DE29915326U1 - Chromate reducer for the reduction of chromates in hydraulically setting masses - Google Patents
Chromate reducer for the reduction of chromates in hydraulically setting massesInfo
- Publication number
- DE29915326U1 DE29915326U1 DE29915326U DE29915326U DE29915326U1 DE 29915326 U1 DE29915326 U1 DE 29915326U1 DE 29915326 U DE29915326 U DE 29915326U DE 29915326 U DE29915326 U DE 29915326U DE 29915326 U1 DE29915326 U1 DE 29915326U1
- Authority
- DE
- Germany
- Prior art keywords
- iron
- chromate
- reduction
- tin
- chromates
- 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.)
- Expired - Lifetime
Links
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 title claims description 16
- 239000003638 chemical reducing agent Substances 0.000 title claims description 7
- 230000009467 reduction Effects 0.000 title description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 19
- 229910052742 iron Inorganic materials 0.000 claims description 9
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- FAKFSJNVVCGEEI-UHFFFAOYSA-J tin(4+);disulfate Chemical compound [Sn+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O FAKFSJNVVCGEEI-UHFFFAOYSA-J 0.000 claims description 3
- 229910000358 iron sulfate Inorganic materials 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims 1
- -1 tin (II) ions Chemical class 0.000 claims 1
- 239000004568 cement Substances 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 6
- 230000008901 benefit Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 150000002506 iron compounds Chemical class 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 230000002110 toxicologic effect Effects 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000005569 Iron sulphate Substances 0.000 description 1
- 229910006653 SnII Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000011505 plaster Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- IUTCEZPPWBHGIX-UHFFFAOYSA-N tin(2+) Chemical compound [Sn+2] IUTCEZPPWBHGIX-UHFFFAOYSA-N 0.000 description 1
- 231100000759 toxicological effect Toxicity 0.000 description 1
- 231100000027 toxicology Toxicity 0.000 description 1
Classifications
-
- 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Chemical Treatment Of Metals (AREA)
Description
BESCHREIBUNGDESCRIPTION
Die deutsche Zementindustrie hat sich aber aus Kostengründen entschieden den Chromatgehalt beim Zement in der Regel durch Eisen II - sulfat zu reduzieren. Die praktisch technische Durchführung einer solchen Reduktion sieht in der Regel so aus ,dass besonders unter der Berücksichtigung der Lagerfähigkeit ,die Mindestdosierung bei 0,4% bis 0,5 % Eisen II - sulfat pro Tonne Zement liegt. Im Einzelfall kann die Höchstdosierung bis zu 1,5 % und darüber betragen.However, for cost reasons, the German cement industry has decided to reduce the chromate content of cement using iron II sulfate. The practical technical implementation of such a reduction is generally such that the minimum dosage is 0.4% to 0.5% iron II sulfate per ton of cement, particularly taking storage capacity into account. In individual cases, the maximum dosage can be up to 1.5% and more.
Dieses Verfahren hat jedoch viele Nachteile bezüglich der Lager - und Temperaturstabilität. Ein Zement der zum Beispiel 10 ppm Chromat enthält und mit 0,5 % Eisen II -sulfat versetzt wurde , zeigt nach dem direkten Zusatz des Reduktors einen Chromatgehalt von 0,3 ppm und liegt damit unterhalb des gesetzlichen Grenzwertes. Wird dieser Zement einer Temperatur von 65° C längere Zeit ausgesetzt steigt der Chromatgehalt an. Dieser zu beobachtende Anstieg des Chromatgehaltes nimmt mit der Länge der Lagerzeit und ebenso mit steigender Temperatur drastisch zu und übersteigt die Grenze von 2 pm . Weiterhin wird dem Zement sehr viel Sulfat durch den Reduktor zugesetzt und farbliche Veränderungen , hervorgerufen durch das Eisensulfat, in den Zementprodukten sind nicht auszuschließen. Eisenverbindungen sind auch aus toxikologischer, arbeitsmedizinischer Sicht zu mindestens diskutierbar. This process, however, has many disadvantages with regard to storage and temperature stability. For example, a cement which contains 10 ppm chromate and has been mixed with 0.5% iron II sulfate, will have a chromate content of 0.3 ppm after the direct addition of the reductant, which is below the legal limit. If this cement is exposed to a temperature of 65° C for a longer period of time, the chromate content increases. This observed increase in chromate content increases dramatically with the length of storage and also with increasing temperature, and exceeds the limit of 2 pm. Furthermore, a lot of sulfate is added to the cement by the reductant, and color changes in the cement products caused by the iron sulfate cannot be ruled out. Iron compounds are also at least debatable from a toxicological and occupational health point of view.
Durch ein Gemisch von Fe II - und Zinn II - salzen sind die Nachteile des Eisens erheblich reduziert und die Vorteile der teueren Zinn II - verbindungen sinnvoll genutzt.By using a mixture of Fe II and tin II salts, the disadvantages of iron are significantly reduced and the advantages of the expensive tin II compounds are sensibly utilized.
-2--2-
Somit wird ein Gemisch aus 7 % Zinnsulfat und 93 % Eisensulfat hergestellt. Dem Zement mit einem Chromatgehalt von 10 ppm werden dann 0,2 % des obigen Gemisches zugesetzt und bei 650C längere Zeit erhitzt .Das Resultat zeigt, dass der Chromatwert vor dem Erhitzen 0,3 ppm und nach dem Erhitzen 1 ppm beträgt. Das heißt der Grenzwert von 2 ppm Chromat wird nicht erreicht. Wird das System längere Zeit erhitzt ist eine signifikante Änderung des Chromatwertes nicht zu erwarten (s. Tabelle Anhang) Weitere Vorteile sind hierdurch erreicht worden :This produces a mixture of 7% tin sulphate and 93% iron sulphate. 0.2% of the above mixture is then added to the cement with a chromate content of 10 ppm and heated for a longer period at 65 ° C. The result shows that the chromate value is 0.3 ppm before heating and 1 ppm after heating. This means that the limit value of 2 ppm chromate is not reached. If the system is heated for a longer period, a significant change in the chromate value is not to be expected (see table in the appendix). This has resulted in further advantages:
1. Das Gemisch ist auf den Anwendungsfall der Chromatreduziening bezogen im Zement dosierbar ( s. Tabelle Anhang)1. The mixture can be dosed in the cement depending on the application of chromate reduction (see table in the appendix)
2 . Lager - und Temperatur - Stabilität sind gewährleistet.2 . Storage and temperature stability are guaranteed.
3 . Starke Reduktion des Sulfatgehaltes.3 . Strong reduction of sulfate content.
4. Durch das Absenken des Eisengehaltes wird die Anfälligkeit von farblichen Veränderungen in Zementprodukten wesentlich verringert.4. By reducing the iron content, the susceptibility to colour changes in cement products is significantly reduced.
5. Mögliche toxikologische Einflüsse des Eisens werden erheblich reduziert. 5. Possible toxicological effects of iron are considerably reduced .
6. Die gesamten Vorteile werden ausschließlich aus dem Zinn II-produkt hergeleitet. Da Zinnverbindungen bis zu 20 mal teuerer sind als Eisenverbindungen werden dieses Gemisch und die damit verbundenen Vorteile ökonomisch einsetzbar. 6 . All the benefits are derived exclusively from the tin II product. Since tin compounds are up to 20 times more expensive than iron compounds, this mixture and the associated benefits are economically viable.
7. Schon geringe Mengen von Zinn II vermögen das Eisen II - sulfat zu stabilisieren . Eine Zugabe von nur O, Ol % Zinnsulfat erhöht die Lebensdauer des Eisenproduktes. 7. Even small amounts of tin II can stabilize the iron II sulfate. Addition of only 0.10% tin sulfate increases the life of the iron product.
In der Zementmatrix fallen Eisenverbindungen sofort als Hydroxide aus während Zinn amphoter ist und somit auch steigende Chromatgehalte über die Zeit sicher reduziert, dies ist z.B. beim verzögerten Transportmauermörtel, Werkfrischputz, Werkfrischmörtel und Werkfrischestrichen zu beobachten.In the cement matrix, iron compounds immediately precipitate as hydroxides, while tin is amphoteric and thus also reliably reduces increasing chromate contents over time. This can be observed, for example, in delayed transport masonry mortar, freshly applied plaster, freshly applied mortar and freshly applied screeds.
-3--3-
-J--J-
AnhaneAnhane ::
Chrom -VI- gehalt ppm Std. Temp. 0C Fell - redukt. (0,5%) Fell / SnII (0,2%)Chromium -VI- content ppm Std. Temp. 0 C Fell - reduced (0.5%) Fell / SnII (0.2%)
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE29915326U DE29915326U1 (en) | 1999-09-01 | 1999-09-01 | Chromate reducer for the reduction of chromates in hydraulically setting masses |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE29915326U DE29915326U1 (en) | 1999-09-01 | 1999-09-01 | Chromate reducer for the reduction of chromates in hydraulically setting masses |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE29915326U1 true DE29915326U1 (en) | 2000-07-13 |
Family
ID=8078306
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE29915326U Expired - Lifetime DE29915326U1 (en) | 1999-09-01 | 1999-09-01 | Chromate reducer for the reduction of chromates in hydraulically setting masses |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE29915326U1 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005016843A3 (en) * | 2003-08-08 | 2005-07-07 | Chryso Sas | Colloidal hydroxide aqueous suspension of at least one transition element serving to reduce chrome in cement |
| WO2005056860A3 (en) * | 2003-11-21 | 2005-08-11 | Grace W R & Co | Sulfate dispersion chromate reducer |
| EP1710215A1 (en) * | 2005-04-08 | 2006-10-11 | Kerr-McGee Pigments International GmbH | Process for manufacturing a hydraulic binder. |
| FR2884509A1 (en) * | 2005-04-18 | 2006-10-20 | Chryso Soc Par Actions Simplif | ADJUVANT FOR REDUCING ION CHROME (VI) IN CHROME (III) |
| CN100441533C (en) * | 2004-02-04 | 2008-12-10 | 格雷斯公司 | A method for reducing hexavalent chromium in cement composition |
| DE102010009444A1 (en) * | 2010-02-23 | 2011-08-25 | MIG Material Innovative Gesellschaft mbH, 33154 | Composition, useful for reducing chromium(VI) ions in cement or cement-containing products, and for preparing storage stable cement or cement-containing products, comprises iron(II) ions and/or antimony(III) ions, and tin(II) ions |
| EP2363386A1 (en) * | 2010-02-23 | 2011-09-07 | Mig Material Innovative Gesellschaft MBH | Reduction of CR(VI) ions in cement or products containing cement |
| US20190135689A1 (en) * | 2005-03-24 | 2019-05-09 | Jacques Bertrand | Dry grout composition and capsule for anchoring reinforcing member, dowel or anchor elements |
-
1999
- 1999-09-01 DE DE29915326U patent/DE29915326U1/en not_active Expired - Lifetime
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7601328B2 (en) | 2003-08-08 | 2009-10-13 | Chryso | Colloidal hydroxide aqueous suspension of at least one transition element serving to reduce chrome in cement |
| WO2005016843A3 (en) * | 2003-08-08 | 2005-07-07 | Chryso Sas | Colloidal hydroxide aqueous suspension of at least one transition element serving to reduce chrome in cement |
| WO2005056860A3 (en) * | 2003-11-21 | 2005-08-11 | Grace W R & Co | Sulfate dispersion chromate reducer |
| US7128782B2 (en) | 2003-11-21 | 2006-10-31 | W.R. Grace & Co.-Conn. | Sulfate dispersion chromate reducer |
| JP2007522061A (en) * | 2003-11-21 | 2007-08-09 | ダブリュー・アール・グレイス・アンド・カンパニー−コネチカット | Sulfate-dispersed chromate reducing agent |
| RU2351559C2 (en) * | 2003-11-21 | 2009-04-10 | В.Р. Грейс Энд Ко.-Конн. | Chromate-treated reducer of sulphate dispersion |
| CN100441533C (en) * | 2004-02-04 | 2008-12-10 | 格雷斯公司 | A method for reducing hexavalent chromium in cement composition |
| US20190135689A1 (en) * | 2005-03-24 | 2019-05-09 | Jacques Bertrand | Dry grout composition and capsule for anchoring reinforcing member, dowel or anchor elements |
| EP1710215A1 (en) * | 2005-04-08 | 2006-10-11 | Kerr-McGee Pigments International GmbH | Process for manufacturing a hydraulic binder. |
| WO2006105984A1 (en) * | 2005-04-08 | 2006-10-12 | Tronox Pigments Int. Gmbh | Method for producing a hydraulic binder |
| FR2884509A1 (en) * | 2005-04-18 | 2006-10-20 | Chryso Soc Par Actions Simplif | ADJUVANT FOR REDUCING ION CHROME (VI) IN CHROME (III) |
| AP2271A (en) * | 2005-04-18 | 2011-08-10 | Chryso | Adjuvant for reducing chromium VI ions into chromium. |
| US8361221B2 (en) | 2005-04-18 | 2013-01-29 | Chryso | Additive for reducing chromium (VI) to chromium (III) ions |
| WO2006111639A1 (en) * | 2005-04-18 | 2006-10-26 | Chryso | Adjuvant for reducing chromium (vi) ions into chromium (iii) |
| DE102010009444A1 (en) * | 2010-02-23 | 2011-08-25 | MIG Material Innovative Gesellschaft mbH, 33154 | Composition, useful for reducing chromium(VI) ions in cement or cement-containing products, and for preparing storage stable cement or cement-containing products, comprises iron(II) ions and/or antimony(III) ions, and tin(II) ions |
| EP2363386A1 (en) * | 2010-02-23 | 2011-09-07 | Mig Material Innovative Gesellschaft MBH | Reduction of CR(VI) ions in cement or products containing cement |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| R207 | Utility model specification |
Effective date: 20000817 |
|
| R081 | Change of applicant/patentee |
Owner name: GRACE BAUPRODUKTE GMBH, DE Free format text: FORMER OWNER: ABC- ANGERSDORFER BAUCHEMIE GMBH, 06179 ANGERSDORF, DE Effective date: 20011112 |
|
| R150 | Utility model maintained after payment of first maintenance fee after three years |
Effective date: 20021024 |
|
| R081 | Change of applicant/patentee |
Owner name: GRACE BAUPRODUKTE GMBH, DE Free format text: FORMER OWNER: TRICOSAL BETON-CHEMIE GMBH & CO. KG, 32676 LUEGDE, DE Effective date: 20040325 |
|
| R151 | Utility model maintained after payment of second maintenance fee after six years |
Effective date: 20050909 |
|
| R152 | Utility model maintained after payment of third maintenance fee after eight years |
Effective date: 20071010 |
|
| R071 | Expiry of right |