EP3204532B1 - Ph neutral deruster composition - Google Patents

Ph neutral deruster composition Download PDF

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EP3204532B1
EP3204532B1 EP15735726.0A EP15735726A EP3204532B1 EP 3204532 B1 EP3204532 B1 EP 3204532B1 EP 15735726 A EP15735726 A EP 15735726A EP 3204532 B1 EP3204532 B1 EP 3204532B1
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deruster
deruster composition
composition according
acid
metal
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German (de)
English (en)
French (fr)
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EP3204532A1 (en
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Martin Webster
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NCH Corp
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NCH Corp
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    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/24—Cleaning or pickling metallic material with solutions or molten salts with neutral solutions
    • C23G1/26—Cleaning or pickling metallic material with solutions or molten salts with neutral solutions using inhibitors
    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/24—Cleaning or pickling metallic material with solutions or molten salts with neutral solutions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/662—Carbohydrates or derivatives
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0073—Anticorrosion compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/04—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors
    • C23G1/06—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors
    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/08—Iron or steel
    • C23G1/088—Iron or steel solutions containing organic acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces
    • C11D2111/16—Metals

Definitions

  • the present invention relates to a deruster composition of neutral pH which is designed to remove corroded metal, including rust or tarnish, from metal surfaces.
  • Oxygen can be obtained from air or water, both of which are often present in the environment surrounding metallic materials. Oxygen readily reacts with ferrous metals to form oxides such as iron oxide, commonly known as rust. Iron oxides such as rust and magnetite are well known, however, sulphides, chlorides, phosphates, chromate films and many other contaminants can also be formed by corrosion.
  • Tarnish changes the appearance of the metal, such that the surface of the metal appears dull and blackened. Although formed in a similar manner to rust, tarnish is self-limiting and only affects the top few layers of the metal. Tarnish can occur on non-ferrous metals, such as copper, brass, silver and other similar metals. Tarnish is generally not flaky or friable, and does not compromise the strength of the metal article. However, the appearance and reflective qualities of the metal are impeded by the layer of tarnish.
  • Products are available which are used to remove the deposits formed by corrosion, such as rust or tarnish, once the rust or corrosion has occurred.
  • the corroded metal parts can be soaked in a rust removal solution, or the solution can be sprayed or otherwise applied to the part.
  • These rust removal solutions or products are generally liquid formulations and are commonly known in the industry as "deruster" compositions or formulations.
  • Several deruster products require elevated temperatures in order to dissolve the deposits from the metals.
  • One of the problems with existing rust removal products is that the solutions which are capable of dissolving the rust are so corrosive that they tend to damage the surface which is being cleaned.
  • the first method involves acidic products based generally, but not exclusively, on hydrochloric acid and phosphoric acid.
  • the acid reacts with the metal oxide and solubilises it.
  • the acid also attacks the base metal generating or evolving hydrogen gas.
  • the acid used for the treatment is corrosive to the skin and eyes.
  • the acid produces corrosive gases or fumes which attack the surrounding equipment.
  • the second method involves the use of highly alkaline products, which are generally caustic based. Most alkaline deruster formulations have lower levels of gas evolution.
  • Flash rusting is a common occurrence after cleaning with an acidic deruster formulation due to the sudden availability of metal surface in a reactive state. In some cases, it is encouraged after cleaning, as a thin layer of oxidised metal can protect the underlying metal from further oxidation. However, the occurrence of flash rusting can make it difficult to apply products (such as paint or rust prevention products) to the metal after cleaning.
  • chelating agent which is used to dissolve the rust.
  • Chelating agents are also known as complexing agents, or sequestrants, and are used to bind metal ions in solution. Chelating agents can be water soluble and can therefore be used in aqueous solutions. Chelation describes a particular way that ions and molecules are bound to metal ions. Chelating agents are chemicals which react with metals to improve their general stability and likelihood of bonding with other metals or chemicals. The metal that remains is known as a "chelate". Most metals have chemical structures that closely resemble chains, but chelating agents join the ends in order to form a ring, known as a ligand.
  • This ring structure makes the ions more stable and helps them move with greater ease through a range of different environments.
  • the chelate effect describes the enhanced affinity of chelating ligands for a metal ion compared to the affinity of a collection of similar non-chelating ligands for the same metal.
  • many chelants are phosphonate based.
  • Chelating agents can form soluble complexes with metal ions in the rinse water thus preventing the formation of metal precipitates. By forming water soluble metal complexes, the metal from the corroded or rusted parts can be easily removed and rinsed away.
  • Surfactants can have multiple uses in a deruster composition.
  • the purpose of surfactants in general can include the following; to act as a dispersing agent, to reduce surface tension, to boost foam formation, to aid emulsion formation and stabilisation, and to act as a wetting agent.
  • one or more surfactants can be added to improve surface wetting of the metal oxide, to assist with the lifting of contamination from the surface of the metal to be cleaned, to assist in the degreasing of metal parts, and/or to assist with maintaining oil and particulates of dirt in suspension. Improving the surface wetting of the metal oxide increases the penetration of the deruster composition into any metal oxide deposits. This reduces the time taken to dissolve the iron oxides, which can be particularly important for any larger encrustations on the metal surface.
  • Surfactants are broadly divided into the following categories: cationic, anionic, non-ionic, and amphoteric. There are a number of different types of non-ionic surfactants which are suitable for use in deruster compositions.
  • Non-ionic surfactants are capable of providing anti-corrosion effects as they have a partially cationic character. These surfactants exhibit good foaming properties, which can be useful for flotation of debris. Non-ionic surfactants do not dissociate in aqueous solutions, and are not affected by water pH or water hardness.
  • non-ionic surfactants include ethyoxylated linear alcohols, ethoxylated alkyl phenols, fatty acid esters, amine and amide derivatives, alkylpolyglucosides, ethyleneoxide copolymers, propyleneoxide copolymers, polyalcohols, ethoxylated polyalcohols, thiols (mercaptans) and derivatives and nitrogenated non-ionic surfactants.
  • This group further includes imidazoles and imides, sorbitan esters (such as SPAN®) and ethoxylated sorbitan (TWEEN® and equivalents).
  • the present invention provides a deruster composition with improved biodegradability whilst enabling operation within a neutral pH range. This reduces the damage caused to the metal parts being cleaned whilst also limiting the operational hazards.
  • the deruster composition can also act as a corrosion removal agent for other forms of corrosion such as tarnish.
  • Both US 2012 021963 A1 and US2012 260938 A1 disclose a deruster aqueous composition having a pH in the range of 5 to 8, and comprising an alkyl polyglycoside and an aminocarboxylic acid.
  • a deruster composition according to claim 1.
  • a second chelating agent may be provided.
  • the second chelating agent can be another aminopolycarboxylic acid, a phosphonate based chelating agent, or an alternative chelating agent such as glycolic acid.
  • the deruster composition can be used for the removal of corrosion, including the removal of rust or tarnish from a metallic surface.
  • the deruster composition can also be referred to as a metal brightener or tarnish remover.
  • the tarnish remover is particularly suitable for removing tarnish from transition metals and their alloys.
  • the tarnish remover has been found to be very effective for the removal of tarnish from copper and its alloys, including brass and bronze.
  • the deruster composition can also act as a corrosion inhibitor for metals.
  • At least one of the chelating agents is an aminopolycarboxylic acid.
  • Aminopolycarboxylic acids are biodegradable chelating agents.
  • the biodegradable ligands contain a basic nitrogen atom or two atoms with an electron pair capable of interacting with metal ions and acidic carboxylic acid groups capable of coordinating metal ions through the oxygen.
  • the biodegradable quality of these chelating agents represents a huge step forward over conventional chelating agents, as they are more resistant to wastewater treatment and purification through conventional physicochemical and biological treatment methods. As environmental protection issues have become more prominent, legislation on chelating agents has become more rigorous.
  • Aminopolycarboxylic acids are phosphate-free and examples from this group of chelating agents include tetrasodium 3-hydroxy-2,2'-iminodisuccinate (HIDS), ethylenediamine-N,N'-disuccinic acid (EDDS), N-(1,2-dicarboxyetyhl)-D,L-aspartic acid (IDS) (also known as iminodisuccinic acid), N,N-bis(carboxymethyl)glutamic acid (GLDA, also known as tetrasodium glutamate diacetate), and methylglycin diacetic acid (MGDA).
  • HIDS tetrasodium 3-hydroxy-2,2'-iminodisuccinate
  • EDDS ethylenediamine-N,N'-disuccinic acid
  • IDDS N-(1,2-dicarboxyetyhl)-D,L-aspartic acid
  • GLDA N,N-bis
  • Tetrasodium glutamate diacetate is a readily biodegradable chelate based on L-glutamic acid.
  • the manufacturers of GLDA claim that it performs better than conventional chelating agents such as EDTA and NTA for hard surface cleaning, and is more effective as a chelating agent than phosphonate-based chelating agents.
  • GLDA is marketed as Dissolvine ® GL by Akzo Nobel N.V. It has high solubility over a wide pH range. It is made from a natural and renewable raw material, a waste product from sugar refining. It therefore has a small ecological footprint.
  • IDS iminodisuccinic acid
  • complexes formed from IDS are also very biodegradable. IDS has demonstrated good stability over a wide range of pH values and is able to form complexes with heavy metal ions.
  • Methylglycin diacetic acid is also known as glycine-N,N-diacetic acid.
  • the developers of methylglycin diacetic acid have conducted long-term aquatic toxicology studies which have provided improved results over conventional biodegradable chelating agents (such as nitrilotriacetic acid (NTA)).
  • NTA biodegradable chelating agents
  • the complexes formed by MGDA have been shown to have a high stability over a wide range of pH and temperatures.
  • MGDA is currently manufactured by BASF The Chemical Company under the brand name Trilon®, and is available as an aqueous solution of 40wt%.
  • a suitable chelating agent for use in a deruster composition is a carboxylic acid.
  • carboxylic acids include glycolic acid, thioglycolate, thioglycolic acid (TGA), also known as mecaptoacetic acid.
  • Glycolic acid is a type of carboxylic acid and is the first member of the series of alpa-hydroxy carboxylic acids. It has both acid and alcohol functionality. It is also readily biodegradable and has low toxicity.
  • Another suitable chelating agent may be sodium thioglycolate.
  • thioglycolate can boost the longevity of the deruster composition.
  • a solution containing thioglycolate is self-indicating; undergoing a colour change in the presence of the ions of iron, molybdenum, silver and tin in particular.
  • sodium gluconate This is formed from the sodium salt of gluconic acid. It is non-toxic and biodegradable (98% after 2 days). It forms stable chelates with calcium, iron, copper, aluminium and other heavy metals. Gluconates such as potassium and sodium gluconate can act as dual purpose chelating agents and wetting agents.
  • a phosphonate metal chelant includes any compound that contains a phosphonate functional group and a second functional group capable of coordinating to a metal ion, e.g. a second phosphonate group, a carboxylic acid group, or an alcoholic group.
  • Examples of phosphonate chelants include polyphosphonic acid, or the alkali metal or amine salt or the ammonium salt of this acid.
  • Specific examples of phosphonate chelants include 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP) and the salts thereof, which include an alkali metal salt, an amine salt, an ammonium salt or combinations thereof.
  • HEDP 1-hydroxyethylidene-1,1-diphosphonic acid
  • Examples include, but are not limited to; amino tri(methylene-phosphonic acid), hexamethylenediamine tetra(methylene-phosphonic acid), 2-phosphonobutane-1,2,4-tricarboxylic acid, ethylenediamine tetra(methylene-phosphonic acid), ethylenediamine tetra(methylene-phosphonic acid), diethylenetriamine penta(methylene-phosphonic acid), hydroxymethlphosphonic acid, amino (methylenephosphonic acid), iminobis (methylenephosphonic acid), nitrilotris (methylenephosphonic acid), ethylenedintrilotetrakis (methylenephosphonic acid), diethylenetrinitrilopentakis (methylene-phosphonic acid), or salts thereof.
  • Phosphonate chelants are often supplied as aqueous solutions.
  • the composition further includes an alkyl polyglycoside.
  • Alkyl polyglycosides (APGs) and alkyl polyglucosides (derived from glucose) are a class of non-ionic surfactants which are commonly used in household and industrial applications.
  • a commercially available example of alkyl glucoside is Glucopon® 215, which is supplied in aqueous solution.
  • Alkyl glucoside is stable in caustic and saline solutions. It has good wetting and dispersing properties which makes it ideal for hard surface cleaning. It demonstrates excellent solubilising properties in highly concentrated surfactant solutions.
  • Alkyl polyglycoside has no phase inversion temperature and so can be used over a wide temperature range.
  • Amine-based solvents can also act as surfactants in a deruster composition. Including an alkylamine (particularly soya alkylamines) in the deruster composition has resulted in improved cleaning and has helped to prevent flash rusting after the rinse step.
  • Ethoxylated aliphatic amine surfactants such as diethoxylated cocoamines or diethoxylated soyamines, for example, have been found to be useful for rust inhibition.
  • Soya alkylamines such as Bis(2-hydroxylethyl)soyaalkylamine (or Ethomeen® S12; or Ethomeen® SV/12) are useful wetting agents.
  • Sodium laureth sulphate (or sodium lauryl ether sulphate) can be added to the deruster composition to increase the amount of foam generated. When mixed with other surfactants it can be used to increase the viscosity of the deruster composition. This is both an anionic surfactant and a detergent, and is readily biodegradable. Studies have shown that it has very low toxicity when ingested orally.
  • Sodium laureth sulphate has a pH of 7.5 when present at 10% in an aqueous solution.
  • Polyethylene glycol monoisotridecyl ether also known as PEG monoisotridecyl ether, Berol 048, ⁇ -isotridecyl- ⁇ -hydroxypoly(oxy-1,2-ethanediyl); Arlypon IT 10; Dehscoxid 732; Ethox 2400; Ethox TDA 9; Ethoxylated isotridecanol; Ethoxylated Isotridecyl Alcohol; Eusapon S; Exxal F 5716; Genapol V 4739; Genapol X; Gezetol 138; Imbentin T 050; Isotridecanol Ethoxylate; Isotrideceth 15; Leocol TD 120; Leocol TD 150; Leocol TD 50; Leocol TD 90; Leocol TDA 400-75; Lutensol TO 10; Marlipal 013/40; Marlosol TA 3050; Marlosol TA 3090; or
  • Berol 048 has a pH of 5-7 when present at 1% in an aqueous solution.
  • amphoteric surfactant is ⁇ -Alanine, N-(2-carboxyethyl), N-(2-ethylhexyl) monosodium salt, supplied commercially by Lakeland Laboratories Limited as AMA LF at various concentrations (for instance AMA LF40 is a 40wt% of surfactant in aqueous solution). The same salt is also available as AMA LF70.
  • AMA LF40 is a 40wt% of surfactant in aqueous solution.
  • AMA LF70 is also available as AMA LF70.
  • This type of surfactant exhibits good detergency with excellent dirt lifting properties.
  • Amphoteric surfactants are good cleaning agents for hard surfaces such as metals. These types of surfactant produce little foam, resulting in good rinse properties.
  • AMA LF has exhibited low toxicity in studies. Amphoteric surfactants can be used to restore stability in formulation used in hard water areas (where other surfactants have become unstable).
  • ⁇ -Alanine N-(2-carboxyethyl)-N-(n-octyl) mono salt, which is available commercially as LF 60 (60wt% aqueous solution).
  • amphoteric surfactant is ⁇ -Alanine, N-(2-carboxyethyl)-N-[3-(decyloxy)propyl]-, monosodium salt, or Tomamine®.
  • Tomamine® is available in a biodegradable, high foaming, hydrotroping surfactant form (Tomamine Amphoteric 16).
  • the viscosity of the deruster composition can be increased by creating a mixture of coconut diethanolamide and sodium laureth sulphate, and including this mixture within the deruster composition.
  • coconut diethanolamide also known as Surfac CDE
  • the mixture comprises coconut diethanolamide and sodium laureth sulphate at a ratio of between 1:30 to 1:9. A ratio of 1:9 is preferred.
  • the surfactants can be of the same type, for example, non-ionic, or they can be of different types, for example, at least one surfactant could be non-ionic and at least one surfactant could be an amphoteric surfactant.
  • Solvents may be added to the deruster formulation. Solvents are used to dissolve any oils, grease, lubricants and other contaminants which may be present on the surface of the metal parts.
  • the solvent is used in addition to water, and is preferably an organic solvent.
  • Ammonium hydroxide is a powerful cleaning agent and solvent and can be used in the deruster composition as a solvent for this purpose.
  • Ammonium hydroxide has a low upper limit of solubility in water.
  • the maximum concentration at which ammonium hydroxide can be supplied is 0.88g/mol (or about 35wt% ammonia in water) at 15°C.
  • Amines such as triethanolamine (TEA or TEOA) are multifunctional, acting as a solvent, a surfactant and/or a buffer.
  • Triethanolamine can be used in the deruster composition to dissolve oils or grease in water.
  • 2-amino-2-methyl-1-propanol is another amine based solvent that could be used as a solvent in the deruster composition.
  • buffering agents are essentially neutralising agents and are used to maintain the pH of a solution such that it is neutral, or as close to neutral as possible.
  • Buffering agents can either be weak acids or weak alkalis and are usually added to water to form a buffer solution.
  • the buffer solution only slightly changes its pH in response to the addition of other acids or alkali (regardless of the strength of the acid or alkali).
  • buffering agents examples include potassium hydroxide and sodium hydroxide.
  • the use of one or more buffering agents helps to maintain the deruster composition at a neutral pH despite the use of strong acidic or alkaline components in the formulation.
  • Potassium hydroxide and sodium hydroxide are soluble in water at room temperature and are usually supplied as aqueous solutions, for example, in the range of 40wt% to 60wt%.
  • buffering agents examples include tetra potassium pyrophosphate (TKPP, diphosphoric acid), triethanolamine and monoethanolamine.
  • Tetra potassium pyrophosphate (TKPP) is often supplied as a solution of 50-60wt% in water.
  • Triethanolamine (TEA or TEOA) is used to neutralise fatty acids, and to adjust and buffer the pH of an aqueous solution.
  • An example of an alkali solvent which can also act as a buffer is 2- amino-2-methyl-1-propanol (also known as AMPTM). It is soluble in water, with a pH of 11.3 in 0.1M aqueous solution.
  • Compositions according to the invention further comprise at least one source of ferrous ions, added as a catalyst to accelerate the removal of metal oxides by the metal chelants in solution.
  • Any water soluble ferrous salt can be used for this purpose, such as any salt from the group of ferrous sulphates.
  • a specific example of a suitable source of a ferrous ion for use in the composition is ammonium iron (II) sulphate hexahydrate.
  • two chelating agents can be combined with a surfactant, a buffering agent, a salt (to provide a source of ferrous ions) and solvent.
  • Another formulation may comprise two chelating agents, three surfactants, a buffering agent, a solvent and a salt.
  • water is present from about 20wt% to about 98wt%, more preferably between 20wt% and 80wt% of the liquid deruster composition.
  • the deruster composition is usually supplied in concentrated form for further dilution before use.
  • the following examples of quantities are provided for the concentrated form of the deruster product, where the water concentration is preferably less than 50wt%.
  • At least one chelating agent is an aminopolycarboxylic acid and is present in concentrations from about 0.2wt% to about 60wt%, more preferably between 0.2wt% and 40wt%, more preferably between 0.4wt% and 25wt%, most preferably between 0.4wt% and 20wt%.
  • a second chelating agent can be present in quantities of between 0.5wt% to 60wt%, more preferably between 1wt% and 30wt%, most preferably between 1wt% and 20wt%.
  • a third chelating agent can be present in quantities of between 0.5wt% and 15wt%, more preferably between 0.5wt% and 10wt%.
  • At least one surfactant is an alkyl polyglycoside. The surfactant can be present in quantities of between 0.05wt% to 5wt%, more preferably between 0.05wt% and 2.5wt%, most preferably between 0.1wt% and 2wt%. Optionally, more than one surfactant may be present.
  • a second surfactant is a soya-alkylamine
  • it can be present in amounts from about 0.2wt% to about 5wt%, more preferably between 0.5wt% and 2.5wt%.
  • At least one solvent may be present in the deruster composition, preferably in concentrations of between 0.1wt% and 15wt%, more preferably between 0.5wt% and 10wt%, most preferably between 0.5wt% and 8wt%.
  • a buffering agent may be present in quantities between 0.5wt% and 40wt%, more preferably between 1wt% and 30wt%, most preferably between 1wt% and 20wt%. All of these buffering agents are usually supplied at concentrations of about 50wt%-60wt% in water and the quantities discussed are for the aqueous solution.
  • At least one source of ferrous ions may be present in quantities of between 0.01wt% and 5wt%, but preferably between 0.1wt% and 2wt%.
  • a gluconate such as sodium gluconate
  • a gluconate may be added, and may be present in quantities of between 0.1wt% and 5wt%, preferably between 0.1wt% and 2wt%, more preferably between 0.1wt% and 1.5wt%.
  • a thioglycolate such as sodium thioglycolate can be added, which may be present in quantities from about 1wt% to about 20wt%, more preferably between 5wt% and 10wt%.
  • the components of the deruster composition are slowly added to one another and mixed well until dissolved or homogenously mixed (as appropriate).
  • the pH is adjusted to a range of 5 to 8. Most preferably, the pH is adjusted to fall in the range from 6 to 7.5.
  • the deruster composition product for application onto the metal surface is further diluted from 1 to 4, up to 1 to 20, preferably 1 to 10 (10%) before use. Any clean source of water free from particulates would be suitable for use. Water does not necessarily have to be purified; however, filtered, distilled or de-ionised water can be used. For tarnish removal, the deruster composition product is diluted further, up to a dilution of 1 part deruster composition to 25 parts water, before use.
  • the deruster composition is designed to be applied after the metal objects have been initially cleaned to remove any loose soils, oil and grease.
  • the deruster composition is designed to be used at a temperature of between 10°C and 60°C, more preferably between 20°C and 40°C. There is no need to heat the composition in order for the deruster composition to dissolve the rust, and the composition can be applied at room temperature.
  • the step of contacting the contaminated metal with the deruster composition can be carried out by any conventional method. These methods include, but are not limited to contacting by immersion and spray methods. Alternatively, the product can be painted or sponged onto the object. Metals which have been contacted with the deruster composition for a sufficient length of time can be referred to as 'treated metals'.
  • the deruster composition can be applied to the metal to be cleaned by a combination of spray and immersion processes. Alternating steps of separate spray processes or separate immersion processes can be used in order to achieve the desired result.
  • the contacting step is performed for a length of time sufficient to result in the contaminants or rust being at least partially dissolved.
  • Application of the deruster composition by a spray process requires optimisation of nozzle selection and arrangement as well as consideration of the spray. Immersion cleaning can be aided by the use of agitation methods to reduce immersion time.
  • the contacting times required for rust removal depends on the severity of the deposition or contamination.
  • the contacting step is preferably performed for less than 36 hours, more preferably, for less than 24 hours, most preferably for less than 12 hours.
  • the contacting step is preferably performed for less than 10 hours, more preferably about 7.5 hours, most preferably about 6 hours.
  • the contacting step is preferably performed for less than 2 hours, more preferably less than 1 hour.
  • 30 minutes contact time with the diluted deruster composition can be sufficient to remove all the rust from the surface of the metal, even when applied at room temperature.
  • the contacting step is then preferably performed for less than 6 hours, more preferably less than 5 hours. Most preferably, the contacting step is less than 4 hours.
  • a contacting time of less than 2 hours can be sufficient to remove a thin to moderate layer of tarnish.
  • a contacting time of up to 5 hours may be required, preferably up to 4 hours.
  • the required contacting times are provided at room temperature. By increasing the temperature, the required contacting times can be reduced, however, this increases the energy requirements (and therefore the cost) of the process.
  • the metal may undergo a rinsing stage to remove any particulates from the surface of the metal.
  • the rinse step can be performed using additional "fresh" deruster composition.
  • the deruster composition can leave behind a temporary protective coating that helps to prevent flash rusting.
  • Formulation 6 An example of a formulation supplied in a "ready to use” form is Formulation 6, as shown in Table 1.
  • Formulation 6 is a composition which does not require further dilution prior to use, and is designed to be sprayed onto or painted onto vertical surfaces where prolonged contact is required (although the composition can also be applied by equivalent methods such as sponging or dipping).
  • Formulation 6 has improved degreasing and soil cleaning properties.
  • the following quantities are examples provided for the dilute form of the deruster product, where the water concentration is preferably more than 50wt%.
  • the water concentration of the dilute deruster composition may be between 50wt% and 80wt%.
  • At least one chelating agent in the dilute deruster composition is an aminopolycarboxylic acid and is present in concentrations from about 0.1wt% to about 20wt%. More preferably, it can be present in quantities of between 0.2wt% and 15wt%, most preferably between 0.2wt% and 10wt%.
  • a second chelating agent is a phosphonate chelating agent it can be present in the dilute deruster composition in quantities of between 0.1wt% to 20wt%, more preferably between 0.2wt% and 15wt%, most preferably between 0.2wt% and 10wt%.
  • At least one surfactant in the dilute deruster composition is an alkyl polyglycoside. Alkyl polyglycoside can be present in quantities of between 0.05wt% to 5wt%, more preferably between 0.05wt% and 1wt%.
  • a solvent can be present in the dilute deruster composition, preferably in concentrations of between 0.1wt% and 10wt%, more preferably between 0.1wt% and 5wt%, most preferably at concentrations between 0.1wt% and 2wt%.
  • the deruster composition can be designed to provide protection as well as to remove the corrosion from the metal.
  • Compositions can be formulated to be applied to the metal for prolonged contact such that they can be left on the surface of the metal to prevent corrosion, or to reduce the rate at which corrosion occurs. These compositions act as corrosion inhibitors.
  • Metal surfaces which have been cleaned with a deruster composition prepared according to the present invention (such as the examples compositions 1-2, 4-6 and 10-11 provided in Table 1) have demonstrated improved resistance to flash rusting compared with existing deruster products.
  • Formulations 3, 7-9 and 12 in table 1 are not according to the invention.
  • Table 1 Example Formulations 1 2 3 4 5 6 7 8 9 10 11 12 % w/w % w/w % w/w % w/w % w/w % w/w % w/w % w/w % w/w % w/w % w/w % w/w % w/w % w/w % w/w % w/w % w/w Water 38.55 39.75 54.45 33.75 36.72 75.18 44.50 44.50 44.50 39.15 39.15 35.50 MGDA, Methyl glycine diacetic Acid, tri sodium salt (40wt%) 5.0 5.0 4.2 4.3 4.74 1.21 36 36 36 5 IDS (Tetrasodium Iminodisuccinate) 34wt% 10 6 GLDA (Tetrasodium Glutamate Diacetate
  • Formulations 1 to 5 and 7 to 12 are further diluted prior to use.
  • a cleaned and degreased steel panel Q was placed outside in a vertical position for a period of approximately one month in order to allow it to become rusted.
  • the panel Q had rusted sufficiently, it was partially dipped into a 10% by weight dilution of a solution of deruster composition (which included MGDA and HEDP as chelating agents) prepared according to the present invention and then left for 4 hours until all the rust had been removed.
  • deruster composition which included MGDA and HEDP as chelating agents
  • the panel Q was removed from the de-ruster and carefully rinsed with water. The previous day, a further panel R had been cleaned and then degreased overnight. The two panels were then tethered to a fence (i.e. outdoors) in a vertical position. The panels were inspected at regular intervals noting the amount of re-rusting, this continued until a difference could be seen between the two panels.
  • Figure 1 is a photograph demonstrating the results of this experiment. It can be seen that after treatment with a deruster composition in accordance with the present invention, the metal surface on the lower portion of panel Q showed improved resistance to repeated rusting after 12 days of exposure. These results demonstrate that the deruster composition can be used as a rust inhibitor.
  • a chain which was heavily incrusted with rust was immersed in a solution of deruster composition prepared in accordance with the present invention.
  • the deruster composition was diluted to 10% by weight with water and included MGDA and HEDP as chelating agents.
  • the chain was left in the solution for 24 hours.
  • a chain comprises many crevices and is time consuming to manually scrub or clean.
  • the rust needs to be removed. Only then can the structural integrity of the chain be properly assessed. Removal of rust also allows the parts to be painted.
  • Figure 2 is a photograph of a chain before immersion in a deruster composition according to this invention and Figure 3 is a photograph of the same chain after immersion in a deruster composition according to this invention.
  • Figure 3 demonstrates that the rust has been completely removed after immersion in the deruster formulation. The chain is much easier to inspect for structural integrity after immersion in the deruster composition.
  • FIGs 4 and 5 are photographs of the copper strip after partial immersion in the deruster composition. After removal from the deruster composition, the portion of the copper which had been immersed appeared to be fully restored to its original state, and was no longer tarnished, as can be seen in Figures 4 and 5 . The treated metal was considerably brighter and had regained its light reflective properties. Other compositions prepared in accordance with the present invention produce a similar result.
  • a tarnished section of copper tube was almost fully immersed into a solution of deruster composition prepared in accordance with the present invention.
  • the deruster composition contained MGDA as a chelating agent. Before immersion, the copper tube was coated in a moderate layer of tarnish, and had a dull appearance.
  • FIG. 6 is a photograph of the copper tube after partial immersion in the deruster composition. After removal from the deruster composition, the tarnish had been removed and the portion of the copper which had been immersed appeared to be restored to its original state, as can be seen in Figure 6 . The treated metal was considerably brighter and more reflective.
  • a tarnished section of brass piping was partially contacted with a solution of deruster composition prepared in accordance with the present invention.
  • the deruster composition comprised MGDA as a chelating agent, although other compositions prepared in accordance with the present invention produce a similar result.
  • the brass piping was coated in a thick layer of tarnish, and the brass had a dark, dull appearance.
  • Figure 7 is a photograph of the brass piping after partial contact with the deruster composition. One end of the brass piping was exposed to the deruster composition for 4 hours. After removal of the deruster composition, the tarnish had been removed from the brass piping and the portion of the brass which had been contacted with the deruster composition appeared to be restored to its original state. This can be seen in Figure 7 . The treated metal was considerably brighter and lighter in colour.
  • Form Chelates contained 4 IDS -10 MGDA+IDS 6 IDS -15 MGDA+IDS 10 GDLA -10 MGDA+GDLA 12 GDLA -15 MGDA+GDLA 16 NaTG -10 MGDA+ NaTG 18 NaTG -15 MGDA+ NaTG 26 0.4g Tri M HEDP+MGDA 27 0.6g Tri M HEDP+MGDA 33 0.4g IDS HEDP+IDS 34 0.6g IDS HEDP+IDS 40 0.4g GDLA HEDP+GDLA 41 0.6g GDLA HEDP+GDLA
  • biodegradable chelating agent improves the biodegradability of the deruster composition and any waste generated and therefore reduces the ecological impact of the deruster composition.
  • the deruster composition can be used to remove rust or tarnish from corroded metal objects, or can be used as a corrosion inhibitor in order to prevent or reduce further corrosion.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Detergent Compositions (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
EP15735726.0A 2014-10-06 2015-06-26 Ph neutral deruster composition Active EP3204532B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB1417633.3A GB2535131B (en) 2014-10-06 2014-10-06 pH neutral deruster composition
PCT/GB2015/051869 WO2016055758A1 (en) 2014-10-06 2015-06-26 Ph neutral deruster composition

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EP3204532B1 true EP3204532B1 (en) 2018-12-19

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AU (1) AU2015329756B2 (ja)
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CN110257843A (zh) * 2019-07-15 2019-09-20 江苏方成生物科技有限公司 一种新型中性除锈剂
RU2715204C1 (ru) * 2019-10-17 2020-02-25 ГОДЗОЕВ Олег Александрович Композиция для растворения/удаления коррозионных отложений
CN111254447B (zh) * 2020-03-24 2022-05-20 太仓市宝马环境工程有限公司 一种中性除锈钝化清洗剂及其使用方法
CN111647895A (zh) * 2020-05-21 2020-09-11 上海毅诺生物科技有限公司 一种非voc水基软金属清洗剂
CN111790094A (zh) * 2020-07-31 2020-10-20 南通乐尔环保科技有限公司 一种飞灰螯合剂及其制备方法和应用
CN112176355B (zh) * 2020-10-23 2022-05-17 山东大学 一种环境友好型中性除锈剂及其制备方法
JP7066155B1 (ja) 2021-01-22 2022-05-13 株式会社トクヤマデンタル 次亜塩素酸水溶液用防錆剤並びに防錆効果を有する殺菌・洗浄剤及びその調製方法
CN114807950A (zh) * 2021-01-28 2022-07-29 江苏悦锌达新材料有限公司 一种铝合金清洗剂及其制备方法
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Publication number Publication date
GB2535131A (en) 2016-08-17
AU2015329756A1 (en) 2017-04-27
JP6715828B2 (ja) 2020-07-01
EP3204532A1 (en) 2017-08-16
GB201417633D0 (en) 2014-11-19
WO2016055758A1 (en) 2016-04-14
ES2716074T3 (es) 2019-06-10
AU2015329756B2 (en) 2020-09-10
JP2017531735A (ja) 2017-10-26
GB2535131B (en) 2022-05-04

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