EP1137651A1 - 1-hydroxy-3-sulfonoalkan-1,1-diphosphonsäuren - Google Patents

1-hydroxy-3-sulfonoalkan-1,1-diphosphonsäuren

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Publication number
EP1137651A1
EP1137651A1 EP99958148A EP99958148A EP1137651A1 EP 1137651 A1 EP1137651 A1 EP 1137651A1 EP 99958148 A EP99958148 A EP 99958148A EP 99958148 A EP99958148 A EP 99958148A EP 1137651 A1 EP1137651 A1 EP 1137651A1
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EP
European Patent Office
Prior art keywords
mol
water
formula
acid
mixture
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.)
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Application number
EP99958148A
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German (de)
English (en)
French (fr)
Inventor
Christoph Holzner
Roland KLEINSTÜCK
René GRAUPNER
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Bayer AG
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Bayer AG
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Publication of EP1137651A1 publication Critical patent/EP1137651A1/de
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • 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
    • C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
    • C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
    • C02F5/14—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
    • C07F9/3839—Polyphosphonic acids
    • C07F9/3865—Polyphosphonic acids containing sulfur substituents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/52—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning
    • C09K8/528—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning inorganic depositions, e.g. sulfates or carbonates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/54—Compositions for in situ inhibition of corrosion in boreholes or wells
    • 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/36—Organic compounds containing phosphorus
    • 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
    • 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
    • C23F11/167—Phosphorus-containing compounds
    • C23F11/1676—Phosphonic acids

Definitions

  • the present invention relates to l-hydroxy-3-sulfonopropane-l, l-diphosphonic acids and phosphonate-containing mixtures containing these acids, a process for their preparation and their use as water treatment chemicals and
  • water treatment chemicals or sequestering agents are used to protect against unwanted deposits of poorly soluble calcium salts (scale) and, if necessary, also against corrosion of the iron-containing materials.
  • l-Hydroxyalkane-l, l-diphosphonic acids with the structural element -C (OH) (PO 3 H 2 ) 2 have long been known as water treatment chemicals. They are obtained by reacting carboxylic acids or carboxylic acid derivatives with inorganic compounds of trivalent phosphorus under dehydrating conditions and subsequent hydrolysis.
  • HEDP is prepared from an acetyl derivative used in excess and an inorganic compound of trivalent phosphorus under initially dehydrating conditions, for example by reaction of 2.4 mol of acetic acid, 1 mol of PC1 3 and 0.6 mol of water, subsequent hydrolysis and removal of excess acetic acid (see US-A-4,060,546, Example 2).
  • the most important The application for HEDP is the inhibition of scale formation in cooling water (PR Puckorius, SD Strauss; Power, May 1995, pages 17 to 28, especially page 18).
  • HEDP high-density polyethylene glycol
  • a disadvantage of HEDP is the fact that it forms a very poorly soluble calcium salt. When the calcium content in the cooling water is high, the HEDP-Ca salt precipitates, so that the effective concentration of the inhibitor in the solution decreases and deposits of the HEDP-Ca salt can occur instead of the calcium carbonate deposits to be prevented.
  • n can take integer values between 3 and 10 and X can be OH or NH 2 .
  • the calcium tolerance of a stone inhibitor can easily be determined in a standardized turbidity test by gradually increasing the concentration of the inhibitor at a fixed calcium concentration and a fixed pH until a clouding-causing precipitate occurs. The higher the inhibitor can be dosed without significant precipitation, the higher its calcium tolerance.
  • a high calcium tolerance means that a high effective inhibitor concentration is set with an inhibitor in water with a high calcium content can be. This is a necessary but not sufficient condition for the use of an inhibitor in very hard water. The actual effectiveness of the inhibitor must also be proven in a stone inhibition test.
  • Sulfono-l, l-diphosphonic acids as stone inhibitors compared to HEDP shows.
  • a clear disadvantage of the sulfonated species from this publication compared to HEDP is their costly synthesis: expensive ⁇ -bromoalkanecarboxylic acids are used as raw materials for the preparation of the l-hydroxy- ⁇ -sulfonoalkane-l, l-diphosphonic acids. These are first reacted with phosphorus trichloride and water under dehydrating conditions to give ⁇ -bromo-1-hydroxyalkane-l, l-diphosphonic acids.
  • the bromine is then replaced by the sulfonic acid group by treating the reaction mixture with aqueous sodium sulfite solution and alkali metal hydroxide solution.
  • the bromide that is split off remains dissolved in the aqueous product solution. It cannot be separated and recovered with reasonable effort.
  • the present invention was based on the object of providing a stone and corrosion inhibitor which
  • R 1 and R 2 independently of one another are hydrogen or methyl and M 1 to M 5 independently of one another represent a hydrogen, alkali, ammonium or an alkylated ammonium ion,
  • R 1 and R 2 are hydrogen and M 1 to M 5 independently of one another represent a hydrogen, alkali, ammonium or an alkylated ammonium ion or those in which R 1 is methyl and R 2 is hydrogen and M 1 to M 5 independently of one another represent a hydrogen, alkali, ammonium or an alkylated ammonium ion or those in which
  • R 1 is hydrogen and R 2 is methyl and M 1 to M 5 independently of one another represent a hydrogen, alkali, ammonium or an alkylated ammonium ion
  • R 1 and R 2 are independently hydrogen or methyl
  • M 1 to M 5 and M 1 independently of one another represent a hydrogen, alkali, ammonium or an alkylated ammonium ion
  • Z represents a group of the formula -COOM 1 or -C (OH) (PO 3 M 1 M 2 ) 2
  • n can assume integer values from 1 to 5 and the mean value for n over all compounds of types (II) and (III) is between 1 and 2.
  • Formula (III) is at least 5 to 1, particularly preferably at least 10 to 1,
  • the proportion of phosphorus in the individual compounds of the mixture is determined by the relative intensity of the signals of the respective compounds in the 31 P-NMR
  • the phosphonate of formula (I) shows a characteristic triplet with a coupling constant J PH of 14.8 Hz (aqueous solution of the free acid at pH 0 to 1).
  • Signals to the -CHR 2 -COOM signals determined.
  • the signal intensity of the protons inside is determined from the intensity of the very broad signals in the range from 1.3 to 2.3 ppm (at pH 6 to 7, compared to sodium 3- (trimethylsilyl) tetradeuteropropionic acid in D 2 O) or in Range from 1.3 to 2.55 ppm (at pH 0 to 3, compared to 3- (trimethylsilyl) tetradeuteropropionic acid sodium salt in D 2 O).
  • n ⁇ according to the following formula:
  • the formula must be modified accordingly for methacrylic acid or crotonic acid as raw materials.
  • R 1 and R 2 are independently hydrogen or methyl
  • step b) optionally treating the reaction mixture from step a) with a strongly acidic cation exchanger in the H + form;
  • step a) or d) recovery of the amine added in step a) or d) by alkalizing the reaction mixture with alkali metal hydroxide solution, separating off the released amine and reusing the amine in process step a) or d).
  • the unsaturated carboxylic acids to be used in process step a) are, for example, acrylic acid, methacrylic acid or crotonic acid, preferred are acrylic acid and crotonic acid, particularly preferably acrylic acid. Mixtures of the carboxylic acids mentioned can also be used, for example a mixture of acrylic acid and crotonic acid.
  • the monovalent base to be used in process step a) can be an alkali metal hydroxide, ammonia or an aliphatic primary, secondary or tertiary amine.
  • Sodium hydroxide or a tertiary amine is preferably used, particularly preferably tributylamine.
  • the type of base used influences, inter alia, the proportion of oligomers in the end product.
  • sodium hydroxide for example, significantly more oligomers are obtained than with tributylamine as the base.
  • the factor in the above formula preferably takes values from 0 to 1, particularly preferably values from 0.3 to 0.9. Any amine salt possibly formed in process step a) can advantageously also be used in this amount in the later process step d).
  • the preferred amount of water to be used if sodium hydroxide is used as the base, is 20 to 30 mol. If a tertiary amine is used as the base, the preferred amount of water is significantly smaller. The reason for this difference is on the one hand the different solubility of the salts, on the other hand the advantageous fact that dewatering according to process step c) can be saved if an amine is used as the base and if the amount of water in
  • Step a) is adapted to the substantially lower amount of water preferred in step d). If tributylamine is used as the base in step a) and as the P (III) -containing raw material in later process step d) PC1 3 , 3 to 5.8 mol, preferably 3.8 to 4.6 mol, are preferred in process step a) Water used. This amount of water already corresponds to the amount required in process step d) plus the amount of water (1 mol) consumed by chemical reaction in process step a), so that dewatering (process step c) and ion exchange (process step b) can be dispensed with.
  • the preferred amount of carboxylic acid to be used if sodium hydroxide is used as the base, is 1 to 2 mol, particularly preferably 1.05 to 1.15. If a tertiary amine is used as the base, 0.90 to 0.98 mol of carboxylic acid are preferably used.
  • the molar amounts just mentioned are total amounts over the entire decay step a).
  • the amount of base added and the amount of water can step-wise execution of process step a) can be divided: So it turned out to be advantageous, initially
  • This division into two sub-steps 1) and 2) has the advantage that the pH can more easily be kept constant during the reaction with the unsaturated carboxylic acid.
  • the preferred pH range for substep 2) is 3 to 8, particularly preferably pH 5 to 6.
  • Process step a) is particularly simple if
  • Sodium hydroxide is used as the base. Instead of reacting SO 2 with sodium hydroxide solution and water, a solution of the commercially available sodium disulfite in water can be prepared directly here and reacted with a solution of carboxylic acid and sodium hydroxide in water. If the sodium disulfite solution is initially introduced and the sodium carboxylate solution is added, the proportion of oligomers in the end product is lower than if the sodium carboxylate solution is initially introduced and then the sodium disulfite solution is added.
  • the preferred reaction temperature for substep 1) is 0 to 40 ° C.
  • 20 to 80 ° C. are preferred if an alkali metal hydroxide is used as the base, and 40 to 100 ° C. if an amine is used as the base.
  • Process step b) is only necessary if an alkali hydroxide was used as base in step a). In the ion exchange process, at least 50%, preferably at least 70%, of all alkali ions should be exchanged for H + ions. If an amine is used as the base, step b) can be omitted.
  • a resin with SO 3 H groups, such as LEWATIT® S 100, can be used as the ion exchanger.
  • Process step c) is necessary if the aqueous solution from process step a) or b) contains more than 4.8 mol of water per mol of SO used.
  • Process step c) is usually necessary after process step b), since the eluates from the ion exchange resin usually contain too much water. If an amine is used as the base, step c) can be omitted, provided that no more than 5.8 mol of water was used in step a).
  • Dewatering is preferably carried out by distillation in vacuo at a pressure greater than or equal to 20 mbar and a bottom temperature of less than or equal to 90 ° C.
  • a membrane process for concentrating the solution is also suitable.
  • the P (III) -containing raw material to be used in process step d) can be one of the following pure compounds or a mixture of the same compounds of trivalent phosphorus: phosphorus trichloride (PC1 3 ), phosphorus tribromide (PBr 3 ), phosphorus trioxide (PO 6 ), pyrophosphorous Acid (H 4 P 2 O 5 ), Phosphorous acid
  • the raw material containing P (III) only gives the desired reaction under dehydrating conditions.
  • Dehydrating conditions means that in the
  • the initial molar ratio of the oxygen atoms bound to phosphorus (mol Op -bound ) to all the phosphorus atoms present in the mixture (mol P total ) must not be greater than 2.4.
  • this initial molar ratio (mol Op -bound ) / (mol P total ) all oxygen atoms from the phosphorus-containing raw materials plus the oxygen atoms from possibly added water or from the water already present in the reaction mixture and divided by the number of P atoms from all added phosphorus-containing raw materials.
  • the oxygen atoms from raw materials other than water and P (III) raw material are not counted.
  • the suitable raw materials show as pure substances the following initial molar ratios (mol O P born and s y (m ol Pg tal).
  • Phosphorus trichloride and phosphorus trihalides bromide (0), phosphorus trioxide (1.5), pyrophosphoric acid (2.5 ), Phosphorous acid and its esters (3)
  • phosphorus trioxide can be used as pure substances, all other substances must be mixed with another suitable P (III) raw material or in a mixture to achieve the desired molar ratio be used with water.
  • Preferred P (III) raw materials are the readily available and inexpensive chemicals phosphorus trichloride and phosphorous acid. If these preferred raw materials are used, an initial molar ratio (mol O P. Bound ) / (mol P total ) of 1.4 to 1.8 is very particularly preferred. To achieve an initial molar ratio (mol O P-bonded ) / (mol P total ) of 1 > 5, for example, 1 mol of phosphorus trichloride must be used together with 0.5 mol of phosphorous acid or together with 1.5 mol of water. Phosphorus trichloride, phosphorous acid and water can also be used in a combination of three. The use of 3/3 mol PC1 3 to 2/3 mol water and 1/3 mol H 3 PO 3 is particularly advantageous because
  • Phosphorous acid can then be used in the form of a particularly inexpensive 70% aqueous solution, a waste product of fatty acid chlorination.
  • Reaction step d) can be carried out in the presence of an amine salt, the amine salt of the amine which has already been added in process step a) preferably being used.
  • an amine salt the amine salt of the amine which has already been added in process step a) preferably being used.
  • Process step d) added free acids plus the acids formed by hydrolysis of PC1 3 , PBr 3 or P 4 O 6 are greater than the molar amount of the free amine, ie the reaction mixture must have an excess of acid. If, for example, PC1 3 , water and H 3 PO 3 are used as raw materials, this condition can be expressed in the following inequality:
  • the amine salt accelerates the reaction and leads to a higher yield of phosphonate in a shorter time.
  • the reaction in the presence of an amine salt the reaction in
  • Process step d) at 75 ° C for about one to three hours.
  • the temperature in process step d) can be 40 to 180 ° C. Reaction temperatures of 60 to 130 ° C are preferably used. If low-boiling PC1 3 is used as raw material, the reaction temperature is 130 ° C
  • the order in which the raw materials are put together is arbitrary.
  • reaction mixture from process step d) is hydrolyzed.
  • at least as much water or aqueous hydrochloric acid is added that all PCI or PBr bonds or P-O-P- used in process step d)
  • Bridges can be hydrolyzed.
  • the one already used in process step d) The amount of water is taken into account. For example, if 1.5 mol PC1 3 and 1 mol water were used in addition to other raw materials in process step d), at least 2 mol water must be added again in process step c).
  • the preferred amount of water is 1.1 to 20 times the minimum amount.
  • the hydrolysis is preferably carried out at temperatures from 70 to 120 ° C., particularly preferably at 90 to 110 ° C.
  • the hydrolysis can also be carried out at elevated pressure.
  • the preferred time for the hydrolysis is one hour to 24 hours, particularly preferably 12 to 20 hours.
  • step f volatile constituents of the reaction mixture, especially water and hydrogen chloride, are distilled off.
  • the mixture is preferably heated to temperatures of up to 130 ° C. and aqueous hydrochloric acid is taken off at normal pressure or in vacuo.
  • process step g) If process step d) was carried out in the presence of an amine salt, the process is completed by process step g).
  • the reaction mixture is adjusted to a pH greater than 7, preferably to pH 10-14, by adding alkali metal hydroxide solution, preferably sodium hydroxide solution.
  • alkali metal hydroxide solution preferably sodium hydroxide solution.
  • trimethylamine, triethylamine or tripropylamine it can be separated off by distillation. Due to their low water solubility, tributyl-, tripentyl- or trihexylamine can be separated from the phosphonate mixture very well by phase separation.
  • the recovered amine can be reused in process step a) or d).
  • the substances and mixtures according to the invention can be used in many ways, for example as scale inhibitors and also as corrosion inhibitors. Areas of application of such agents can be, for example: water treatment (e.g. treatment of cooling water, process water, injection water for secondary oil production and water treatment in mining) as well as industrial and institutional cleaning applications (e.g. container and equipment cleaning in the food industry, bottle cleaning, institutional dishwashing detergents and detergents) .
  • water treatment e.g. treatment of cooling water, process water, injection water for secondary oil production and water treatment in mining
  • industrial and institutional cleaning applications e.g. container and equipment cleaning in the food industry, bottle cleaning, institutional dishwashing detergents and detergents
  • Such agents contain an l-hydroxy-3-sulfonopropane-l, l-diphosphonic acid of the formula (I) or a phosphonate-containing mixture of substances of the formulas (II) to (V), optionally also (II) to (VII), preferably in a total phosphonic acid concentration of 1 to 20%. Calculating the concentration of free
  • Phosphonic acid is described in Example 1, process step g).
  • the agents can of course also contain the phosphonic acids in the form of their alkali metal, ammonium or alkylammonium salts.
  • Zinc salts molybdates, borates, silicates, azoles (e.g. tolyl or benzotriazole), other phosphonic acids, homo-, co- and terpolymers based on acrylic acid, methacrylic acid, maleic acid, and possibly also co-monomers with phosphonate Containing sulfonate and / or hydroxy side groups, further polyaspartic acids, lignin sulfonates, tannins, phosphates, complexing agents, citric acid, tartaric acid, gluconic acid, surfactants, disinfectants, dispersants, biocides.
  • acids e.g. "phosphonic acids”
  • their salts phosphonates
  • vice versa can also be used.
  • Substances and mixtures according to the invention, to which polyaspartic acids and / or their salts have been added as an additional component, have proven particularly advantageous.
  • Preferred embodiments of the polyaspartic acids are described in DE 4 439 193 AI, which are also included in the present application.
  • the present invention further relates to a method for water treatment, which is characterized in that the substances or mixtures according to the invention are introduced into the water to be treated.
  • the present invention relates to a process for alkaline cleaning, characterized in that the substances or mixtures according to the invention are used as incrustation inhibitors / sequestering agents.
  • the substances or mixtures according to the invention for preventing deposits and deposits when used in cooling systems with fresh water cooling are added to the incoming water in concentrations between about 0.1 and 1 omg / l of active ingredient.
  • the additives for stone and / or corrosion protection are often dosed depending on the quantity of the make-up water.
  • the concentrations are between about 1 and 50 mg / 1 active ingredient in the circulating cooling water, the water hardness of which is usually much higher than that of fresh water cooling. Even higher water hardness often occurs - at least temporarily - in smaller cooling water systems, e.g. B. for air conditioners for hospitals or large office buildings, due to insufficient monitoring. Additives with a high calcium tolerance are particularly desirable for such systems. Dosages are around 10 to 500 mg / 1 active ingredient in the circulating cooling water.
  • the active ingredient concentrations used to inhibit incrustation and sequestering in alkaline cleaning are based in particular on the technical and physical conditions, such as, for. B. pH values, residence times, temperatures, water hardness.
  • 3,940,436 is in principle not suitable for the preparation of compounds of the formula (I), since sulfono group and -C (OH) (PO 3 H 2 ) 2 - Group because of the synthetic route via the epoxyethane-l, l-diphosphonic acid sodium salt can only be separated from one another by a maximum of one CH 2 group, but not by two CH 2 groups.
  • the production process according to the invention is thus the only one which enables the preparation of compounds of the formula (I) in good yields.
  • 312 g of the above solution are placed in a 1 1 multi-necked flask with stirrer, internal thermometer, 2 dropping funnels, pH electrode and reflux condenser with an air line connected to it.
  • the mixture is preheated to 60 ° C. 72.42 g (1 mol) of acrylic acid (99.5%) and 78.5 g (0.42 mol) of tributylamine are then added dropwise from this at this temperature from two separate dropping funnels.
  • the pH of the reaction mixture is between 5 and 5.5. After the dropwise addition, stirring is continued at 60 ° C. for at least two hours.
  • reaction mixture is cooled to 40 to 50 ° C. and 136 g (1.53 mol) of 45% sodium hydroxide solution are added with stirring.
  • the 60 ° C warm, two-phase mixture is transferred to a separatory funnel.
  • Phase consists of 70.4 g of tributylamine, which can be used again in the synthesis without further purification (the degree of recovery for tributylamine in this experiment is 97.9%).
  • the heavier aqueous phase (490.4 g) is the desired phosphonate mixture.
  • a phosphorus content of the solution of 3.41% is calculated from the mass of the aqueous phase, the molar amount of PC1 3 used and the loss of PCl 3 by evaporation.
  • Residues of tributylammonium ions appear at 0.93, 1.38, 1.7 and 3.1 ppm.
  • the total mixture corresponds to the amounts of 1 mol of sulfur dioxide, 2.025 mol of sodium hydroxide solution, 1.1 mol of acrylic acid and 25.6 mol of water.
  • the solution from process step a) is passed through a column with 1.4 1 LEWATIT® S 100 ion exchanger (acid form).
  • the eluate from process step b) is first dewatered on a rotary evaporator at a heating bath temperature of 60 ° C. and a pressure of 50 mbar, and finally at 90 ° C. and 20 mbar for a further 10 minutes. 161 g of a solid residue are obtained.
  • the triplet of a -CH 2 -OH species appears, at 4.25 to 4.45 ppm a signal group for various -CH 2 -O-CO group-containing compounds.
  • the molar ratio of -CH 2 -SO 3 M to (-CH 2 -OH + -CH 2 -O-CO-) is 7.9.
  • the very broad signals for the inner protons of the various oligomers are at 1.5 to 2.55 ppm.
  • the average degree of oligomerization n- n i tt ,,] is calculated to be 1.18 (no change compared to the analysis after process step a)).
  • the mixture presented corresponds to the use amounts of originally 0.091 mol SO 2 and 0.1 mol acrylic acid and currently 0.2 mol amine and 0.3 mol water.
  • the heavier aqueous phase (216 g) is the desired phosphonate mixture. From the mass of the aqueous phase, the molar amount of PC1 3 used and the estimated PCl 3 loss of 8% by evaporation and sampling for analysis, a phosphorus content of the solution of 2.72% is calculated.
  • a sample of the solution is mixed with sodium hydroxide solution and after the
  • the added amount of phosphorus is calculated such that the molar ratio of employed amount of phosphorus to be inserted SO 2 quantity 2, or the Molar ratio of the amount of SO 2 used to the amount of phosphorus used is 0.5.
  • the molar ratio of free water before the PCl 3 addition to the phosphorus used is 1.7. After the addition of PCl 3 , the reaction mixture is stirred at 70 to 80 ° C. for a further 3 hours.
  • the reaction mixture is cooled to 60 ° C. and 213 g (2.4 mol) of 45% sodium hydroxide solution are added with stirring.
  • the 60 ° C warm, two-phase mixture is transferred to a separatory funnel.
  • the lighter, organic phase which separates out consists of 102.5 g of tributylamine, which can be used again in the synthesis without further purification (the degree of recovery for tributylamine in this experiment is 98.9%).
  • the heavier aqueous phase (724.5 g) is the desired phosphonate mixture.
  • a phosphorus content of the solution of 3.11% is calculated from the mass of the aqueous phase, the molar amount of PC1 3 used and the PCl 3 loss by evaporation.
  • step a) the methacrylic acid is reacted at 80 ° C. from the start.
  • a sample of the reaction solution obtained there is mixed with sodium hydroxide solution and, after the amine has been separated off on a rotary evaporator, concentrated at 20 mbar and 90 ° C.
  • a phosphite of the formula (IV) at 3.7 ppm (29.4% of the phosphorus) and a phosphate of the formula (V) at 4.6 ppm are also detectable (16.1% of the phosphorus). Together with other phosphonates of unknown structure, a total of 54.5% of the phosphorus is present in phosphonates.
  • the 31 P-NMR spectrum shows a triplet characteristic of the -CH 2 -C (OH) (PO 3 M 2 ) 2 group of achiral compounds at 18.8 ppm. Only 13.2% of the phosphorus is contained in this -CH 2 -C (OH) (PO 3 M 2 ) 2 group.
  • a compound of the formula can also be used
  • This compound contains 11.5% of the phosphorus. Together with other phosphonates of unknown structure, a total of 91.0% of the phosphorus is present in phosphonates. The majority of the phosphonates contained cannot be assigned here either in terms of their structure. 8.0% of the phosphorus is present as phosphate of the formula (V), the chemical shift of which is 2.9 ppm.
  • the reaction mixture is alkaline immediately after the solution is added dropwise. After heating to 95-100 ° C., the pH drops to approximately 6. The mixture is heated to 100 ° C. with stirring for 19 hours.
  • the solution obtained (129.9 g) has a final pH of 4.3.
  • the 3, P-NMR spectrum shows a triplet characteristic of the -CH 2 -C (OH) (PO 3 M 2 ) 2 group of achiral compounds at 19.0 ppm. This group contains 23.1% of the phosphorus. Together with other phosphonates of unknown structure, a total of 87.8% of the phosphorus is present in phosphonates. The majority of the phosphonates contained can be obtained from the
  • the pH of the solution is adjusted to 9.0 by adding sodium hydroxide solution or hydrochloric acid, and the volume is then made up to 1 liter.
  • This solution contains 500 mg / 1
  • the sealed bottles are stored in a forced-air drying cabinet at 75 ° C for 24 h. After cooling, the pH is measured (control) and - after stirring in any salts which may have precipitated for homogenization - the turbidity of the samples measured in a turbidity photometer according to EN 27027 in a 50 mm cuvette and given as FNU (formazin - nephelometry unit).
  • a high calcium tolerance is a prerequisite for an effective calcium carbonate inhibition in water with a high calcium concentration.
  • Three different waters which are oversaturated in calcium carbonate, are synthetically prepared from demineralized water by dissolving salts and adjusting the pH with sodium hydroxide solution or hydrochloric acid. In these waters, the deposition of solids during storage is examined depending on the added stone inhibitors of different structure and concentration.
  • a synthetic tap water of the following composition is produced: 100 mg / 1 Ca 2+ and 12 mg / 1 Mg 2+ , corresponding to 3 mmol / 1 alkaline earth ions and a total hardness of 300 ppm CaCO 3 or 17 ° d GH,
  • the total hardness (initial hardness) of this water is determined by titration with EDTA.
  • a small amount of the inhibitor is added to this water so that its concentration in the test solution, calculated as free inhibitor acid, is 2, 5, 10 or 25 ppm.
  • the substance according to the invention is able to stabilize a higher residual hardness than all other comparison substances.
  • the minimum inhibitor concentration which just prevents scale from being separated from double-concentrated synthetic water is 5 mg / l for the substance according to the invention from Example 1, and for the substances from the comparative examples claimed by US Pat. No. 5,221,487 3 and 4 at 10 mg / 1, in the case of the manufacturing process provided sample from comparative example 1 at 25 mg / 1 and at HEDP above 25 mg / 1.
  • the substance according to the invention therefore already achieves the same effect as the substances described there at half the dosage.
  • Example 6a In comparison to Example 6a), a synthetic water with four times the ion concentration is used.
  • a synthetic cooling water which has twice the ion concentrations in comparison to example 6a).
  • An inhibitor concentration of 30 mg / l is established in 12 liters of this synthetic water by adding de-neutralized inhibitor.
  • This solution is poured into a 12 liter container in which four steel tube rings made of carbon steel (St 37) degreased by pretreatment with acetone are moved through the solution at a speed of 0.6 m / s on a stirrer.

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EP99958148A 1998-12-11 1999-12-01 1-hydroxy-3-sulfonoalkan-1,1-diphosphonsäuren Withdrawn EP1137651A1 (de)

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DE19857251 1998-12-11
DE19857251A DE19857251A1 (de) 1998-12-11 1998-12-11 1-Hydroxy-3-sulfonoalkan-1,1-diphosphonsäuren
PCT/EP1999/009337 WO2000035926A1 (de) 1998-12-11 1999-12-01 1-hydroxy-3-sulfonoalkan-1,1-diphosphonsäuren

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MY129053A (en) 2001-06-06 2007-03-30 Thermphos Trading Gmbh Composition for inhibiting calcium salt scale
EP1392914B1 (en) 2001-06-06 2010-12-22 Dequest AG Method and aqueous composition for the production of improved pulp
KR100666826B1 (ko) * 2006-09-06 2007-01-10 박종화 등밀이형 및 장갑형 겸용 목욕타올

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US3940436A (en) * 1970-04-13 1976-02-24 Monsanto Company Substituted ethane diphosphonic acids and salts and esters thereof
US5221487A (en) * 1991-10-24 1993-06-22 W. R. Grace & Co.-Conn. Inhibition of scale formation and corrosion by sulfonated organophosphonates

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