WO1983002607A1 - Procede empechant la formation d'incrustations - Google Patents

Procede empechant la formation d'incrustations Download PDF

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Publication number
WO1983002607A1
WO1983002607A1 PCT/US1982/000121 US8200121W WO8302607A1 WO 1983002607 A1 WO1983002607 A1 WO 1983002607A1 US 8200121 W US8200121 W US 8200121W WO 8302607 A1 WO8302607 A1 WO 8302607A1
Authority
WO
WIPO (PCT)
Prior art keywords
copolymer
aqueous system
molecular weight
acid
metal surfaces
Prior art date
Application number
PCT/US1982/000121
Other languages
English (en)
Inventor
Chemical Company Dearborn
Original Assignee
Kuhn, Vincent, R.
Ventura, Ederlyna, M.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kuhn, Vincent, R., Ventura, Ederlyna, M. filed Critical Kuhn, Vincent, R.
Priority to GB08325799A priority Critical patent/GB2125025B/en
Priority to PCT/US1982/000121 priority patent/WO1983002607A1/fr
Priority to EP19820900853 priority patent/EP0099883A4/fr
Priority to DE19823249177 priority patent/DE3249177T1/de
Priority to ES519364A priority patent/ES519364A0/es
Priority to SE8301135A priority patent/SE8301135L/
Publication of WO1983002607A1 publication Critical patent/WO1983002607A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
    • C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
    • C02F5/12—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing nitrogen

Definitions

  • the present invention relates to the treatment of aqueous systems, and, more particularly, to inhibiting or preventing the deposition of scale onto metal surfaces in contact with the aqueous systems.
  • Typical apparatus in which the metal parts are fouled by scale deposition include evaporators, single and multi-pass cooling towers and associated equipment and the like. As the aqueous system is passed through or over the apparatus a portion of the aqueous system evaporates causing a concentration of the dissolved salts either naturally or synthetically contained in the system. These dissolved materials approach and reach a concentration at which they deposit out of the system (in certain instances they have solubility- in inverse relation to temperature) and form scale on the metal surfaces. This is especially true when the aqueous system is formed from nearby natural resources which contain various amounts of dissolved solids such as of calcium, magnesium and phosphates. Such deposits typically reduce heat transfer rates, and may impede the flow of the aqueous systems.
  • a method of inhibiting the formation of scale, particularly calcium phosphate and the like, depositions on metal surfaces of apparatus in contact with circulating aqueous systems is highly desired. It is especially desired to have a method which uses an agent which is stable, non-corrosive, and easily handled, which is effective at very low dosages and which is capable of inhibiting the formation of scale on metal surfaces of apparatus in contact with aqueous systems which tend to concentrate.
  • the present invention is directed to a method of inhibiting sc le formation on metal surfaces which are in contact with aqueous systems by incorporating into the aqu ous system a threshold quantity of a copoly er of 2-acrylamido-2-methylpropane sulfonic acid and acrylic or methacrylic acid or water soluble salts of said copolymers.
  • the present invention is directed to a method which is more effective in inhibiting and preventing scale deposition, especially deposition of calcium phosphate found in hard water, to a greater degree than is currently available.
  • ⁇ & surfaces can be achieved to a very high degree by the - ⁇ inclusion of threshold quantities of a specific copolymer of 2-acrylamido-2-methylpropane sulfonic acid and acrylic or methacrylic acid.
  • the subject copolymer is formed from 2-acrylamido-2-methylpropane sulfonic acid with either acrylic acid or methacrylic acid.
  • the molar ratio of the two types of monomeric units in the copolymer should be from 5:1 to 1:5, and more preferably from 2:1 to 1:2.
  • the copolymer should be of low molecular weight with a weight average molecular weight of from 1,000 to 10,000, preferably from 4,000 to 6,000 and most preferably of about 5,000. Although small amounts of high molecular weight copolymer can be tolerated in the system, such high molecular weight copolymers tend to behave as flocculating agents and, therefore, their presence should be avoided.
  • the copolymer is formed from carboxylic acid and sulfonic acid containing monomeric units. These acid units may be in the form of the free acid or preferably at least partially neutralized to a water soluble salt i.e. salts of alkali metals, such as sodium or potassium or ammonium salt with sodium being most preferred.
  • a water soluble salt i.e. salts of alkali metals, such as sodium or potassium or ammonium salt with sodium being most preferred.
  • copolymers required for use in the subject invention may contain minor amounts of up to about 5 mole percent of other monomeric units which are substantially inert with respect to the subject process such as lower (C,-C 5 ) esters of acrylic or methacrylic acid, «t» acrylonitrile and the like.
  • copolymers required for use in the subject *• invention are surprisingly effective in inhibiting scale formation, particularly of calcium phosphate, when present in the aqueous system in threshold amounts which will depend, to some extent, on the nature of the aqueous
  • OMPI system Normally dosages of from 0.1 to 100 parts per million and more preferably from 1 to 25 parts per million provide effective inhibition.
  • the copolymer may be added to the aqueous system coming in contact with the metal surfaces of an apparatus by any convenient mode, such as by first forming a concentrated solution of the copolymer with water and then feeding the concentrated solution to the a ⁇ ueous system at some convenient point in the operation. Alternately, the subject copolymer can be added directly to the aqueous system.
  • the copolymer found useful in performing the subject process can be formed by conventional vinyl polymerization techniques.
  • the monomers of 2-acrylamido-2-methylporpane sulfonic acid, methacrylic acid and acrylic acid (as appropriate) are each commercially available.
  • the monomers are mixed in appropriate molar ratios to form the desired product and are polymerized using conventional redox or free radical initiators. Formation of low molecular weight copolymers may require the presence of chain terminators such as alcohols and the like in manners known in the art.
  • the subject copolymers have been found surprisingly effective in inhibiting scale formation especially with respect to inhibiting calcium phosphate deposition onto metal surfaces.
  • Calcium ions are normally present in hard water such as obtained from natural sources as, for example, seawater, lakes, rivers, etc.
  • Phosphates are normally present in aqueous systems either naturally or through treatment of the water for various purposes.
  • the calcium and the phosphate form a precipitate which can be generally represented as the normal phosphate C «(PO ) although it has also been proposed to be a calcium phosphate known as hydroxyapatite which has the formula Ca (PC> 4 ) OH or 3Ca 3 ( 0 4 ) • Ca(OH) .
  • a copolymer of 2-acrylamido-2-methylpropane sulfonic acid and methacrylic acid (mole ratio 1:2) as its sodium salt and having a molecular weight of about 5,000 was evaluated as a calcium phosphate scale inhibitor in a dynamic test apparatus.
  • the apparatus comprises a vertical glass cylinder having an eight kilowatt cylindrical stainless steel cartridge heater inside.
  • the cylinder was closed with a ballcock at the top and was equipped with temperature measurement probes at the inlet and outlet ports.
  • An open plastic vessel having a five liter capacity was used as the open reservoir. This reservoir had an outlet tube connected to a centrifical pump which fed (via a rotometer) into the bottom inlet port of the cylinder.
  • the outlet port is connected to the reservoir to return the aqueous fluid thereto.
  • the reservoir also contains a cooling coil to maintain the reservoir water at 123° F. and a water make-up actuated by a diaphragm pump.
  • the apparatus was maintained at a circulation rate of one
  • OMPI gallon per minute with an inlet temperature of 123° F. , an outlet temperature of 130° F. and a pH of 8.2 + 0.1 using a. Precision pH probe.
  • the aqueous system which circulates through the dynamic test apparatus was a water solution containing 750 ppm potassium chloride, 374 ppm calcium sulfate hemihydrate, 136 ppm calcium chloride, 341 ppm sodium chloride, 518 ppm magnesium sulfate heptahydrate, 380 ppm calcium as calcium carbonate and 15 ppm phosphate as PO (phosphoric acid) to simulate a hard natural water source.
  • Total hardness of the aqueous system (as Ca and Mg) was 591 ppm.
  • a concentrate of 1,000 ppm of the copolymer was formed and an aliquot portion was taken and mixed into the reservoir to provide a 20 ppm total dosage of copolymer in the aqueous system.
  • the aqueous system being tested was circulated through the apparatus for a 22 hour period.
  • the amount of calcium phosphate on the metal surface of the heater was determined by dissolving the scale formed with hydrochloric acid and conducting standard colorimetric analysis for phosphate.
  • As a standard a duplicate test was performed in which the aqueous system did not contain the copolymer agent. The analysis showed that 102.6 mg. of phosphate scale formed in the standard while only 43.0 mg. formed when the subject copolymer was present in the aqueous system. This shows a 58.1 % inhibition to calcium phosphate scale formation.
  • Example II A test was performed in the same manner as described in Example I above except that the copolymer used therein was replaced by a copolymer of

Abstract

Procédé empêchant la formation d'incrustations sur des surfaces métalliques en contact avec des systèmes aqueux et consistant à ajouter une quantité limite de copolymères d'acide 2-acrylamido-2-méthylpropane sulfonique et d'acide acrylique ou méthacrylique ou de leurs sels solubles dans l'eau.
PCT/US1982/000121 1982-01-29 1982-01-29 Procede empechant la formation d'incrustations WO1983002607A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
GB08325799A GB2125025B (en) 1982-01-29 1982-01-29 Process for inhibiting scale
PCT/US1982/000121 WO1983002607A1 (fr) 1982-01-29 1982-01-29 Procede empechant la formation d'incrustations
EP19820900853 EP0099883A4 (fr) 1982-01-29 1982-01-29 Procede empechant la formation d'incrustations.
DE19823249177 DE3249177T1 (de) 1982-01-29 1982-01-29 Verfahren zur Unterdrückung der Kesselsteinbildung
ES519364A ES519364A0 (es) 1982-01-29 1983-01-28 Procedimiento para inhibir la formacion de cascarilla sobre superficies metalicas en contacto con sistemas acuosos.
SE8301135A SE8301135L (sv) 1982-01-29 1983-03-01 Forfarande for inhibering av pannstensbildning

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US1982/000121 WO1983002607A1 (fr) 1982-01-29 1982-01-29 Procede empechant la formation d'incrustations

Publications (1)

Publication Number Publication Date
WO1983002607A1 true WO1983002607A1 (fr) 1983-08-04

Family

ID=22167790

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1982/000121 WO1983002607A1 (fr) 1982-01-29 1982-01-29 Procede empechant la formation d'incrustations

Country Status (6)

Country Link
EP (1) EP0099883A4 (fr)
DE (1) DE3249177T1 (fr)
ES (1) ES519364A0 (fr)
GB (1) GB2125025B (fr)
SE (1) SE8301135L (fr)
WO (1) WO1983002607A1 (fr)

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4575425A (en) * 1984-12-24 1986-03-11 Calgon Corporation Process for controlling calcium oxalate scale over a wide pH range
US4640793A (en) * 1984-02-14 1987-02-03 Calgon Corporation Synergistic scale and corrosion inhibiting admixtures containing carboxylic acid/sulfonic acid polymers
US4711725A (en) * 1985-06-26 1987-12-08 Rohm And Haas Co. Method of stabilizing aqueous systems
EP0271035A2 (fr) * 1986-12-08 1988-06-15 The B.F. Goodrich Company Traitement des milieux aqueux par des copolymères contenant de l'acide acrylamidoalcane-sulfonique
US4836933A (en) * 1987-01-16 1989-06-06 National Starch And Chemical Corporation Water treatment polymer
US4885097A (en) * 1986-12-08 1989-12-05 The B. F. Goodrich Company Stabilization of metal ions with terpolymers containing styrene sulfonic acid
US4889637A (en) * 1986-12-08 1989-12-26 Zahid Amjad Scale control with terpolymers containing vinyl alcohol
US4936987A (en) * 1983-03-07 1990-06-26 Calgon Corporation Synergistic scale and corrosion inhibiting admixtures containing carboxylic acid/sulfonic acid polymers
US4952326A (en) * 1986-12-08 1990-08-28 The B. F. Goodrich Company Dispersion of particulates in an aqueous medium
US4952327A (en) * 1986-12-08 1990-08-28 The B. F. Goodrich Company Scale control with terpolymers containing styrene sulfonic acid
US5282976A (en) * 1992-07-21 1994-02-01 Rhone-Poulenc Inc. Terpolymer useful as a scale inhibitor
US5380782A (en) * 1993-10-04 1995-01-10 Rohm And Haas Company Polymeric dispersants for ceramic materials
EP0877002A2 (fr) * 1997-05-09 1998-11-11 Rohm And Haas Company Agents antitartres
US6995120B2 (en) * 2001-10-03 2006-02-07 National Starch And Chemical Investment Holding Corporation Scale control composition for high scaling environments
EP2130898A1 (fr) 2008-06-04 2009-12-09 Rohm and Haas Company Polymères et leur utilisation pour l'inhibition de la formation de tartre dans des applications de lavage de vaisselle automatique

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4221381C1 (de) * 1992-07-02 1994-02-10 Stockhausen Chem Fab Gmbh Pfropf-Copolymerisate von ungesättigten Monomeren und Zuckern, Verfahren zu ihrer Herstellung und ihre Verwendung

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3709815A (en) * 1971-07-01 1973-01-09 Calgon Corp Boiler water treatment
US3709816A (en) * 1971-07-01 1973-01-09 Calgon Corp Control of alluvial and other deposits in aqueous systems
US3806367A (en) * 1972-06-01 1974-04-23 Bitz Lab Inc Acrylamido-sulfonic acid polymers and their use as rust and tubercle removing agents
US3928196A (en) * 1973-12-05 1975-12-23 Calgon Corp Inhibition of scale deposition

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3709815A (en) * 1971-07-01 1973-01-09 Calgon Corp Boiler water treatment
US3709816A (en) * 1971-07-01 1973-01-09 Calgon Corp Control of alluvial and other deposits in aqueous systems
US3806367A (en) * 1972-06-01 1974-04-23 Bitz Lab Inc Acrylamido-sulfonic acid polymers and their use as rust and tubercle removing agents
US3928196A (en) * 1973-12-05 1975-12-23 Calgon Corp Inhibition of scale deposition

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP0099883A4 *

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4936987A (en) * 1983-03-07 1990-06-26 Calgon Corporation Synergistic scale and corrosion inhibiting admixtures containing carboxylic acid/sulfonic acid polymers
US4640793A (en) * 1984-02-14 1987-02-03 Calgon Corporation Synergistic scale and corrosion inhibiting admixtures containing carboxylic acid/sulfonic acid polymers
US4575425A (en) * 1984-12-24 1986-03-11 Calgon Corporation Process for controlling calcium oxalate scale over a wide pH range
US4711725A (en) * 1985-06-26 1987-12-08 Rohm And Haas Co. Method of stabilizing aqueous systems
US4952327A (en) * 1986-12-08 1990-08-28 The B. F. Goodrich Company Scale control with terpolymers containing styrene sulfonic acid
EP0271035A2 (fr) * 1986-12-08 1988-06-15 The B.F. Goodrich Company Traitement des milieux aqueux par des copolymères contenant de l'acide acrylamidoalcane-sulfonique
US4885097A (en) * 1986-12-08 1989-12-05 The B. F. Goodrich Company Stabilization of metal ions with terpolymers containing styrene sulfonic acid
US4889637A (en) * 1986-12-08 1989-12-26 Zahid Amjad Scale control with terpolymers containing vinyl alcohol
EP0271035A3 (en) * 1986-12-08 1990-01-10 The B.F. Goodrich Company Treatment of aqueous medium with copolymers containing acrylamidoalkane sulfonic acid
US4952326A (en) * 1986-12-08 1990-08-28 The B. F. Goodrich Company Dispersion of particulates in an aqueous medium
US4836933A (en) * 1987-01-16 1989-06-06 National Starch And Chemical Corporation Water treatment polymer
US5282976A (en) * 1992-07-21 1994-02-01 Rhone-Poulenc Inc. Terpolymer useful as a scale inhibitor
US5380782A (en) * 1993-10-04 1995-01-10 Rohm And Haas Company Polymeric dispersants for ceramic materials
EP0877002A2 (fr) * 1997-05-09 1998-11-11 Rohm And Haas Company Agents antitartres
EP0877002A3 (fr) * 1997-05-09 1999-03-24 Rohm And Haas Company Agents antitartres
US6114294A (en) * 1997-05-09 2000-09-05 Rohm And Haas Company Copolymeric scale inhibitors for (Poly)phosphate scale control
US6995120B2 (en) * 2001-10-03 2006-02-07 National Starch And Chemical Investment Holding Corporation Scale control composition for high scaling environments
EP2130898A1 (fr) 2008-06-04 2009-12-09 Rohm and Haas Company Polymères et leur utilisation pour l'inhibition de la formation de tartre dans des applications de lavage de vaisselle automatique

Also Published As

Publication number Publication date
GB2125025B (en) 1985-07-03
SE8301135L (sv) 1983-07-30
SE8301135D0 (sv) 1983-03-01
EP0099883A1 (fr) 1984-02-08
GB2125025A (en) 1984-02-29
GB8325799D0 (en) 1983-10-26
ES8406566A1 (es) 1984-07-01
ES519364A0 (es) 1984-07-01
DE3249177T1 (de) 1984-09-06
EP0099883A4 (fr) 1984-05-29

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