US20060234878A1 - Additive for reducing chromium (vi) ions to chromium (iii) ions - Google Patents

Additive for reducing chromium (vi) ions to chromium (iii) ions Download PDF

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Publication number
US20060234878A1
US20060234878A1 US11/279,974 US27997406A US2006234878A1 US 20060234878 A1 US20060234878 A1 US 20060234878A1 US 27997406 A US27997406 A US 27997406A US 2006234878 A1 US2006234878 A1 US 2006234878A1
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US
United States
Prior art keywords
additive
tin
ions
chromium
carboxylic acid
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.)
Abandoned
Application number
US11/279,974
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English (en)
Inventor
Pierre-Antoine Andreani
Bruno Pellerin
Karen Ayme
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chryso SAS
Original Assignee
Chryso SAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Chryso SAS filed Critical Chryso SAS
Assigned to CHRYSO reassignment CHRYSO ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: ANDREANI, PIERRE-ANTOINE, AYME, KAREN, PELLERIN, BRUNO
Publication of US20060234878A1 publication Critical patent/US20060234878A1/en
Priority to US12/498,231 priority Critical patent/US8361221B2/en
Abandoned legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/40—Compounds containing silicon, titanium or zirconium or other organo-metallic compounds; Organo-clays; Organo-inorganic complexes
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/40—Compounds containing silicon, titanium or zirconium or other organo-metallic compounds; Organo-clays; Organo-inorganic complexes
    • C04B24/405—Organo-inorganic complexes
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/14—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/0028—Aspects relating to the mixing step of the mortar preparation
    • C04B40/0039—Premixtures of ingredients
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/0004—Compounds chosen for the nature of their cations
    • C04B2103/002—Compounds of elements having a valency of 2
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/10—Compositions or ingredients thereof characterised by the absence or the very low content of a specific material
    • C04B2111/1075—Chromium-free or very low chromium-content materials
    • C04B2111/1081—Chromium VI, e.g. for avoiding chromium eczema

Definitions

  • the Sn(OH) 4 2 ⁇ ion is able to reduce CrO 4 2 ⁇ to Cr(OH) 3 ⁇ by the oxidation/reduction reaction of Equation 2.
  • Another aim of the present invention was to propose an additive of this type that does not modify the properties and the behaviour of the added materials.
  • the invention relates to a process for preparing the additive described above, which includes the steps of bringing a tin(II) salt into contact with carboxylic acid or a salt thereof in the presence of an appropriate amount of water.
  • the molar ratio of carboxylic acid to tin(II) compound is preferably from 0.5:1 to 5:1.
  • the structure of the tin(II)/carboxylic acid complex formed is not specified, it will be noted that the stability of the solution (clear solution without precipitation) at low temperature and at alkaline pH is particularly high for a ratio higher than from 1.5:1 to 2:1. This stability is maintained for higher ratios.
  • tin(II) compound used is of no particular incidence. In practice, it will be selected from water-soluble tin(II) salts, such as tin(II) chloride, tin sulphate, tin fluoride and tin acetate.
  • the reaction between the tin(II) compound and the carboxylic acid or its salt is rapid and complete.
  • the order in which the reagents are introduced is of no particular incidence.
  • the tin(II) thus complexed is stable with respect to oxidation, but available for an oxidation/reduction reaction with chromium(VI).
  • the additive described is particularly useful for producing materials having a low chromium(VI) content.
  • the invention relates to a process for preparing a material having a low chromium(VI) content, including the step of bringing the material into contact with an appropriate amount of additive as described.
  • low chromium(VI) content intends especially to refer to a water-soluble chromium(VI) content of less than 2 ppm.
  • cementing medium-type materials are especially intended.
  • cementing medium (or “hydraulic binder”) especially refers to cements, but also to calcium sulphate and its hydrated forms, fly ash and slag.
  • the invention relates to the use of the additive described for the preparation of a material having a low chromium(VI) content.
  • the admixing is carried out during the step in which the cement is prepared at the cement works. It consists in introducing the additive, after the step in which the clinker is obtained, during the preparation of the cement.
  • the additive is used, within the cement preparation process, during grinding.
  • the proportions will advantageously be determined as a function of the water-soluble chromium(VI) ion content of the sampled material.
  • the specified percentages are percentages by mass of the type in question, i.e. tin chloride (SnCl 2 ) or sodium gluconate.
  • Example 1 was repeated, but the amounts of tin chloride and sodium gluconate were modified to the amounts indicated in Table 1.
  • Example 6 is highly viscous and has a sediment. It is assumed to be a supersaturated solution.
  • the NMR tin tests were carried out at 300 K on a Bruker Avance 300 spectrometer (111.9 MHz for tin 119) equipped with a 5 mm BBI probe.
  • the solutions were studied without dilution or the addition of a lock solvent, the resonance width being considerably greater than the stability of the magnetic field ( ⁇ 2 Hz).
  • the pulse sequence consisted of a single pulse of 30°, followed by the acquisition of the free precession signal at 16 k points.
  • the pulse interval is 0.244 seconds and corresponds to the acquisition time.
  • solutions prepared with a gluconate/tin molar ratio of 1.5:1 and 2:1 are clear at ambient temperature and do not precipitate, even after prolonged storage at 0° C.
  • concentration As far as the concentration is concerned, it will be noted that the solutions prepared with an amount of SnCl 2 between 15 and 25% are stable for a gluconate/tin molar ratio of 2:1, while the solutions prepared with an SnCl 2 amount of 25% are clear after storage at 0° C., even for a molar ratio of 1.5:1.
  • the turbidity measurement clearly reveals the difference between a clear solution (low turbidity) and a milky solution (high turbidity).
  • Example 7 A turbidity measurement taken after 24 hours (measured value 927) in Example 7 demonstrates the appearance of a precipitate.
  • the solutions prepared in Examples 3, 8 and 9 remain at the same level of turbidity even after prolonged storage (for longer than 1 month). This would seem to indicate that there is a turbidity threshold, below which the turbidity of the solution remains low over a prolonged storage time.
  • the cement was treated by addition to the cement at the inlet of the grinder.
  • the quantity of additive is indicated in ppm of solution relative to ppm of chromium(VI) present in the cement, as determined by prior analysis.
  • the chromium(VI) of the cement thus treated was subsequently determined immediately, then after ageing in a bag for 1 month, in accordance with Standard EN 196-10, which specifies the protocol for the analysis of chromium(VI) in cements.
  • the pH stability of the solutions prepared was assessed as follows.
  • the stability of the complex imparts a very considerable degree of formulation freedom, facilitating, in particular, compatibility with a broad range of additives. It may also help to stabilise the additive in materials having a very alkaline pH such as, in particular, cement, thus allowing the reductive effect of the chromium(VI) ions to be perpetuated. Finally, the stability of the additives provides them with a certain robustness with respect to variations in the processing conditions.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Anti-Oxidant Or Stabilizer Compositions (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
  • Fats And Perfumes (AREA)
  • Processing Of Solid Wastes (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Cosmetics (AREA)
  • Catalysts (AREA)
US11/279,974 2005-04-18 2006-04-17 Additive for reducing chromium (vi) ions to chromium (iii) ions Abandoned US20060234878A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US12/498,231 US8361221B2 (en) 2005-04-18 2009-07-06 Additive for reducing chromium (VI) to chromium (III) ions

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0503855A FR2884509B1 (fr) 2005-04-18 2005-04-18 Adjuvant pour reduire les ions chrome (vi) en chrome (iii)
FR0503855 2005-04-18

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US12/498,231 Division US8361221B2 (en) 2005-04-18 2009-07-06 Additive for reducing chromium (VI) to chromium (III) ions

Publications (1)

Publication Number Publication Date
US20060234878A1 true US20060234878A1 (en) 2006-10-19

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ID=35045076

Family Applications (2)

Application Number Title Priority Date Filing Date
US11/279,974 Abandoned US20060234878A1 (en) 2005-04-18 2006-04-17 Additive for reducing chromium (vi) ions to chromium (iii) ions
US12/498,231 Active 2027-11-04 US8361221B2 (en) 2005-04-18 2009-07-06 Additive for reducing chromium (VI) to chromium (III) ions

Family Applications After (1)

Application Number Title Priority Date Filing Date
US12/498,231 Active 2027-11-04 US8361221B2 (en) 2005-04-18 2009-07-06 Additive for reducing chromium (VI) to chromium (III) ions

Country Status (28)

Country Link
US (2) US20060234878A1 (ar)
EP (1) EP1871722B1 (ar)
JP (1) JP4319244B2 (ar)
KR (1) KR100939007B1 (ar)
AP (1) AP2271A (ar)
AT (1) ATE432913T1 (ar)
AU (1) AU2006238499B2 (ar)
CA (1) CA2542712C (ar)
CY (1) CY1109358T1 (ar)
DE (1) DE602006007119D1 (ar)
DK (1) DK1871722T3 (ar)
EG (1) EG26212A (ar)
ES (1) ES2326432T3 (ar)
FR (1) FR2884509B1 (ar)
HR (1) HRP20090392T1 (ar)
IL (1) IL184651A (ar)
MA (1) MA29228B1 (ar)
NO (1) NO341059B1 (ar)
NZ (1) NZ556498A (ar)
PL (1) PL1871722T3 (ar)
PT (1) PT1871722E (ar)
RS (1) RS51165B (ar)
RU (1) RU2363677C2 (ar)
SI (1) SI1871722T1 (ar)
TN (1) TNSN07266A1 (ar)
UA (1) UA88667C2 (ar)
WO (1) WO2006111639A1 (ar)
ZA (1) ZA200603066B (ar)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070034118A1 (en) * 2005-08-12 2007-02-15 Jardine Leslie A Dosage efficient, storage stable compositions for reducing chromium (VI) in cement
US20090162273A1 (en) * 2007-12-21 2009-06-25 Howmedica Osteonics Corp. Chromium oxide powder having a reduced level of hexavalent chromium and a method of making the powder

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9725364B2 (en) * 2012-07-06 2017-08-08 Lanxess Deutschland Gmbh Method for reducing hexavalent chromium in oxidic solids
US9540287B2 (en) * 2013-03-13 2017-01-10 United States Gypsum Company Particle stabilized foam, and slurries, product, and methods related thereto

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3607352A (en) * 1968-11-29 1971-09-21 Enthone Electroless metal plating
US5487906A (en) * 1994-12-15 1996-01-30 Colgate-Palmolive Company Method of forming stable aqueous solutions of stannous compounds
US7087110B2 (en) * 2004-02-04 2006-08-08 W. R. Grace & Co.-Conn. Liquid additive for intergrinding cement
US7128782B2 (en) * 2003-11-21 2006-10-31 W.R. Grace & Co.-Conn. Sulfate dispersion chromate reducer
US7232483B2 (en) * 2005-02-01 2007-06-19 W. R. Grace & Co.-Conn. Cement composition having chromium reducer

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL298693A (ar) * 1962-10-02 1900-01-01
US4780153A (en) * 1987-02-06 1988-10-25 Guhde Donald J Chromium-containing low-cure coating composition
EP0960865A1 (de) * 1998-05-25 1999-12-01 Chemische Werke Zell-Wildshausen GMBH Mittel zur Reduzierung von Chrom (VI)-Ionen in einer hydraulisch abbindenden Masse
DE29915326U1 (de) * 1999-09-01 2000-07-13 ABC- Angersdorfer Bauchemie GmbH, 06179 Angersdorf Chromatreduzierer zur Reduktion von Chromaten in hydraulisch abbindenden Massen
FR2858612B1 (fr) * 2003-08-08 2006-02-24 Chryso Sas Suspension aqueuse colloidale d'hydroxyde d'etain destinee a la reduction de chrome dans le ciment
DE202004010467U1 (de) * 2004-07-02 2004-09-16 Mig Mbh Material Innovative Gesellschaft Mbh Zinn-II-Chlorid zur Verbesserung der Frühfestigkeit und Zementqualität
WO2006132762A2 (en) * 2005-06-02 2006-12-14 W.R. Grace & Co.-Conn. Biomass-derived grinding aids
US20070034118A1 (en) * 2005-08-12 2007-02-15 Jardine Leslie A Dosage efficient, storage stable compositions for reducing chromium (VI) in cement

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3607352A (en) * 1968-11-29 1971-09-21 Enthone Electroless metal plating
US5487906A (en) * 1994-12-15 1996-01-30 Colgate-Palmolive Company Method of forming stable aqueous solutions of stannous compounds
US7128782B2 (en) * 2003-11-21 2006-10-31 W.R. Grace & Co.-Conn. Sulfate dispersion chromate reducer
US7087110B2 (en) * 2004-02-04 2006-08-08 W. R. Grace & Co.-Conn. Liquid additive for intergrinding cement
US7232483B2 (en) * 2005-02-01 2007-06-19 W. R. Grace & Co.-Conn. Cement composition having chromium reducer

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070034118A1 (en) * 2005-08-12 2007-02-15 Jardine Leslie A Dosage efficient, storage stable compositions for reducing chromium (VI) in cement
US20090162273A1 (en) * 2007-12-21 2009-06-25 Howmedica Osteonics Corp. Chromium oxide powder having a reduced level of hexavalent chromium and a method of making the powder

Also Published As

Publication number Publication date
ZA200603066B (en) 2008-02-27
FR2884509B1 (fr) 2007-07-06
EP1871722A1 (fr) 2008-01-02
DE602006007119D1 (de) 2009-07-16
WO2006111639A1 (fr) 2006-10-26
US20090266272A1 (en) 2009-10-29
RU2363677C2 (ru) 2009-08-10
CY1109358T1 (el) 2014-07-02
AU2006238499A1 (en) 2006-10-26
DK1871722T3 (da) 2009-08-17
ES2326432T3 (es) 2009-10-09
EP1871722B1 (fr) 2009-06-03
SI1871722T1 (sl) 2009-12-31
CA2542712A1 (fr) 2006-10-18
FR2884509A1 (fr) 2006-10-20
ATE432913T1 (de) 2009-06-15
AU2006238499B2 (en) 2011-09-29
AP2007004073A0 (en) 2007-08-31
IL184651A0 (en) 2007-12-03
PL1871722T3 (pl) 2009-11-30
RU2007135744A (ru) 2009-04-10
AP2271A (en) 2011-08-10
JP2008532919A (ja) 2008-08-21
IL184651A (en) 2011-06-30
NZ556498A (en) 2011-09-30
KR100939007B1 (ko) 2010-01-28
UA88667C2 (ru) 2009-11-10
TNSN07266A1 (fr) 2008-12-31
NO341059B1 (no) 2017-08-14
RS51165B (sr) 2010-10-31
HRP20090392T1 (hr) 2009-08-31
MA29228B1 (fr) 2008-02-01
PT1871722E (pt) 2009-09-02
CA2542712C (fr) 2013-12-03
EG26212A (ar) 2013-04-28
KR20070096002A (ko) 2007-10-01
NO20073745L (no) 2007-11-15
US8361221B2 (en) 2013-01-29
JP4319244B2 (ja) 2009-08-26

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Owner name: CHRYSO, FRANCE

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:ANDREANI, PIERRE-ANTOINE;PELLERIN, BRUNO;AYME, KAREN;REEL/FRAME:017712/0415

Effective date: 20060516

STCB Information on status: application discontinuation

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