acid copolymer is a terpolymer. The repeating unit may be a terpolymer or terpolymer that includes repeating units characterized by the following chemical formula:

[0051] [ka] (Chemical formula A)

[0052] where n is in the range of about 1 to 100 and Z is H, Na, K, Ca, or NH4. do.

[0053] In some embodiments, the silica inhibitor described in the present method is 1-hydroxyethyl. The dispersant is a sulfonated / sulfated acrylic acid copolymer. 1. A sulfonated polymer comprising a repeating unit characterized by the formula A It is an acrylic acid polymer.

[0054] The water systems disclosed herein include membrane desalination plants, influents to industrial plants, drinking water plants, and the like. It should be understood that the above-mentioned substances may be present in, but are not limited to, the influent water to the port. In some embodiments, the aqueous system comprises a reverse osmosis (RO) or nanofiltration (NF) membrane.

[0055] In some embodiments, the aqueous stream comprises a silica content of at least 300 ppm. In other embodiments, the aqueous stream comprises a silica content of from about 300 ppm to about 350 ppm. In some embodiments, the aqueous stream comprises a pH of at least 7. In one embodiment, the aqueous stream comprises a pH of about 7.5. In another embodiment, the aqueous stream comprises a pH of about 7.5. and has a silica content of at least 300 ppm.

[0056] In some embodiments, the scale inhibitor composition is present in an amount of about 1 ppm to about 100 ppm. In some embodiments, the scale inhibitor composition is added to the aqueous stream at about 3 ppm. It is added to the aqueous stream in an amount of about 30 ppm. EXAMPLES

[0057] The present technology is further described in the following examples, which should be considered as illustrative. and should not be construed as narrowing the scope of the technology of the present disclosure or limiting the scope to specific embodiments. It shouldn't be.

[0058] The scale inhibitor compositions and methods disclosed herein are compatible when mixed together. The results showed synergy and enhanced performance compared to other targeted silica water treatments. The synergistic effect is the threshold silica scale inhibition of silica inhibitors and the particle size reduction in high silica concentrate feedwaters. It is believed that this is provided by the dispersant's ability to suspend the dispersion.

[0059] Figures 1-4 show the results for the Water-A treatment (300 ppm silica, 161 ppm CCPP and 7. 5)。 Provides comparative data on the performance of silica scale inhibitor compositions at pH 5. Product A is a phosphonic acid, and product B is a phosphonic acid with a polymer. As shown, HEDP is a silica suppressor and "Formula I" is a sulfonated / sulfated Acrylic acid copolymers, terpolymers or repeating units characterized by the chemical formula A It is a sulfonated acrylic acid polymer containing a carboxylic acid unit.

[0060] The results, as shown in Figures 1-4, are consistent with the presently disclosed scale inhibitor compositions and methods. However, before the accumulation of such scale on the membrane surface is observed (i.e., before the permeability is reduced), It is described as providing silica inhibition for at least 2 hours. The scale inhibitor composition and method are effective in preventing scale buildup in field RO / NF systems for 30 0 ppm silica is believed to provide improved performance without added acid. , showing a decrease in transmission within the first hour and / or more transmission within 2 hours This is in contrast to treatment with other commercially available products (e.g., Product A and Product B), which showed a decrease in do.

[0061] Referring to FIG. 1, the mixture of HEDP and Formula I was found to be more effective than the other two commercial products in the Water-A treatment. The mixture of HEDP and Formula I was recirculated for 6 hours. The decrease in membrane permeability was much lower during the experiment. (Note: The HEDP+Chemical Formula I observed in Figure 1) The transmittance of the test is reduced by 10% due to the accelerated test mode conditions.

[0062] FIG. 2 shows the synergistic effect of the presently disclosed compositions. Specifically, the silica scale inhibitor A composition (e.g., a mixture of HEDP and Formula I) may be realized by the individual components alone. The lowest membrane permeability decrease was achieved by the Water-A treatment, demonstrating a synergistic effect.

[0063] FIG. 3 provides a repeatability test of the disclosed silica scale inhibitor composition.

[0064] Figure 4 shows the results for the water-H treatment (350 ppm silica, 369 ppm CCPP and 7.5 ppm The presently disclosed compositions show a synergistic effect on the pH of the skin. A similar synergistic effect of the selected scale inhibitor composition was observed in the water-H treatment, and the silica scale This shows that the treatment effect is reliable and generally applicable to a variety of water chemistries.

[0065] Figure 5A-D provide the SEM and EDS image results of the water-H treatment. As shown, when the disclosed scale inhibitor composition was provided (HEDP and A significant reduction in surface deposits was observed, which was accompanied by a slight increase in membrane resistance. As a result, the decrease in membrane permeability was mitigated in a 6-hour recirculation test.

[0066] FIG. 5A shows the effect of no treatment and 4.9% Si and 8% Ca on the membrane surface. Figure 5B shows the effect of HEDP treatment alone, resulting in 8% S on the membrane surface. i and 0% Ca. FIG. 5C shows the effect of Formula I treatment alone, resulting in There was 12.3% Si and 0.3% Ca on the membrane surface. The effect of the Formula I treatment composition was shown, and the results showed that 2.3% Si and 0% Ca were applied to the membrane surface. There existed.

[0067] Although the embodiment of the technology of the present disclosure has been described, the present disclosure is not limited thereto, and It is understood that modifications may be made without departing from the spirit and scope of the present disclosure. As defined by the claims, either literally or by equivalents, All devices, processes and methods that come within the meaning of the claims are included therein. It is intended that

Claims

1. A scale inhibitor composition, the composition comprising: a silica inhibitor composition; A dispersant composition; A scale inhibitor composition comprising:

2. The silica inhibitor composition is an organophosphate, phosphonate-based compound or a carboxylate-based compound. The composition of claim 1 comprising a sulfonated copolymer.

3. The organic phosphoric acid is 1-hydroxyethylidene-1,1-diphosphonic acid.

3. The composition described in 2.

4. 10. The composition of claim 1, wherein the silica inhibitor is present in a concentration of about 5-40% active material. Composition.

5. The composition of claim 1, wherein the dispersant composition comprises a sulfonated acrylic acid polymer. 。

6. The sulfonated acrylic acid polymer has the chemical formula 【Chemistry 1】 and comprising a repeat unit characterized by where n ranges from about 1 to 100 and Z is H, Na, K, Ca, or NH ４ Yes R, The composition of claim 1.

7. The composition of claim 6, wherein n is about 1 to 20.

8. Z may be the same or different in c, d and e. composition.

9. The molar ratio of c:d:e is in the range of about 20:10:1 to 1:1:

20. The composition described above.

10. The molecular weight of the sulfonated acrylic acid polymer ranges from about 10,000 to about 30,000. The composition of claim 6,

11. 10. The method of claim 1, wherein the concentration ratio of the silica inhibitor composition to the dispersant composition is about 1:

2. The composition described in

12. The concentration ratio of the silica inhibitor composition to the dispersant composition is about 1:1.

6. Item 2. The composition according to item 1.

13. The composition of claim 1 wherein the silica suppressor and the dispersant composition are mixed together.

14. A scale inhibitor composition, the composition comprising: (i) a silica inhibitor composition, wherein the silica inhibitor composition comprises a 1-hydrogen silane. (ii) a silica inhibitor composition comprising a sulfo-1,1-diphosphonic acid; Scale inhibitors, including mixtures of sulphated / sulphated acrylic acid polymers or terpolymers Agent composition.

15. The sulfonated acrylic acid polymer or terpolymer has the formula 【Chemistry 2】 and comprising a repeat unit characterized by where n ranges from about 1 to 100 and Z is H, Na, K, Ca, or NH ４ That is, The composition of claim 14.

16. 15. The method of claim 14, wherein the silica inhibitor and the dispersant composition are mixed together at about 25°C. The composition described.

17. 1. A method for inhibiting scale formation in a membrane system, the method comprising: Providing a scale inhibitor composition, the scale inhibitor composition comprising silica Providing a scale inhibitor composition comprising an inhibitor and a dispersant; adding the scale inhibitor composition to an aqueous stream of a water system; 1. A method for inhibiting scale formation in a membrane system, comprising:

18. The silica inhibitor may be an organophosphate, phosphonate-based compound or a carboxylic acid sulfone-based compound. The method of claim 17, comprising a copolymer.

19. 17. The dispersant of claim 17, wherein the dispersant is a sulfonated acrylic acid polymer or terpolymer. The method described above.

20. The scale inhibitor composition is a mixture of the silica inhibitor and the dispersant. Item 18. The method according to item 17.

21. The silica inhibitor comprises 1-hydroxyethylidene-1,1-diphosphonic acid; 2. The dispersant of claim 1, wherein the dispersant is a sulfonated / sulfated acrylic acid polymer or terpolymer. The method according to claim 0.

22. The sulfonated acrylic acid polymer or terpolymer has the formula 【Chemistry 3】 and comprising a repeat unit characterized by where n ranges from about 1 to 100 and Z is H, Na, K, Ca, or NH ４ Yes 20. The method of claim 19 .

23. 18. The method of claim 17, wherein the aqueous stream comprises a silica content of at least 300 ppm. Law.

24. 18. The method of claim 17, wherein the aqueous stream comprises a silica content of about 300 ppm to about 350 ppm. The method described.

25. The method of claim 17 , wherein the aqueous stream comprises a pH of at least 7.

26. 20. The method of claim 17, wherein the aqueous stream comprises a pH of about 7.

5.

27. The aqueous stream has a pH of about 7.5 and a silica content of at least 300 ppm. The method according to claim 17.

28. 20. The method of claim 17, wherein the aqueous system comprises a reverse osmosis or nanofiltration membrane.

29. The scale inhibitor composition is added to the aqueous stream in an amount of from about 1 ppm to about 100 ppm. The method according to claim 17.

30. The scale inhibitor composition is added to the aqueous stream in an amount of about 3 ppm to about 30 ppm.

30. The method of claim 29.

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