Classifications

• • C—CHEMISTRY; METALLURGY
  • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F1/00—Treatment of water, waste water, or sewage
  • C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
• • 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
• • C—CHEMISTRY; METALLURGY
  • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F1/00—Treatment of water, waste water, or sewage
  • C02F1/70—Treatment of water, waste water, or sewage by reduction
• • C—CHEMISTRY; METALLURGY
  • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F2101/00—Nature of the contaminant
  • C02F2101/10—Inorganic compounds
• • C—CHEMISTRY; METALLURGY
  • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F2303/00—Specific treatment goals
  • C02F2303/08—Corrosion inhibition

Definitions

• the invention relates to a liquid preparation for the reduction of free oxygen and the preservation of water.
• the preparation is preferably formulated as a concentrate.
• the invention further relates to the use of the preparation (in particular in the form of the concentrate) for the reduction of free oxygen and the preservation of water, and also to correspondingly additivated water.
• microbiological corrosion plays a role which must not be underestimated.
• overgrowth with microorganisms is a problem.
• Slime-forming bacteria can block pipelines.
• Other microorganisms can initiate corrosion (sulphuric acid production).
• Sulphate-reducing organisms generate interfering hydrogen sulphide.
• biofilms can form which are very difficult to remove again. Whole fields can be infected. Microorganisms can therefore cause enormous economic damage.
• biocides are used, such as quaternary ammonium compounds (quats), glutaraldehyde (GDA), acrolein, isothiazolinones, tetrakis (hydroxymethyl)phosphonium sulphate (THPS) and also dibromonitrilopropionamide (DBNPA), for example.
• quats quaternary ammonium compounds
• GDA glutaraldehyde
• acrolein isothiazolinones
• THPS tetrakis (hydroxymethyl)phosphonium sulphate
• DBNPA dibromonitrilopropionamide
• the oxygen dissolved in water primarily plays an important role. Depending on the temperature and salt content, up to about 10 ppm of O 2 dissolve in the water. At an oxygen content of 8 ppm, the corrosion rate is already 25 times higher than in oxygen-free water.
• hydrotesting In the installation and repair of pipelines and pressure vessels, it is therefore customary to test the resistance to relatively high pressures in the system with water (what is termed hydrotesting).
• water which is available on site is taken off, in the case of drilling platforms seawater, in other pipelines also water from rivers and lakes. This water generally has a certain microbial count and a dissolved oxygen fraction of up to about 10 ppm.
• Fluids for stabilizing boreholes and pipelines in gas and oil extraction up until onset of regular extraction (what are termed completion fluids), fluids used for the same purpose during interruptions to operation (what are termed workover fluids) and also water-based hydraulic fluids for power transmission must also be adequately protected from corrosion and microbial infection.
• biocides such as, e.g., glutaraldehyde, acrolein, isothiazolinones, DBNPA etc.
• glutaraldehyde, acrolein, isothiazolinones, DBNPA etc. cannot be formulated as stable, storable, alkaline concentrate, since the biocides are not stable in an alkaline environment.
• the water must therefore be first freed from dissolved oxygen in the alkaline pH range and then preserved. This separation of the operations for removing the dissolved oxygen and the subsequent elimination of microorganisms is time-consuming and costly, and separating the degassed water is not always possible without problems. Since the dissolved oxygen must be removed first and the oxygen scavenger is used in excess, in addition the amount of biocide used must be such that the excess of oxygen scavenger can react to completion and a still sufficiently active amount of biocide is present.
• N-formals and diethylhydroxylamine are known from other applications.
• WO 2011/000794 A1 and WO 2010/142790 A1 relate to coatings which are stabilized with aziridine compounds that are adsorbed onto carrier materials.
• formaldehyde-releasing compounds such as bisoxazolidines and hydroxylamines such as diethylhydroxylamine are described.
• WO 2004/050733 A2 discloses phenol resins. Curing agents which are described are oxazolidines and hydroxylamines.
• GB 2 354 771 A discloses bactericidal combinations in detergents.
• BPD list active bactericidal compounds
• diethylhydroxylamine and 3,3′-methylene bis-5-methyloxazolidine are listed.
• US 2011/0180759 A1 describes methods and compositions for the reduction of stress corrosion cracking in steel transport and storage vessels containing bioethanol.
• the compositions contain a combination of oxygen scavengers and film-forming additive.
• oxygen scavenger is diethylhydroxylamine.
• film-forming additive is diisopropanolamine.
• WO 2004/029119 A1 describes a method for curing phenol-formaldehyde resins.
• Suitable additives are formaldehyde slow-release compounds such as oxazolidines.
• Optional polymerization inhibitors which are suitable are, for example, N-propylhydroxylamine and diethylhydroxylamine.
• EP 0 902 017 A1 describes a method for transesterification of polymerizable monomers.
• One alcohol suitable for the transesterification is hydroxyethyl-oxazolidine.
• One example of a polymerization inhibitor is diethylhydroxylamine.
• the object of the present invention is to provide preparations for the reduction of free oxygen in water (in particular for hydrotesting and as injection water) and the preservation of this water.
• the preparations should be stable and easy to meter even as concentrates.
• the liquid preparation is used for the simultaneous reduction of free oxygen and preservation of water, in particular salt water. Furthermore—for a constant biocidal activity—the activity of the oxygen scavenger is markedly increased without further additions before use.
• the invention is based, inter alia, on the fact that it has been found that mixing N-formals with dialkylhydroxylamines is not only outstandingly compatible, but the activity of dialkylhydroxylamines is considerably improved by the formaldehyde-releasers. The activity of dialkylhydroxylamines is also markedly increased by the pH elevation. This synergistic activity is evident not only in mains water but also in a 3% solution of sodium chloride in mains water.
• Preparations according to the invention contain at least one N-formal.
• the advantages of these microbicidal active ingredients are disclosed, inter alia, in DE 103 40 830 A1 and DE 10 2009 033 161 A1.
• Particularly suitable N-formals are reaction products of formaldehyde and amines (preferably alkanolamines) having a molar formaldehyde excess. Preference is given to low-water formaldehyde slow-release compounds which react in an alkaline manner in water.
• N-formals condensation products of paraformaldehyde and isopropanolamine in the molar ratio 3:2, condensation products of paraformaldehyde and isopropanolamine in the molar ratio 3:2 and urea and condensation products of paraformaldehyde and isopropanolamine in the molar ratio 3:2, and also urea and ethylene glycol.
• N-Formals which are preferably used according to the invention are N,N′-methylenebis(5-methyloxazolidine), ⁇ , ⁇ ′, ⁇ ′′-trimethyl-1,3,5-triazine-1,3,5-(2H,4H,6H)-triethanol, 4,4-dimethyloxazolidine, dimethylolurea, 5-ethyl-3,7-dioxa-1-azabicyclo[3.3.0]octane, 2-(hydroxymethylamino)ethanol, methylenebistetrahydro-1,3-bisoxazine, N-methylolchloroacetamide, bis(hydroxymethyl)-5,5-dimethylhydantoin, diazolidinylurea, sodium hydroxymethylglycinate, 3,4,4-trimethyloxazolidine, 2,2′,2′′-(hexahydro-1,3,5-triazine-1,3,5-triyl)triethanol and tetrahydro-1,3,
• formaldehyde slow-release compound is given to 3,3′-methylenebis(5-methyloxazolidine), 2,2′,2′′-(hexahydro-1,3,5-triazine-1,3,5-triyl)-triethanol, ⁇ , ⁇ ′, ⁇ ′′-trimethyl-1,3,5-triazine-1,3,5-(2H,4H,6H)triethanol, tetrahydro-1,3,4,6-tetrakis-(hydroxymethyl)imidazo[4,5-d]imidazole-2,5-(1H,3H)-dione, dimethylol urea and also the products Grotan® OF (methylenebis(5-methyloxazolidine)+urea) and Grotan® OK (methylenebis(5-methyloxazolidine)+urea+ethylene glycol).
• Grotan® OF methylenebis(5-methyloxazolidine)+urea
• Grotan® OK methylenebis(5-methylo
• Preparations according to the invention contain at least one dialkylhydroxylamine of the formula RR′NOH, wherein R and R′ independently of one another are selected from linear, branched and cyclic C 1 -C 10 alkyl groups. Examples of R and R′ are independently of one another methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl and decyl. Particular preference as component b) is given to diethylhydroxylamine (DEHA).
• DEHA diethylhydroxylamine
• the weight ratio of component a) to component b) is typically 30:1 to 1:5, preferably 25:1 to 1:1, in particular 20:1 to 3:1, for instance 9:1.
• the preparation according to the invention further preferably contains c) at least one antioxidant.
• Preferred antioxidants are, at room temperature, liquid or sufficiently soluble in the formaldehyde slow-release compound.
• antioxidants are selected from sterically hindered phenols, amines, vitamin E and derivatives thereof, and alkyl esters of gallic acid, preferably 3-tert-butyl-4-hydroxyanisole (BHA), 2,6-di-tert-butyl-p-cresol (BHT), 2,6-di-tert-butylphenol, lauryl gallate and vitamin E.
• the preparation according to the invention in addition contains preferably d) at least one alkalizing agent which has the effect that, in the ready-to-use dilution (additivated water), a sufficiently alkaline pH is maintained, which is particularly advantageous for the short-time activity of the oxygen scavenger.
• alkalizing agents are amines or alkanolamines such as isopropanolamine, propanolamine, monoethanolamine, diethanolamine, triethanolamine, aminomethylpropanol and aminobutanol.
• the alkalizing agent increases the activity of the oxygen scavenger and should be able to elevate the pH of the additivated water at the ready-to-use concentration.
• Suitable alkalizing agents are all substances which are stable in the mixture according to the invention of the components a) and b) and are readily soluble in water.
• alkalizing agents are inorganic compounds such as alkali metal hydroxides or alkali metal salts such as KOH, NaOH, Na carbonate, potassium or sodium waterglass, amines or alkanolamines such as ethanolamine, isopropanolamine, fatty amines, medium-chain amines or alkanolamines such as diisopropanolamine, hydroxylamine and ammonium hydroxide.
• alkalizing agents are ethanolamine, isopropanolamine, NaOH, KOH, waterglass, hydroxylamine and ammonium hydroxide.
• preferred preparations further contain e) at least one of stabilizers, activators, corrosion inhibitors, scale inhibitors, complexing agents, fungicides, algicides, antifoams, cold stabilizers, solvents and boosters.
• further antimicrobial active ingredients can also be present.
• further antimicrobial active ingredients which can be present in the compositions according to the invention are aldehydes such as GDA, formaldehyde slow-release compounds such as ethylene glycol bishemiformal, THPS, organohalogen compounds such as DBNPA, quats such as benzalkonium chloride, amines such as Lonzabac 12, phenols, iso-thiazolones such as MI, CMI, OIT, DCOIT, BIT, n-Bu-BIT and Bunte salts.
• aldehydes such as GDA
• formaldehyde slow-release compounds such as ethylene glycol bishemiformal
• THPS organohalogen compounds
• quats such as benzalkonium chloride
• amines such as Lonzabac 12
• iso-thiazolones such as MI, CMI, OIT, DCOIT, BIT, n-Bu-BIT and Bunte salts.
• preparations according to the invention can be combined with further biocidal active ingredients, functional additives and auxiliaries, as are disclosed, eg. in WO2009/060057 A2, DE 10 2006 035013 A1, or DE 103 40 830 A1.
• preparations according to the invention are typically formulated as liquid concentrates.
• the fraction of component a) is preferably at least 30% by weight, more preferably at least 35% by weight, in particular at least 40% by weight, such as at least 45% by weight, for example about 50% by weight.
• the fraction of component b) is typically at least 0.25% by weight, preferably at least 1% by weight, in particular at least 2% by weight, for instance 5% by weight.
• liquid concentrates which consist of the components a), b) and optionally c) and/or d), that is to say, in addition, contain no further components.
• the concentrate contains 0.0001 to 10% by weight, more preferably 0.001 to 1% by weight, particularly preferably 0.002 to 0.1% by weight, for instance 0.02% by weight, of antioxidant c).
• Liquid concentrates contain, when alkalizing agent d) is present, preferably at least 20% by weight, more preferably at least 30% by weight, in particular at least 40% by weight, such as at least 45% by weight of component d), for example about 50% by weight of component d).
• the concentrates according to the invention preferably contain at most 30% by weight of water, more preferably at most 20% by weight of water, particularly preferably at most 12% by weight of water, in particular at most 5% by weight of water, such as, for example, less than 1.0% by weight of water.
• a particularly preferred liquid concentrate consists of:
• the liquid concentrate is prepared by charging component a) (for example 3,3′-methylenebis(5-methyloxazolidine)) and then dissolving component b), for example DEHA, with stirring.
• component a) for example 3,3′-methylenebis(5-methyloxazolidine)
• dissolving component b for example DEHA
• Liquid concentrates according to the invention are used prophylactically in concentrations of 100 to 2000 mg/1 (ppm), preferably 200 to 1000 ppm, based on the total amount of active ingredient a) and b) and also optionally c) and d), without solvent or diluent.
• the invention further relates to the use of the preparation according to the invention for the reduction of free oxygen in water with simultaneous preservation of the water.
• the water can be a fluid for stabilizing boreholes and pipelines in the extraction of gas and oil up until uptake of regular extraction (what is termed completion fluid), fluid used for the same purpose during interruption to operations (what is termed workover fluid) and also a water-based hydraulic fluid for power transmission.
• preparations according to the invention are the reduction of free oxygen and preservation of process water, aqueous systems, industrial water, seawater, salt water, drilling fluids, hot water, injection water, wastewaters (such as industrial wastewaters, wastewaters from agriculture, from the extraction of crude oil or natural gas), transport and storage fluids (for example minerals, coal, fuels), heating water, aqueous and/or alkaline cleaning solutions, recycling water, water and condensate water which are deaerated and optionally charged with inert gas.
• wastewaters such as industrial wastewaters, wastewaters from agriculture, from the extraction of crude oil or natural gas
• transport and storage fluids for example minerals, coal, fuels
• heating water for example minerals, coal, fuels
• aqueous and/or alkaline cleaning solutions recycling water, water and condensate water which are deaerated and optionally charged with inert gas.
• the combination of the components a), b) and optionally c) is used in water preferably by adding a fluid concentrate.
• a fluid concentrate it is possible to add the components a), b) and optionally c) singly, but this alternative is not preferred.
• the invention relates to an additivated water which comprises the components a) and b) (and also optionally c) and/or d)—and, when present e)).
• liquid preparations according to the invention offer the following advantages in this case:
• composition of selected N-formals that are used in the examples.
• Reaction product of ethanolamine and formaldehyde (91%) in the molar ratio 3:3. This forms N,N′,N′′-tris(2-hydroxyethyl)hexahydrotriazine. Reaction water and water from the formaldehyde remain in the product.
• Reaction product of isopropanolamine and formaldehyde (91%) in the molar ratio 3:3. This forms N,N′,N′′-tris-(2-hydroxypropyl)hexahydrotriazine. Reaction water and water from the formaldehyde remain in the product.
• Reaction product of isopropanolamine and formaldehyde (91%) in the molar ratio 2:3. This forms 3,3′-methylenebis(5-methyloxazolidine).
• the reaction water and water from the formaldehyde are distilled off.
• Reaction product of isopropanolamine and formaldehyde (91%) in the molar ratio 2:3. This forms 3,3′-methylenebis(5-methyloxazolidine).
• the reaction water and water from the formaldehyde are distilled off. Addition of urea for reduction of the free formaldehyde (mixture contains about 4% urea).
• Reaction product of isopropanolamine and formaldehyde (91%) in the molar ratio 2:3. This forms 3,3′-methylenebis(5-methyloxazolidine).
• the reaction water and water from the formaldehyde are distilled off. Addition of urea and ethylene glycol for reduction of the free formaldehyde and for reducing the amine odour (mixture contains about 4.6% urea and about 9.5% ethylene glycol).
• Glutardialdehyde (obtainable as up to 50% strength solution in water) is currently one of the most used biocides in these applications.
• the oxygen sensor is immersed and stirred until the indicated oxygen content remains constant (approximately 1-2 minutes). After the measurement the sample is allowed to stand and the measurement repeated after 3 hours.
• the table for experiment 2 shows the activity of the oxygen reduction of the mixtures of various formaldehyde slow-release compounds with diethylhydroxylamine (DEHA).
• DEHA diethylhydroxylamine
• Experiment 3 shows the oxygen reduction with addition of an alkalizing agent (isopropanolamine).
• an alkalizing agent isopropanolamine
• the activity of the mixture of N-formal OX is somewhat better than diethylhydroxylamine (DEHA) alone or with other formals or glutaraldehyde (GDA).
• DEHA diethylhydroxylamine
• GDA glutaraldehyde
• the presolutions with 3% sodium chloride in mains water and 3% sodium chloride with 300 ppm of isopropanolamine in mains water are cooled down to approximately 4° C. using an icebath.
• Experiment 5 shows the good stability of N-formals towards glutaraldehyde (both without and also with isopropanolamine).
• the concentrate of GDA and DEHA is not stable after addition of isopropanolamine. Without isopropanolamine, even after 2 months' storage at 25° C., almost half of the glutaraldehyde used, and at 40° C., 2 ⁇ 3 of the glutaraldehyde used, are no longer present.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Organic Chemistry (AREA)
• Materials Engineering (AREA)
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• Environmental & Geological Engineering (AREA)
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• Life Sciences & Earth Sciences (AREA)
• Water Supply & Treatment (AREA)
• Agricultural Chemicals And Associated Chemicals (AREA)
• Gas Separation By Absorption (AREA)
• Solid-Sorbent Or Filter-Aiding Compositions (AREA)
• Food Preservation Except Freezing, Refrigeration, And Drying (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Preventing Corrosion Or Incrustation Of Metals (AREA)

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