DE1200756B - Treatment of chloride-containing industrial water with phosphates - Google Patents

Treatment of chloride-containing industrial water with phosphates

Info

Publication number
DE1200756B
DE1200756B DEG35540A DEG0035540A DE1200756B DE 1200756 B DE1200756 B DE 1200756B DE G35540 A DEG35540 A DE G35540A DE G0035540 A DEG0035540 A DE G0035540A DE 1200756 B DE1200756 B DE 1200756B
Authority
DE
Germany
Prior art keywords
chloride
phosphate
phosphates
treatment
water
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.)
Pending
Application number
DEG35540A
Other languages
German (de)
Inventor
Giulio Gross
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.)
BK Giulini Chemie GmbH
Original Assignee
Giulini Gebrueder GmbH
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 Giulini Gebrueder GmbH filed Critical Giulini Gebrueder GmbH
Priority to DEG35540A priority Critical patent/DE1200756B/en
Priority to BE628246D priority patent/BE628246A/xx
Priority to DK68263A priority patent/DK102899C/en
Priority to FR20105A priority patent/FR1351943A/en
Priority to NL295026D priority patent/NL295026A/xx
Priority to GB2894263A priority patent/GB1005691A/en
Publication of DE1200756B publication Critical patent/DE1200756B/en
Pending 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
    • 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
    • C23F11/184—Phosphorous, arsenic, antimony or bismuth containing compounds
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00—Compositions for glass with special properties
    • C03C4/0035—Compositions for glass with special properties for soluble glass for controlled release of a compound incorporated in said glass
    • 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
    • C23F11/187—Mixtures of inorganic inhibitors
    • C23F11/188—Mixtures of inorganic inhibitors containing phosphates
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28G—CLEANING OF INTERNAL OR EXTERNAL SURFACES OF HEAT-EXCHANGE OR HEAT-TRANSFER CONDUITS, e.g. WATER TUBES OR BOILERS
    • F28G9/00—Cleaning by flushing or washing, e.g. with chemical solvents

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Combustion & Propulsion (AREA)
  • General Engineering & Computer Science (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Glass Compositions (AREA)

Description

BUNDESREPUBLIK DEUTSCHLANDFEDERAL REPUBLIC OF GERMANY

DEUTSCHESGERMAN

PATENTAMTPATENT OFFICE

AUSLEGESCHRIFTEDITORIAL

Int. CL: Int. CL:

Nummer:
Aktenzeichen:
Anmeldetag:
Auslegetag:Number:
File number:
Registration date:
Display day:

C02bC02b

Deutsche Kl.: 85 b-1/01 German class: 85 b -1/01

G 35540IV a/85 bG 35540IV a / 85 b

24. Juli 1962July 24, 1962

9. September 1965September 9, 1965

Bei aggressiven Brauchwässern werden zum Korrosionsschutz der wasserführenden, metallischen Leitungen und Apparate Chromate, Silikate und Phosphate eingesetzt. Es ist bekannt, daß man bei den aggressiven Brauchwässern die leichtlöslichen Orthophosphate oder kondensierten Phosphate, aber auch die schwerlöslichen, kondensierten Phosphate, z. B. des Natrium-Calciums oder Natrium-Magnesiums im Phosphatimpfverfahren verwendet. In neuerer Zeit sind auch schwerlösliche siliciumhaltige Natrium-Calcium-Phosphate im Phosphatimpfverfahren eingesetzt worden. Diese Verfahren haben bei weichen, kohlensäure- und sauerstoffaggressiven Brauchwässern Korrosionen bei wasserdurchströmten metallischen Werkstoffen herabsetzen können, versagten aber vielfach bei stärker korrosiven Brauchwässern, z. B. chloridhaltigen.In the case of aggressive process water, the water-bearing, metallic Pipes and apparatuses chromates, silicates and phosphates are used. It is known that at the easily soluble orthophosphates or condensed phosphates, but the aggressive process water also the sparingly soluble, condensed phosphates, e.g. B. of sodium-calcium or sodium-magnesium used in the phosphate inoculation process. Lately there are also sparingly soluble silicon-containing sodium-calcium-phosphates been used in the phosphate inoculation process. These processes are used for soft, carbonic acid and oxygen-aggressive process water Corrosion in metallic materials through which water flows, but often failed for more corrosive service water, e.g. B. chloride-containing.

Überraschenderweise ergibt die Anwendung eines kondensierten siliciumhaltigen Natrium-Calcium-Zink-Phosphates mit einem ZnO-Gehalt von 5 bis 15°/0, vorzugsweise 10%, gegenüber den angeführten Verfahren in stärker korrosiven Brauchwässern eine entscheidend verminderte Korrosionsgeschwindigkeit.Surprisingly, the application of a fused siliceous resulting sodium-calcium-zinc phosphate having a ZnO content of from 5 to 15 ° / 0, preferably 10%, compared to the processes mentioned in more corrosive process water a critical reduced corrosion rate.

Bei chloridhaltigen, aggressiven Brauchwässern können z. B. die Abtragungen an metallischen Werk-Stoffen bis zu 2 mm und mehr pro Jahr betragen. Nach den bisher üblichen Phosphatimpfverfahren ließ sich diese Korrosion auf etwa 1 mm pro Jahr vermindern. Bei siliciumhaltigen Phosphaten war sogar eine Verminderung auf 0,4 mm pro Jahr möglich. Das erfindungsgemäße Verfahren gestattet nunmehr eine weitere Herabsetzung der Korrosion auf g 0,05 mm pro Jahr. Besonders vorteilhaft ist das Verfahren, wenn es mit einer Stoßbehandlung beginnt. In diesem Falle sind für begrenzte Zeit, mindestens jedoch 4 Tage lang, siliciumhaltige Natrium-Calcium-Zink-Phosphat-Mengen in etwa 10 fach stärkerer Dosierung anzuwenden.In the case of chloride-containing, aggressive process water, z. B. the removal of metallic materials up to 2 mm and more per year. According to the phosphate inoculation process that has been customary up to now this corrosion could be reduced to about 1 mm per year. In the case of silicon-containing phosphates even a reduction to 0.4 mm per year is possible. The method according to the invention allows now a further reduction in corrosion to 0.05 mm per year. Is particularly advantageous the procedure if it starts with a shock treatment. In this case, for a limited time, but at least 4 days, silicon-containing sodium-calcium-zinc-phosphate amounts approximately Use 10 times stronger dosage.

Es werden nur chloridhaltige Brauchwässer, z. B. für Kühlzwecke, mit kondensiertem siliciumhaltigem Natrium-Calcium-Zink-Phosphat behandelt. Eine Behandlung von Trinkwässern ist ausgeschlossen.Only process water containing chloride, e.g. B. for cooling purposes, with condensed silicon containing Sodium-Calcium-Zinc-Phosphate treated. One Treatment of drinking water is excluded.

Das kondensierte siliciumhaltige Natrium-Calcium-Zink-Phosphat wird zum Zwecke der Dosierung in Durchflußfiltern aus beliebigen Werkstoffen, z. B. Stahl, Rotguß, Aluminiumlegierung oder Kunststoffen, dem strömenden Wasser ausgesetzt, wodurch dem Wasser Mengen von 1 bis 10 mg/1 P2O5 und 0,1 bis 2,0 mg/1 Zn zugesetzt werden.The condensed silicon-containing sodium-calcium-zinc-phosphate is used for metering in flow filters made of any material, eg. B. steel, gunmetal, aluminum alloy or plastics, exposed to the flowing water, whereby amounts of 1 to 10 mg / 1 P 2 O 5 and 0.1 to 2.0 mg / 1 Zn are added to the water.

Das kondensierte siliciumhaltige Natrium-Calcium-Zink-Phosphat wurde nach an sich bekannter Methode durch Schmelzen einer Mischung von 100 kg MonoBehandlung von chloridhaltigen Brauchwässern mit PhosphatenThe condensed silicon-containing sodium-calcium-zinc-phosphate was made according to a method known per se by melting a mixture of 100 kg mono-treatment of chloride-containing industrial water with phosphates

Anmelder:Applicant:

Gebrüder GiuliniGiulini brothers

Gesellschaft mit beschränkter Haftung,Company with limited liability,

Ludwigshafen/Rhein, Giulinistr. 2Ludwigshafen / Rhine, Giulinistr. 2

Als Erfinder benannt:Named as inventor:

Giulio Gross, Mailand (Italien)Giulio Gross, Milan (Italy)

natriumphosphat krist, 2,1 kg Rohphosphat, 5,7 kg Zinkoxyd bei Temperaturen von 1000 bis 1200° C und langsames Abkühlen der Schmelze in einer Aluminiumwanne in einer Schichtdicke von etwa cm an der Luft hergestellt.Sodium phosphate crystalline, 2.1 kg rock phosphate, 5.7 kg zinc oxide at temperatures from 1000 to 1200 ° C and slowly cooling the melt in an aluminum pan in a layer thickness of about cm made in the air.

Beim Zusammenschmelzen obiger Komponenten entsteht im Endprodukt ein kondensiertes Phosphat.When the above components melt together, a condensed phosphate is formed in the end product.

Die Zusammensetzung des Produktes war folgende: 62,5°/0 P8O5, 1,5% CaO, 1,0% SiO2, 7,8% ZnO, 27,5% Na2O.The composition of the product was as follows: 62.5 ° / 0 P 8 O 5, 1.5% CaO, 1.0% SiO 2, 7.8% ZnO, 27.5% Na 2 O.

Ein weiteres kondensiertes siliciumhaltiges Natrium-Calcium-Zink-Phosphat wurde durch Schmelzen einer Mischung von 125 kg Mononatriumphosphat krist., 7,6 kg Rohphosphat, 9,6 kg Zinkoxyd bei Temperaturen von 1000 bis 12000C und langsames Abkühlen der Schmelze in einer Aluminiumwanne in einer Schichtdicke von etwa 10 cm an der Luft hergestellt.Another condensed silicon-containing sodium calcium zinc phosphate was crystalline by melting a mixture of 125 kg of monosodium phosphate., 7.6 kg rock phosphate, 9.6 kilograms of zinc oxide at temperatures of 1000 to 1200 0 C and slowly cooling the melt into an aluminum pan produced in a layer thickness of about 10 cm in the air.

Die Zusammensetzung des Produktes war folgende: 59,8% PA, 3,6% CaO, 0,3% SiO2, 9,8% ZnO, 25,5% Na2O.The composition of the product was as follows: 59.8% PA, 3.6% CaO, 0.3% SiO 2 , 9.8% ZnO, 25.5% Na 2 O.

Aus dem folgenden Beispiel ist die Wirkung dieses kondensierten siliciumhaltigen Natrium-Calcium-Zink-Phosphates ersichtlich. Das Wasser hatte folgende Kennzahlen:The following example shows the effect of this condensed silicon-containing sodium-calcium-zinc-phosphate evident. The water had the following key figures:

pH 7,5 bis 8,0pH 7.5 to 8.0

Gesamthärte 25° dHTotal hardness 25 ° dH

Karbonathärte 4° dHCarbonate hardness 4 ° dH

Nichtkarbonathärte 21° dHNon-carbonate hardness 21 ° dH

Chlorid 400 mg/1Chloride 400 mg / 1

Sauerstoff 8 mg/1Oxygen 8 mg / 1

509 660/410509 660/410

Beispielexample

Bei Behandlung des Wassers mit kondensiertem siliciumhaltigem Natrium-Calcium-Phosphat (Handelsmarke Siliphos) in einer Impf schleuse wurden folgende Korrosionswerte bei Eisen festgestellt:If the water is treated with condensed silicon-containing sodium-calcium-phosphate (trademark Siliphos) in an inoculation lock, the following corrosion values were found for iron:

IOIO

Zeit in TagenTime in days Korrosionen in Millimeter
pro JahrCorrosion in millimeters
per year 11 1,001.00 33 0,900.90 77th 0,750.75 1414th 0,600.60 2121 0,480.48 2828 0,400.40 3535 0,350.35 4242 0,320.32 4949 0,310.31 5656 0,300.30 6363 0,280.28

Zeit in TagenTime in days Korrosionen in Millimeter
pro JahrCorrosion in millimeters
per year 11 0,070.07 33 0,0550.055 44th 0,0350.035 77th 0,0510.051 1414th 0,0480.048 2828 0,050.05 4242 0,0450.045 5656 0,0430.043 6363 0,0400.040

Das kondensierte siliciumhaltige Natrium-Calcium-Zink-Phosphat bewirkt hingegen vom ersten Tage an eine fast völlige Unterbindung jeglicher Korrosionen an Eisen. Es wurden folgende Werte ermittelt:The condensed silicon-containing sodium-calcium-zinc-phosphate, however, works from the first day an almost complete suppression of any corrosion on iron. The following values were determined:

Claims (2)

Patentansprüche:Patent claims: 1. Behandlung von korrosiven chloridhaltigen Brauchwässern zum Zwecke des Korrosionsschutzes an Metallen im Phosphatimpfverfahren, dadurch gekennzeichnet, daß kondensierte siliciumhaltige Natrium-Calcium-Zink-Phosphate verwendet werden, die einen Zinkoxydgehalt von 5 bis 15%, vorzugsweise 10°/0, enthalten. 1. Treatment of corrosive, chloride-containing process water for the purpose of corrosion protection on metals in the phosphate inoculation process, characterized in that condensed silicon-containing sodium-calcium-zinc phosphates are used which contain a zinc oxide content of 5 to 15%, preferably 10 ° / 0. 2. Verfahren gemäß Anspruch 1 bei chloridhaltigen Brauchwässern mit mehr als 50 mg/1 Chlorid, dadurch gekennzeichnet, daß innerhalb von 24 Stunden und während 4 Tagen zum Zwecke einer Stoßbehandlung die Dosierung auf die lOfache Menge des Normalen gesteigert wird.2. The method according to claim 1 for chloride-containing industrial water with more than 50 mg / 1 Chloride, characterized in that within 24 hours and during 4 days for the purpose a shock treatment, the dosage is increased to ten times the normal amount. 509 660/410 8.65 © Bundesdruckerei Berlin509 660/410 8.65 © Bundesdruckerei Berlin
DEG35540A 1962-07-24 1962-07-24 Treatment of chloride-containing industrial water with phosphates Pending DE1200756B (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
DEG35540A DE1200756B (en) 1962-07-24 1962-07-24 Treatment of chloride-containing industrial water with phosphates
BE628246D BE628246A (en) 1962-07-24 1963-02-11
DK68263A DK102899C (en) 1962-07-24 1963-02-14 Process for treating chloride-containing water with phosphates.
FR20105A FR1351943A (en) 1962-07-24 1963-03-26 Process for treating water containing chlorides by means of phosphates
NL295026D NL295026A (en) 1962-07-24 1963-07-05
GB2894263A GB1005691A (en) 1962-07-24 1963-07-22 Treatment of water

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEG35540A DE1200756B (en) 1962-07-24 1962-07-24 Treatment of chloride-containing industrial water with phosphates

Publications (1)

Publication Number Publication Date
DE1200756B true DE1200756B (en) 1965-09-09

Family

ID=7125190

Family Applications (1)

Application Number Title Priority Date Filing Date
DEG35540A Pending DE1200756B (en) 1962-07-24 1962-07-24 Treatment of chloride-containing industrial water with phosphates

Country Status (6)

Country Link
BE (1) BE628246A (en)
DE (1) DE1200756B (en)
DK (1) DK102899C (en)
FR (1) FR1351943A (en)
GB (1) GB1005691A (en)
NL (1) NL295026A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0142038A1 (en) * 1983-10-18 1985-05-22 International Standard Electric Corporation Corrosion inhibitor for cooling systems of vehicles
FR2571745A1 (en) * 1984-10-17 1986-04-18 Trest Juzhvodoprovod ANTICORROSIVE FOR PROTECTING THE INTERNAL SURFACE OF A CORROSION CHANNEL, METHOD FOR OBTAINING THE SAME, AND METHOD FOR PROTECTING THE INTERNAL SURFACE OF A CORROSION LINE USING THE SAME

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3432428A (en) * 1965-06-24 1969-03-11 Nalco Chemical Co Polyphosphate glasses and water treatment uses thereof
DE2940695A1 (en) * 1979-10-08 1981-04-16 Hoechst Ag, 6000 Frankfurt CORROSION INHIBITING PIGMENT
US4849171A (en) * 1987-02-09 1989-07-18 Bruce Murray Corrosion inhibition of sodium and calcium chloride

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0142038A1 (en) * 1983-10-18 1985-05-22 International Standard Electric Corporation Corrosion inhibitor for cooling systems of vehicles
FR2571745A1 (en) * 1984-10-17 1986-04-18 Trest Juzhvodoprovod ANTICORROSIVE FOR PROTECTING THE INTERNAL SURFACE OF A CORROSION CHANNEL, METHOD FOR OBTAINING THE SAME, AND METHOD FOR PROTECTING THE INTERNAL SURFACE OF A CORROSION LINE USING THE SAME

Also Published As

Publication number Publication date
NL295026A (en) 1965-04-26
GB1005691A (en) 1965-09-29
BE628246A (en) 1963-05-29
DK102899C (en) 1965-10-18
FR1351943A (en) 1964-02-07

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