WO2007021617B1 - Dosage efficient, storage stable compositions for reducing chromium (vi) in cement - Google Patents
Dosage efficient, storage stable compositions for reducing chromium (vi) in cementInfo
- Publication number
- WO2007021617B1 WO2007021617B1 PCT/US2006/030577 US2006030577W WO2007021617B1 WO 2007021617 B1 WO2007021617 B1 WO 2007021617B1 US 2006030577 W US2006030577 W US 2006030577W WO 2007021617 B1 WO2007021617 B1 WO 2007021617B1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- cement
- chromium
- reducer
- association complex
- composition
- Prior art date
Links
Classifications
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- 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
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- 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
- C04B7/00—Hydraulic cements
- C04B7/32—Aluminous cements
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- 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
- C04B22/08—Acids or salts thereof
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- 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
- C04B24/04—Carboxylic acids; Salts, anhydrides or esters thereof
- C04B24/06—Carboxylic acids; Salts, anhydrides or esters thereof containing hydroxy groups
-
- 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
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/52—Grinding aids; Additives added during grinding
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
Abstract
An association complex formed in a liquid environment from a metal- based chromium (VI) reducer and a non-lignosulfonate-based complexing agent is introduced into cement clinker or hydratable cement particles. In preferred embodiments, the formation of the association complex provides storage stability to the chromium reducer within the cement, such that the level of chromium (VI) after water is added to the cement remains less than 2 ppm for certain duration after mixing with water and without the necessity for further additions of chromium reducer during said duration (e.g., 26-84 or more days after addition). Compositions having the association complex are also described.
Claims
1. A method comprising: introducing to cement clinker or to hydratable cement particles a composition having therein an association complexA wherein a metal ion operative to reduce chromium (Vl) to chromium (III) is attached by non-covaleπt coordinate links to two or more nonmetal atoms of a noπ-lignosulfonate-based complexing agent.
2. The method of claim 1 wherein said metal-based chromium (Vl) reducer, in said association complex, is combined with said cement clinker or to said hydratable cement particles in an amount of 20-2000 parts per million (ppm) of chromium reducer for each 5 ppm of chromium (Vl) contained in said cement clinker or hydratable cement particles.
3. The method of claim 2 wherein said association complex is added to cement clinker before or during the intergrinding process used for manufacturing hydratabie cement particles from cement clinker, and said clinker is iπterground to produce hydratable cement particles combined with said chromium (Vl) reducer.
4. The method of claim 3 wherein said hydratable cement particles, after combination with said association complex containing said metal-based chromium (Vl) reducer but without further addition of a chromium (Vl) reducer, have an average level of chromium (Vl) which is less than 2 parts per million by weight of cement, during the successive 28 days after said intergrinding.
5. The method of claim 2 wherein said hydratable cement particles, after combination with said association complex containing said metal-based chromium (Vl) reducer but without further addition of chromium (Vl) reducer, have an average level of chromium Vl which is less than 2 parts per million by weight of cement, during the successive 56 days after said intergrinding.
6. The method of claim 2 wherein said hydratable cement particles, after combination with said association complex containing said metal-based chromium (Vl) reducer but without further addition of chromium (Vl) reducer, have an average level of chromium Vl which is less than 2 parts per million by weight of cement, during the successive 84 days after said intergrinding.
-JJ-
7. The method of claim 1 wherein said association complex is introduced to hydratable cement particles, before, during, or after water is introduced to said cement particles to initiate the process of hydration.
8. The method of claim 1 wherein said metal-based chromium (Vf) reducer is a metal salt.
9. The method of claim 8 wherein said metal salt is formed from chloride, bromide, acetate, oxide, sulfide, hydroxide, or sulfate.
10. The method of claim 1 wherein said chromium (Vl) reducer is stannous (tin II) sulfate.
11. The method of claim 1 wherein said chromium (Vl) reducer is selected from the group of stannous sulfate, stannous chloride, ferrous sulfate, ferrous chloride, manganese sulfate, and manganese chloride.
12. The method of claim 1 wherein said association complex is stannous gluconate which is formed from combining stannous chloride, stannous sulfate, or mixture thereof with calcium gluconate, sodium gluconate, or mixture thereof.
13. The method of claim 1 wherein said noπ-lignosulfonate-based complexing agent is a gluconic acid or salt thereof.
14. The method of claim 1 wherein said non-lignosulfαnate-based complexing agent is sodium gluconate.
15. The method of claim 1 wherein said πon-lignosulfoπate-based complexing agent comprises a monocarboxylic acid, dicarboxylic acid, polyhydroxyalcohol, aldehydo acid, or the salt thereof.
16. The method of claim 1 wherein said non-lignosulfonate-baεed complexing agent is a metal ion chelating agent 17. The method of claim 1 wherein said non-lignosulfoπate-based complexing agent is selected from the group consisting of ethylenediaminetetraacetic acid (EDTA), mitrilotriacetic acid (N(CH2COOH)3, and ethyleneglyco[-bis(B-ammoethyl ether)-N,N- tetraacetic acid (NOOCCH≥^NCHaCH≤OCH≤CHaOCHaCH∑NfCHaCOOH)^ ethylene glycol, glycerine, glucose, dextrose, sucrose, polyvinyl alcohol, tripolyphosphates, copolymers of vinyl methyl ether, maleic anhydride, N-benzoyl-N-pheπylhydroxylamine, acetylacetone, benzoylacetone, dibeπzoylmethane, salicylaldehyde, 8- hydroxyhydroquinoπe. and 8-quinolinol.
-36-
18. The method of claim 2 wherein said non-ligπosulfonate-based complexing agent is employed in the amount of 0.0005-0.1% based on dry weight of cement being interground.
19. The method of claim 2 wherein said non-lignosulfonate-based complexing agent is employed in the amount of 0.001-0,02% based on dry weight cement being interground.
20. The method of claim 1 wherein said composition is an aqueous liquid.
21. The method of claim 1 further comprising introducing to cement dinker or to hydratable cement particles at least one cement additive.
22. The method of claim 21 wherein said at least one cement additive is selected from the group consisting of triisopropanolamine, triethanolamine, glycols, sugars and chloride salts,
23. A cement composition provided by the method of claim 1.
24, A cement composition comprising hydratable cement particles and a metal-based chromium (Vl) reducer introduced to said cement particles in the form of an association complex formed by combining a metal-based chromium (Vl) reducer and a non-lignosulfonate-based complexing agent, whereby said metal-based chromium (Vl) reducer is attached by non-covalent coordinate links to two or more nonmetal atoms of said non-lignosulfonate-based complexing agent
25. The composition of claim 24 wherein said cement has an average level of chromium (Vl) which is Jess than 2 parts per million by weight of cement during the successive 26 days after said association complex is combined with said cement.
26. The composition of claim 24 wherein said cement has an average level of chromium (VI) which is less than 2 parts per million by weight of cement during the successive 56 days after said association complex is combined with said cement.
27. The composition of claim 24 wherein said cement has an average level of chromium (Vl) which is less than 2 parts per million by weight of cement during the successive 84 days after said association complex is combined with said cement.
28. A method comprising: introducing to cement clinker or to hydratable cement particles a composition comprising stannous gluconic acid or a salt thereof,_said stannous gluconic acid or salt thereof being in the form of an association complex whereby stannous ions are attached by non-covalent coordinate links to two or more nonmetal atoms of gluconic acid or salt, and said stannous ions are operative to reduce chromium (Vl) to chromium (III) when water is added to cement particles manufactured from said cement clinker or when water is added to said hydratable cement particles.
29. A composition, comprising: an association complex formed by combining a metal-based chromium (Vl) reducer and a non-Iignosulfonate-based complexing agent, said association complex being present in an amount no less than 10% based on total weight of said composition.
30. The composition of claim 1 wherein said association complex is formed by combining, in an aqueous environment, stannous sulfate and sodium gluconate in a molar ratio of 1 :2 to 2:1.
31. The composition of claim 1 wherein said association complex is formed by combining, in an aqueous liquid environment, stannous sulfate and sodium gluconate in a molar ratio of 1:1 , said association complex comprising at least 20% of said liquid environment by tota! weight.
32. The composition of claim 1 wherein said association complex is formed by combining stannous sulfate and sodium gluconate in a 1:1 molar ratio, said complex having a 13C NMR spectrum, when compared to sodium gluconate alone, as follows:
-38-
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008526094A JP2009504554A (en) | 2005-08-12 | 2006-08-03 | Composition having good administration efficiency and storage stability for reducing chromium (VI) in cement |
| AU2006280182A AU2006280182A1 (en) | 2005-08-12 | 2006-08-03 | Dosage efficient, storage stable compositions for reducing chromium (VI) in cement |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US70790105P | 2005-08-12 | 2005-08-12 | |
| US60/707,901 | 2005-08-12 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| WO2007021617A2 WO2007021617A2 (en) | 2007-02-22 |
| WO2007021617A3 WO2007021617A3 (en) | 2007-04-26 |
| WO2007021617B1 true WO2007021617B1 (en) | 2007-06-21 |
Family
ID=37758067
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/US2006/030577 WO2007021617A2 (en) | 2005-08-12 | 2006-08-03 | Dosage efficient, storage stable compositions for reducing chromium (vi) in cement |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP2009504554A (en) |
| KR (1) | KR20080044246A (en) |
| CN (1) | CN101282917A (en) |
| AU (1) | AU2006280182A1 (en) |
| WO (1) | WO2007021617A2 (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010057225A2 (en) * | 2008-11-11 | 2010-05-20 | Afrisam (South Africa) (Pty) Ltd | ADDITIVES FOR Cr (VI) REDUCTION IN CEMENT, SLAGS, MORTARS, CONCRETE, WASTE WATER AND MINING INDUSTRY WASTE |
| CN104496243B (en) * | 2014-11-06 | 2017-03-22 | 中国建筑材料科学研究总院 | Hexavalent chromium reducing agent and preparation method thereof, cement and preparation method thereof |
| CN104496251B (en) * | 2014-11-25 | 2017-03-22 | 中国建筑材料科学研究总院 | Liquid hexavalent chromium reducing agent and preparation method thereof, cement and preparation method thereof |
| CN105198260A (en) * | 2015-10-13 | 2015-12-30 | 云南锡业股份有限公司 | Special tin-containing additive for removing hexavalent chromium from cement and preparation method of additive |
| CN105924029A (en) * | 2016-04-21 | 2016-09-07 | 张伟 | Liquid cement additive for reducing content of water-soluble Cr<6+> in cement |
| KR101832676B1 (en) * | 2017-11-10 | 2018-02-28 | 조병학 | Cement mixture and manufacturing method thereof |
| KR101891052B1 (en) * | 2018-02-20 | 2018-08-23 | 조병학 | Cement mixture and manufacturing method thereof |
| CN109503000A (en) * | 2018-11-09 | 2019-03-22 | 高正春 | A kind of environmentally friendly cement and preparation method thereof |
| CN112374789B (en) * | 2020-10-13 | 2022-05-24 | 唐山冀东水泥外加剂有限责任公司 | Cement hexavalent chromium reducing agent and preparation method thereof |
| CN113480219A (en) * | 2021-07-15 | 2021-10-08 | 内蒙古宏尔高新材料科技有限公司 | Chromium reducing agent for reducing water-soluble chromium (VI) in cement and preparation method thereof |
| CN117720300A (en) | 2022-09-09 | 2024-03-19 | Sika技术股份公司 | Novel chromium reducing agent for cement |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3981965A (en) * | 1972-08-17 | 1976-09-21 | Allied Chemical Corporation | Suppression of water pollution caused by solid wastes containing chromium compounds |
| US4260491A (en) * | 1978-11-15 | 1981-04-07 | Amchem Products, Inc. | Chrome removal waste treatment process |
| US7128782B2 (en) * | 2003-11-21 | 2006-10-31 | W.R. Grace & Co.-Conn. | Sulfate dispersion chromate reducer |
-
2006
- 2006-08-03 WO PCT/US2006/030577 patent/WO2007021617A2/en active Application Filing
- 2006-08-03 JP JP2008526094A patent/JP2009504554A/en active Pending
- 2006-08-03 AU AU2006280182A patent/AU2006280182A1/en not_active Abandoned
- 2006-08-03 CN CNA2006800374751A patent/CN101282917A/en active Pending
- 2006-08-03 KR KR1020087004051A patent/KR20080044246A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| KR20080044246A (en) | 2008-05-20 |
| AU2006280182A1 (en) | 2007-02-22 |
| JP2009504554A (en) | 2009-02-05 |
| WO2007021617A3 (en) | 2007-04-26 |
| WO2007021617A2 (en) | 2007-02-22 |
| CN101282917A (en) | 2008-10-08 |
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