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    13 views5 pages

    2005 Narayan-Sarathy-2005-CaCO3-US6858180

    Uploaded by

    Izzat W. Kazi

    Copyright:

    © All Rights Reserved
    Download as PDF or read online from Scribd
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    ey co) 6 (2) (58) United States Patent Narayan-Sarathy et al. PROCESS POR INHIBITING SCALE, Inventors: Sridevi Narayan-Sarathy, Hillis, OH (US); Laurence G, Dammann, Povell, O11 (US); Davor Zidovee, Jacksonville, TLS) Assignee: Ashland Ine., Dublin, OH (US) Notice: Subject to any disclaimer, the tem ofthis pateat is extended or adjusted uader 35 USCC. 154(b) by 40 days, Appl. Now 10/147,60 Filed: May 16, 2002 Prior Publication Data US 20089215355 AI Now 20, 2103 Int. C7 C238 11/00; BOS 1700 US.cL 42/7, 42216, 5241807; ‘SBAIBIT7; 526/258; 526/286 Field of Search 42216, 7, 6; 524807, S17 USOOG8S8180B: (10) Patent No. 5) Date of Patent US 6,858,180 B2 Feb. 22, 2005 60) References Cited US. PATENT BOCUMENTS 4.081383 A 1978. Warburton et al 28.6 $699,0 A * L/1987 Mane ea Sars SSSI A 5/1989 Young ot 522/188 Suse & 411902 Bich tl ‘22470 Shower A * 41902 Lis eal saat Sust061 & 71992 Wolt san38, SIS2408 A * 101992 Patel ane S2oqus & 1004 Egra cal. Sava10 eraua7a7 BL * 12002 Chen et a S807 6.447595 BL * 912002 Tsk eta 232180 20030ESTI6 AL * 42003. Ghonh ta 5 * cited by examiner Primary Exaniner—Keisanne Sastezab (74) Attorney, Agent, or Firm—David L. Hedden 6 ABSTRACT. Tis invention relates to a process for scale inhibition using random copolymers of acrylic acid and a monomer that is hydrophobic 10 Claims, No Drawings US 6,858,180 B2 1 PROCESS FOR INHIBITING SCALE CROSS-REFERENCE TO RELATED "APPLICATIONS. ‘Not Applicable. CLAIM TO PRIORITY [Not Applicable, STATEMENT REGARDING FEDERALLY ‘SPONSORED RESEARCH OR DEVELOPMENT. [Not Applicable. REFERENCE TO A MICROFICHE APPENDIX. [Not Applicable, BACKGROUND OF THE INVENTION (1) Field of the lavention ‘This invention relates to a process for seale inhibition using random copolymers of aerylie acd and a eo-mooomer thats hydrophobic, (@) Description of the Related Art tis known to use low molecular weight ionic polymers and copolymers 28 scale inhibitors for cooling water towers tnd boilers in industry. Most commercially available poly- mers in the market today used for this application are based ‘on earboxslic acid, Copolymers of acrylic acid and monomers that have haydkephobie properties ate well known, eg, CARBOPOL® thickeners manufactured by BLEGoodrich Co. Uses for these copolymers have een disclosed for a variety of applications. US. Pat. No. 5,118,435 discloses their use in ant-ieing compositions, while US. Pat. No. 5,106,608 discloses their use as 4 vehicle in cosmetic compositions US. Pat. No. 4,833,179 describes the suspeasion poly merization of a pressure-sensitive acrylate copolymer bead ‘containing a modiier moiety like 2-polystyelethyl meth- acrylate maeromonomer, which renders the copolymer bead ron-agglomerating al room temperature and safely trans- portable. US. Pat. No. 5,294,693 discloses the use of an Acrylic acid copolymer terminated by a fatly hydrophobic ‘chain having at least 26 carbon atoms as a modifier of theological properties, stabilizing agent, and suspensio agent for coarse mineral or organic materials in various applications. Other known applications for these copolymers areas ant-soiling treatment fo carpets and earpet yara (US. Pat. No, 4081,383) and photographic recoating material (US. Pat, No. 5,134,061), Al citations referred to under this description of the “Related AM” sod in the “Detailed Description of the Invention” are expressly incorporated by reference, [BRIEF SUMMARY OF THE INVENTION This invention relates to a process for scale inhibition, hcl comprises adding random copolymer of acrylic acid and a eo-monomer that bas hydrephobie properties, © an aqueous system, The random copalymers are synthesized by the reaction of acrylic acid and) a co-monomer that has hhyrophobie properties, typically in the presence of a mer ‘apto chain transfer agent, a solvent (Iypically toluene), and fn appropriate free radicil initiator, However, i the mer- ‘capto transfer agent contains a hydrophobic group, it cam be % o 2 used 38 the co-monomer and no other monomer is needed to syalliesize the random copolymer. The random copolymers ‘ypically have an average molecular weight of 500 to 5000, as determined by °C NMR. The process can be used t0 prevent scale from building’ up in cooling, water towers, boilers, or other industrial applications. ‘The random copolymers were evaluated for scale inhibi- tion and the data indicated that they were excellent scale inhibitors at very low dosage levels, The random copoly mers were primarily tested for inhibition of caleium earbon- te crystal grow, but itis believed that the random copoly= ners willbe elective in inhibiting the formation of sulfate, phosphate, and oxalate scale BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS [Not Applicable. DETAILED DESCRIPTION OF THE, INVENTION The desiled deseption and examples will ilsate specitc embodiments ofthe invention and wll enable coe fille inthe att practice the invention, inlding the Dest inode is conemplsted that many equivalent embodiments ‘tthe invention wil be operable besides these specially disclosed Co-monomers which ate the source of a hydophobie seoup prefely watersoluble monomers, plbmerze with {ipl sci and include common aces, eg n-by fecvate and Dethyhexstaerylats stato! molecules such as 24Nethylperiuoro octane sulfonamide) thy Secyate (FXC13}; fatty seid modified malami aid, a0 Feaction products of lei anhydride wth ng chain ak ings as well sy monofuncion meeapio compounds having hydrophobic groups. Examples of mereapo gous that contain hydrophobic groups incl Hear meresptans faving» chain length pester than four, sch a fury smeeaptan, buy mereaptan an exyl meraptan, Ifa eo-monomer other than merepto compound having hydkonhabie groups is used as the cosmooomer, ten the reaction mus be cared ou inthe presence of 2 chan transfer agen The function ofthe cha anser age 1 Control polymerization, so tat the molecalar weight ofthe copolymer does nol get too high. Examples inlade Stnereapopropionis sid and 2-mereapiothanal The average molecular weight ofthe copolymer, Bad spon GPC messiroments i peal fom 50016 SO, preferably fem 1000 3000, mest petra from 15006 Stoo. “The reaction aes place inthe presence ofa fre radical innoe Representative examples of fe radial inintors that can bs used include ammonium pesiate, pots Persist, redox intr atl ities VAZO-6 is the preferred intr, The easton is preferably carried out in ibe presence of an tomatic solvent such as oleae ‘Typically, the amount of solvent used is three times the sight ofthe ttl amount of monomers. Reaction tempers: {utes are typically trom room temperate to 100" preferably at aout SO" C. Preferably. the reaction sera St bythe continuous an independent sition ofthe chain osfcr agent, monomer, a nilsor. For the sybeas of Jw molecular weiaht polymes lege amount of initor teed tobe preset inthe reatr atthe beginning of the “The weigh rato of acrylic acto comonomer may vary cover wie anges, for intact from 25 10 10, But US 6,858,180 B2 7 preferably from 5 (0 10, most preferably from 8 to 10. The Amount of fee radical initiator requied is typically from 0.5 02 weight percent, where the weight percent isbssed on the total weight of acrylic acid and cormonomer, peeferahly from 0-5 to 1 weight percent Other components may be added to the scale inhibitor ‘composition, such as corrosion inhibitors, surfactants, oF Agents that inhibit micrebiological growth, The scale inhibitors are used, by adding them to an aqueous system that comes into contact with 2 metal of another surface prone to scaling, for instance codling water, boiler water, and reverse osmosis and geothermal/mining ‘water. The scale inhibitors ate used in amounts of from 0.1 to 1000 ppm, preferably from 1.0 10 100.0 ppm. EXAMPLES The following examples illustrate how to practice the invention. All units age inthe metre system and all amounts fand percentages are by weight, unless otherwise expressiy indicated ‘Several copolymers were prepared from acrylic acd and ‘monomer having hydrophobic popertics in th presence of ‘chain transfer agent anda free radical initiator The average ‘molecular weight ofthe copolymers was determined by 13C NMR, and then they were evaluated as scale inhibitors using the so-called “Dynamic Test” ‘The “Dynamic Test” used, commonly known as tube blocking tests based on monitoring the increase in pressure resulting from scaling inside «eapilary stainless stecl tube, 8 supersaturated solution is pumped through, ‘The solution fal the following composition: 600 ppm jum as CaCO3, 300 ppm Mg. as CaCO, 600 ppm Alkalinity as CaCO, 288 ppm sulfate. The pll Was 8.6 and the temperature 82°°C, The columa was I m in length and ‘mm intraal diameter. The flow rate was 10 mL/min, The test duration was 50 mia, The effet of scale contol treal- iments is measured by determining the percent inhibition, defined here as a relative slope pressure time [slope unlzeated-slope test)/slope untreted100] and the mini- ‘mum dose required to oblain IME inbibition (ae detectable pressure increase). In addition, the time at which a Hist ‘departure from the inital pressure occurs "induction time”) 's noted. In order to account for small differences in the response of the system at diferent times, due to slight ‘variations in solution composition or the condition of the scaling surface (column), a reference material was always fncluded in a sel of tesis. The reference material was hhydroxyethylidene diphesphonie acid (HEDP), for which the normal minimum dose was 1.6 pa. The actual range of the minimum dose for HEDP at dffereot times was 11-16 pm. All doses eported have been coerected proportionally 10 the reference response with respect t0 the nogmal value feported dose=actual dose/HHEDP minimum dosex.6 "The copolymers used in the subject process were com= pared 1 a representative polyacrylic acid of similar molecu- Jar weight (Control) with respect to thie effectiveness in inhibiting calcium carbonate scale according 10 the “Dynamic Tea”, The lest results forthe Conteol (A-E) ate set forth in Table 1, slong with the test results for the ‘copolymers of Examples 1-8. The induction time i the time ‘when a precipitant i ist noticed. Generally, the longer the induction time, the mowe effective the copolymer is al inhibiting scale EXAMPLE 1 Copolymer (95/5) of Acrylic Acid and 2N-ethyl perlluorooetane-sulfonamide)ethy] acrylate ‘To 4-neck, 500 ml. reactor, equipped with a condenser, mechanical sine, thermocouple, 3 addition funnels con- % o 4 nected to metering pumps, and a nitrogen inlet and outlet, was added 150 g toluene. The tluene was heated to 80" C) ‘ver 4 period of 15 miautes under constant niteogen sweep. In the meantime, (065 g of VAZ0-67 in 10 ml. toluene, 5 of 3-mereapiopropionic acid made up to 10 ml. using foluene, and a mixture consisting of 42.75 g of acrylic acid and 2.25 g of 2(N-cthyl perfluorooctane-suonamide)cthyl fcrylite were separately’ adled to each of the 3 addition funnels. Then 0.2 g initiator (VAZO-67) dissolved in 4m toluene was added to reactor. Thereafter, the three compo- ‘ents inthe funnels was started and addled wo the reactor over 4 period of 2 hours, ‘Alter completion of addition, the reaction mixture was sired for another 2hours at 80° C. Precipitation was ‘observed from the beginning of addition. After the reaction was cooled down to room temperature, an almost gel-like solid produet was obtained. This produ was eemoved from the reactor and filtered using @ Buchaer funnel. The product ‘was dried a vacuum oven overnight at 80° C, Detaled °C and "F NMR confirmed the formation ofa random copol fer having acrylic acid groups and hydrophobic groups. GPC analysis showed the average molecular weight of the polymer was about 2000, ‘The calcium carbonate scale inhibition eliciency of this copolymer is set forth as Examples 1-1 to 1-3 in Table EXAMPLE 2 Copolymer (97.5.5) of Acrylic Acid and 24N- ethyl perfiuorooetane sulfonamide)ethyl acrylate The procedure of Example 1 was followed, except the ratio of acrylic acid to 2-(N-ethyl_perfluorooctane- sulfonamide)ethyl acrylate was varied. After drying in the vacuum oven overnight at 80° C,, a solid white product obtained. GPC measurements indicated the molecul ‘weight to be around 2000 and NMR studies confirmed the incorporation of 2(N-cthylperfluorooctane sulfonamide) ethyl aerylate hydrophobie groups into the eopolyme. The calcium carbonate scale inhibition efiiency of this copolymer is sot forth ia Table [as Examples 21 to 2-2. EXAMPLE 3 Copolymer (95/5) of Acrylic Acid and 2-

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