DE3023701A1 - CORROSION INHIBITOR MADE OF ALUMINUM-GLUCONIC ACID COMPLEX, AND A METHOD FOR INHIBITING CORROSION ON IRON AND STEEL SURFACES - Google Patents

CORROSION INHIBITOR MADE OF ALUMINUM-GLUCONIC ACID COMPLEX, AND A METHOD FOR INHIBITING CORROSION ON IRON AND STEEL SURFACES

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Publication number
DE3023701A1
DE3023701A1 DE19803023701 DE3023701A DE3023701A1 DE 3023701 A1 DE3023701 A1 DE 3023701A1 DE 19803023701 DE19803023701 DE 19803023701 DE 3023701 A DE3023701 A DE 3023701A DE 3023701 A1 DE3023701 A1 DE 3023701A1
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DE
Germany
Prior art keywords
corrosion
gluconic acid
aluminum
iron
acid complex
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
DE19803023701
Other languages
German (de)
Inventor
Jose T. Lake Zurich Ill. Jacob
Vincent R. Twin Lakes Wis. Kuhn
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
WR Grace and Co
Original Assignee
Chemed Corp Cincinnati Ohio
Chemed Corp
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 Chemed Corp Cincinnati Ohio, Chemed Corp filed Critical Chemed Corp Cincinnati Ohio
Publication of DE3023701A1 publication Critical patent/DE3023701A1/en
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
    • C07C59/01—Saturated compounds having only one carboxyl group and containing hydroxy or O-metal groups
    • C07C59/10—Polyhydroxy carboxylic acids
    • C07C59/105—Polyhydroxy carboxylic acids having five or more carbon atoms, e.g. aldonic acids
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/12—Oxygen-containing compounds
    • C23F11/124—Carboxylic acids
    • C23F11/126—Aliphatic acids
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/18—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using inorganic inhibitors

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Inorganic Chemistry (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)

Description

Beschreibungdescription

Vorliegende Erfindung betrifft einen neuen Komplex als Korrosionsinhibitor in wäßrigen Systemen.The present invention relates to a new complex as a corrosion inhibitor in aqueous systems.

Es ist bekannt, Gluconate bei der Wasserbehandlung einzusetzen. Die US-PS 3 095 862 beschreibt Calciumgluconat als ein Carbonat-Entf ernungsmittel. Aus US-PS 3 711 246 ist die Verwendung von Natriumgluconat mit Natriumsilikat zur Verhütung oxidativer Korrosion bekannt. US-PS 4 108 790 schlägt die Verwendung von Natrium- und · Ammoniumgluconaten zur Verhinderung der oxidativen Korrosion in Kühlwassersystemen vor. Schließlich ist aus US-PS 4 120 655 bekannt, einen Phosphorsäureester zusammen mit einem Gluconat eines Metalls der Gruppen II bis VIII des Periodensystems zur Verhütung der Eisen(II!-Korrosion einzusetzen.It is known to use gluconates in water treatment. U.S. Patent 3,095,862 describes calcium gluconate as a carbonate remover. US Pat. No. 3,711,246 discloses the use of sodium gluconate with Sodium silicate known for preventing oxidative corrosion. U.S. Patent No. 4,108,790 suggests the use of Sodium and ammonium gluconates to prevent oxidative corrosion in cooling water systems. In the end is known from US-PS 4,120,655, a phosphoric acid ester together with a gluconate of a metal from groups II to VIII of the periodic table for prevention iron (II!) corrosion.

Aufgabe der vorliegenden Erfindung ist es, mit neuen nichttoxischen Verbindungen einen Korrosionsschutz für Metallteile aus Eisen und Stahl, wie z.B. Wärmeaustauscher, Motorengehäuse und Rohrleitungen, insbesondere zur Verhinderung von Metallverlusten, Lochfraß und Rostanfressung bei Eisenlegierungen, die in Kontakt mit Wasser stehen, zu schaffen.The object of the present invention is to use new non-toxic compounds to provide corrosion protection for Metal parts made of iron and steel, such as heat exchangers, motor housings and pipelines, in particular to prevent metal loss, pitting and corrosion of iron alloys that come into contact with Standing water to create.

1 30020/05841 30020/0584

Diese Aufgabe wind erfindungsgemäß gelöst durch einen neuen, sehr wirksamen Korrosionsinhibitor zur Hemmung der Korrosion auf Oberflächen aus Eisen und Stahl in wäßrigen Systemen, der dadurch gekennzeichnet ist, daß er aus einem Aluminium-Gluconsäure-Komplex besteht, der durch Umsetzung von Aluminiumchlorid-Hexahydrat mit GIuconsäure im Molverhältnis von 1:2 bis 2:1 im wäßrigen Medium hergestellt worden ist.This object is achieved according to the invention by a new, very effective corrosion inhibitor to inhibit corrosion on surfaces made of iron and steel in aqueous systems, which is characterized in that it consists of an aluminum-gluconic acid complex, the by reacting aluminum chloride hexahydrate with gluconic acid in a molar ratio of 1: 2 to 2: 1 in the aqueous Medium has been established.

Die Erfindung betrifft ferner ein Verfahren zur Hemmung der Korrosion auf Oberflächen aus Eisen und Stahl in wäßrigen Systemen, das dadurch gekennzeichnet ist, daß man dem wäßrigen System einen Aluminium-Gluconsäure-Komplex, der durch Umsetzung von Aluminiumchlorid-Hexahydrat mit Gluconsäure im Molverhältnis von 1:2 bis 2:1 in wäßrigem Medium hergestellt worden ist, als korrosionshemmendes Mittel zusetzt und in diesem System eine wirksame Konzentration des Korrosionsinhibitors aufrechterhält. The invention also relates to a method for inhibiting corrosion on surfaces made of iron and steel in aqueous systems, which is characterized in that the aqueous system is an aluminum-gluconic acid complex, by reacting aluminum chloride hexahydrate with gluconic acid in a molar ratio of 1: 2 to 2: 1 has been prepared in an aqueous medium as a corrosion inhibitor Agent adds and maintains an effective concentration of the corrosion inhibitor in this system.

Im einzelnen wird der Korrosionsinhibitor-Komplex wie folgt hergestellt:In detail, the corrosion inhibitor complex is produced as follows:

35,8 g Aluminiumchlorid-Hexahydrat (AlCl . 6HpO) werden mit 64,2 g einer wäßrigen Gluconsäurelösung (46,7 % aktiv) bei etwa 25°C ungefähr 60 Minuten lang intensiv35.8 g of aluminum chloride hexahydrate (AlCl. 6HpO) become with 64.2 g of an aqueous gluconic acid solution (46.7% active) at about 25 ° C. for about 60 minutes intensively

130020/0584130020/0584

gemischt. Die Mischung reagiert unter Bildung eines Komplexes von unbestimmter Struktur. Das Produkt wird nicht isoliert, sondern in wäßriger Lösung verwendet. Es wurden auch andere Molverhältnisse von AlCl . 6HO zu Gluconsäure, wie zum Beispiel 1:2 bis 2:1, untersucht und dabei festgestellt, daß Produkte mit diesen Verhältnissen gegenüber dem Komplex mit dem oben angegebenen angenäherten Molverhältnis 1:1 etwa gleichwertige Vorteile zeigen.mixed. The mixture reacts to form a complex of indefinite structure. The product will not isolated, but used in aqueous solution. Other molar ratios of AlCl were also used. 6HO to gluconic acid, such as 1: 2 to 2: 1, and found that products with these Ratios to the complex with the approximate molar ratio 1: 1 given above are approximately equivalent Show advantages.

Der Komplex wurde als Korrosionsinhibitor geprüft, wobei man ein Wasser verwendete, das 110 ppm Calcium, 51 ppm Magnesium, 185 ppm Bicarbonat, 492 ppm Chlorid und 630 ppm Sulfat enthielt. Die für diese Beurteilung angewandten Prüfmethoden sind von J. Jacob und H. Kerst in "Materials Protection and Performance", Band 16, Nr. 4, April 1977, beschrieben. Die Versuche wurden bei einem pH-Wert von 6,5 bis 8 und bei einer Temperatur von 54,4°C 24 Stunden lang durchgeführt. Die Ergebnisse sind in der nachfolgenden Tabelle zusammengestellt.The complex was tested as a corrosion inhibitor using a water containing 110 ppm calcium, Contained 51 ppm magnesium, 185 ppm bicarbonate, 492 ppm chloride and 630 ppm sulfate. The ones for this assessment applied test methods are from J. Jacob and H. Kerst in "Materials Protection and Performance", Volume 16, No. 4, April 1977. The experiments were carried out at a pH of 6.5 to 8 and at one temperature of 54.4 ° C for 24 hours. The results are compiled in the table below.

Es wird darauf hingewiesen, daß die Ergebnisse als Prozentsatz des Korrosionsschutzes angegeben sind, der wie folgt bestimmt wird:It should be noted that the results are expressed as a percentage of the corrosion protection that is determined as follows:

Die Korrosionsgeschwindigkeit in nichtbehandeltem Wasser betrug 1484/um pro Jahr, die des Beispiels 2 (sieheThe rate of corrosion in untreated water was 1484 / um per year, that of example 2 (see

13Ö020/058413Ö020 / 0584

nachfolgende Tabelle) betrug 776,um pro Jahr. Die folgende Gleichung wurde zur Berechnung des Prozentsatzes des Korrosionsschutzes benutzt:table below) was 776 to per year. The following Equation was used to calculate the percentage of corrosion protection:

KPJ(BV) - KPJ(IV) χ 100CPY (BV) - CPY (IV) χ 100

% Korrosionsschutz % Corrosion protection

KPJKPJ

(BV)(BV)

KPJ = Korrosionsgeschwindigkeit pro JahrKPJ = corrosion rate per year

BV = Blindversuch IV = InhibitorversuchBV = blank test IV = inhibitor test

z.B. :e.g.:

1484 - 776 776 1484-776 776

x 100 = 47,7 %x 100 = 47.7%

TabelleTabel

Beispielexample Konzentration des
Aluminium-Glucon-
säure-KomplexesConcentration of
Aluminum glucone
acid complex % des Korrosions
schutzes für
1010 Stahlteile % of corrosion
protection for
1010 steel parts 11 Blindversuch
(keine Behandlung)Blind test
(no treatment) OO 22 3,4 ppm3.4 ppm 47,7 %47.7% 33 6,8 ppm6.8 ppm 76,176.1 44th 6,8 ppm6.8 ppm 73,073.0 55 6,8 ppm6.8 ppm 75,075.0 66th 10,2 ppm10.2 ppm 73,073.0

130020/0584130020/0584

Bei der Behandlung eines wäßrigen Systems mit Hilfe des erfindungsgemäßen Verfahrens wird eine Konzentration von etwa 0,1 bis 500 ppm, besonders bevorzugt von etwa 1 bis 30 ppm, des erfindungsgemäßen Inhibitor-Komplexes in Wasser aufrechterhalten.When treating an aqueous system with the aid of the The method according to the invention becomes a concentration from about 0.1 to 500 ppm, particularly preferably from about 1 to 30 ppm, of the inhibitor complex according to the invention maintained in water.

Dieser Inhibitor kann mit bekannten Zunder-Inhibitoren, Dispersionsmitteln und Korrosionsinhibitoren für Neumessing, wie zum Beispiel Benzotriazol oder Mercaptobenzothiazol, gemischt werden. Typische industrielle Anwendungen, bei denen die vorliegende Erfindung von Nutzen ist, sind die Behandlung von Wasser, Umlaufkühlungen, Druckflüssigkeiten, Frostschutzmitteln, Wärmeübertragungsmitteln sowie die Behandlung bei Erdölbohrungen .This inhibitor can be combined with known scale inhibitors, dispersants and corrosion inhibitors for new brass, such as benzotriazole or mercaptobenzothiazole, be mixed. Typical industrial applications where the present invention of The benefits are the treatment of water, circulation cooling, hydraulic fluids, antifreeze, heat transfer fluids as well as treatment for oil wells.

1 30020/0584.1 30020/0584.

Claims (4)

Korrosionsinhibitor aus Aluminium-Gluconsäure-Komplex sowie ein Verfahren zur Hemmung der
Korrosion auf Oberflächen aus Eisen und StahlCorrosion inhibitor made from aluminum-gluconic acid complex and a method for inhibiting the
Corrosion on iron and steel surfaces PatentansprücheClaims Konnosionsinhibitor zur Hemmung der Korrosion auf Oberflächen aus Eisen und Stahl in wäßrigen Systemen, dadurch gekennzeichnet, daß er aus einem AIuminium-Gluconsäure-Komplex besteht, der durch Umsetzung von Aluminiumchlorid-Hexahydrat mit Gluconsäure im Molverhältnis von 1:2 bis 2:1 im wäßrigen Medium hergestellt worden ist.Conjunction inhibitor to inhibit corrosion on surfaces made of iron and steel in aqueous systems, characterized in that it consists of an aluminum-gluconic acid complex consists of the reaction of aluminum chloride hexahydrate with gluconic acid in a molar ratio of 1: 2 to 2: 1 in the aqueous Medium has been established. 2. Verfahren zur Hemmung der Korrosion auf Oberflächen aus Eisen und Stahl in wäßrigen Systemen,2. Process for inhibiting corrosion on surfaces made of iron and steel in aqueous systems, 1 30020/05841 30020/0584 dadurch gekennzeichnet, daß man dem wäßrigen System einen Aluminium-Gluconsäure- Komplex, der durch Umsetzung von Aluminiumchlorid- Hexahydrat mit Gluconsäure im Molverhältnis von 1:2 bis 2:1 in wäßrigem Medium hergestellt worden ist, als korrosionshemmendes Mittel zusetzt und in diesem System eine wirksame Konzentration des Korrosionsinhibitors aufrechterhält. characterized in that the aqueous system is an aluminum-gluconic acid complex, the by reacting aluminum chloride hexahydrate with gluconic acid in a molar ratio of 1: 2 to 2: 1 Has been prepared in an aqueous medium, added as a corrosion inhibitor and in this System maintains an effective concentration of the corrosion inhibitor. 3. Verfahren nach Anspruch 2, dadurch gekennzeichnet, daß die wirksame Konzentration in dem wäßrigen System im Bereich von 0,1 bis 500 ppm liegt.3. The method according to claim 2, characterized in that the effective concentration in the aqueous System is in the range of 0.1 to 500 ppm. 4. Verfahren nach Anspruch 2, dadurch gekennzeichnet, daß die wirksame Konzentration in dem wäßrigen System im Bereich von 1 bis 30 ppm liegt.4. The method according to claim 2, characterized in that the effective concentration in the aqueous System is in the range of 1 to 30 ppm. 130020/0584130020/0584
DE19803023701 1979-10-01 1980-06-25 CORROSION INHIBITOR MADE OF ALUMINUM-GLUCONIC ACID COMPLEX, AND A METHOD FOR INHIBITING CORROSION ON IRON AND STEEL SURFACES Ceased DE3023701A1 (en)

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US8046279A 1979-10-01 1979-10-01

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Country Status (7)

Country Link
CA (1) CA1169873A (en)
DE (1) DE3023701A1 (en)
ES (1) ES8106682A1 (en)
FR (1) FR2466514B1 (en)
GB (1) GB2059948B (en)
IT (1) IT1140959B (en)
SE (1) SE447914B (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ATE229487T1 (en) * 1999-10-29 2002-12-15 Sika Ag LOW VISCOSITY, STABILIZED SETTING AND HARDENING ACCELERATOR
AU783765B2 (en) * 2001-04-23 2005-12-01 Sika Technology Ag Stabilized setting and hardening accelerator of low viscosity
US20150376799A1 (en) * 2014-06-30 2015-12-31 Baker Hughes Incorporated Non-phosphorous containing corrosion inhibitors for aqueous systems
US10683576B2 (en) * 2017-03-27 2020-06-16 Baker Hughes, A Ge Company, Llc Corrosion inhibitors for passivation of galvanized coatings and carbon steel

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3711246A (en) * 1971-01-06 1973-01-16 Exxon Research Engineering Co Inhibition of corrosion in cooling water systems with mixtures of gluconate salts and silicate salts
US4108790A (en) * 1971-11-02 1978-08-22 Exxon Research & Engineering Co. Corrosion inhibitor
US4120655A (en) * 1976-07-13 1978-10-17 Societe Nationale Elf Aquitaine Method for the inhibition of corrosion of ferrous metals in an aqueous medium

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2529178A (en) * 1947-12-06 1950-11-07 W H And L D Betz Method for obtaining corrosion and tuberculation inhibition in water systems
US2829039A (en) * 1954-03-01 1958-04-01 Hooker Electrochemical Co Corrosion inhibited trichloracetates
FR1462181A (en) * 1963-11-18 1966-04-15 Nalco Chemical Co Cooling water treatment and compositions useful therefor
JPS5913595B2 (en) * 1977-10-21 1984-03-30 日本農薬株式会社 Metal corrosion inhibitor and corrosion prevention method

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3711246A (en) * 1971-01-06 1973-01-16 Exxon Research Engineering Co Inhibition of corrosion in cooling water systems with mixtures of gluconate salts and silicate salts
US4108790A (en) * 1971-11-02 1978-08-22 Exxon Research & Engineering Co. Corrosion inhibitor
US4120655A (en) * 1976-07-13 1978-10-17 Societe Nationale Elf Aquitaine Method for the inhibition of corrosion of ferrous metals in an aqueous medium

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
BEILSTEIN: Handbuch der Org. Chemie III, 3, S.1059, 1962 *
Chemie in unserer Zeit, 3, S.77-83, 1969 *

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SE447914B (en) 1986-12-22
SE8005447L (en) 1981-04-02
ES495541A0 (en) 1981-09-01
FR2466514A1 (en) 1981-04-10
GB2059948A (en) 1981-04-29
ES8106682A1 (en) 1981-09-01
IT8022177A0 (en) 1980-05-19
IT1140959B (en) 1986-10-10
GB2059948B (en) 1983-09-21
FR2466514B1 (en) 1985-10-04
CA1169873A (en) 1984-06-26

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Owner name: DEARBORN CHEMICAL CO. (N.D.GES.D. STAATES DELAWARE

8127 New person/name/address of the applicant

Owner name: W.R. GRACE & CO., NEW YORK, N.Y., US

8128 New person/name/address of the agent

Representative=s name: FRHR. VON UEXKUELL, J., DIPL.-CHEM. DR.RER.NAT. GR

8110 Request for examination paragraph 44
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