CN105924029A - Liquid cement additive for reducing content of water-soluble Cr<6+> in cement - Google Patents
Liquid cement additive for reducing content of water-soluble Cr<6+> in cement Download PDFInfo
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- CN105924029A CN105924029A CN201610263643.4A CN201610263643A CN105924029A CN 105924029 A CN105924029 A CN 105924029A CN 201610263643 A CN201610263643 A CN 201610263643A CN 105924029 A CN105924029 A CN 105924029A
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- cement
- liquid additive
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- sodium
- cement liquid
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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
Abstract
The invention provides a liquid cement additive for reducing the content of water-soluble Cr<6+> in cement. The liquid cement additive has good Cr<6+> elimination ability, and also has the advantages of reasonable price, small mixing amount, and small influences on the performances of cement. The liquid cement additive comprises, by mass, 5-10% of sodium borohydride, 5-10% of sodium sulfite, 5-10% of sodium nitrite, 5-10% of sodium formate, 1-5% of polyglycerol, 0-15% of alcohol amine, 0.5-1% of NaOH, and the balance of water, wherein the alcohol amine is at least one of triethanolamine, triisopropanolamine, diethanol isopropanolamine and methyldiethanolamine, and the pH value of the liquid cement additive is 10-14. The liquid cement additive has good Cr<6+> elimination ability, and has the advantages of reasonable price, small mixing amount, and small influences on the performances (such as water requirement of normal consistency and intensity) of cement.
Description
Technical field
The present invention relates to a kind of reduction cement water-solubility Cr6+The cement liquid additive of content, belongs to building material field.
Background technology
Cement is the basic raw material used by industry and civil buildings concrete, and cement, after the stirring that adds water, wherein contains
Water-solubility Cr6+The rapid dissolution of meeting, is now used in new mixing water slurry body, mortar or concrete, the mud watt of plastic stage
Solubility Cr in work and concreter's Long Term Contact cement6+, if do not used rational labour protection measures, sensitive group will
Cause skin allergy, to such an extent as to form the cement Allergic contact eczema being difficult to cure, be usually expressed as pain, fester, seriously
Time result even in and lose work capacity.Water-solubility Cr in cement6+Source have: 1) the mixing material of cement, as containing chromium Industry Waste
Slag, this is water-solubility Cr in current cement6+Main source；2) containing chromium firebrick, from the thermal zone fire proofed wood of cement rotary kiln
Material；3) ball milling Vertical Mill crushing and grinding equipment, such as chrome-bearing steel ball and liner plate；4) cement raw material, as limestone, clay, iron tailings contain
There is trace chromium, cause and the grog after calcining also contains certain Cr6+.In cement, Cr6+Content generally not over always
The 30% of chromium content.It is found that when making abrasive media pulverizing cement grog with chromium steel ball (containing chromium 17%～28%), cement
In Cr6+Content will increase to Cr in original grog6+2 times of content.Water-solubility Cr in China's cement6+Content is generally
10～30ppm, typically can be higher containing higher chromium industrial residue making cement mixing material if using, sometimes can reach 50～70ppm.
European Union limits water-solubility Cr in cement6+Content is less than 2ppm (2mg/kg).In Asia, cement is produced by Japan and Korea S
Water-solubility Cr in product6+The production internal control index of content is 8ppm.In China, GB31893-2015 " water soluble chromium (VI) in cement
Limitation and assay method " approval of 2015 years JIUYUE 11 Nikkei State Administration for Quality Supervision and Inspection and Quarantine issues, will be in 2016 10
The moon 1 was formally implemented.This core content of the standard is: 1. water-solubility Cr in cement6+Limitation is no more than 10mg/kg；2. in cement
Water-solubility Cr6+Assay method be diphenyl carbazide spectrophotometry.
Water-solubility Cr in current effective reduction cement6+Approach have: 1) use without chromium firebrick；2) at cement flour
Bull ring joint uses reducing agent can make the Cr in cement6+It is reduced into harmless trivalent chromium.For the approach of use reducing agent, current state
Inside and outside patent and data show, use ferrous sulfate heptahydrate and stannous chloride, stannous sulfate, zinc sulfate, zinc chloride and manganese sulfate
This kind of reducing agent has and preferably eliminates Cr6+Ability, but be used alone its volume of ferrous sulfate heptahydrate can be of a relatively high, typically
At cement consumption 0.2%-0.4%, and stannous chloride, stannous sulfate and manganese sulfate have due to price higher market acceptance degree
Limit, and this series products of zinc sulfate, zinc chloride facts have proved except Cr6+Effect is limited；It addition, the aqueous solution homogeneity of these inorganic salts
Performance is also difficult to steadily in the long term, easy laminated segregation；Containing being also easy in the case of chloride ion cause steel bar corrosion.It is reported,
500 DEG C of zeolites calcined after cooling also have certain solidification Cr6+Ability, but mixed cement and cement standard can be made thick
Degree water requirement dramatically increases, and is unfavorable for the production of concrete.
Summary of the invention
Goal of the invention
It is an object of the invention to provide a kind of reduction cement water-solubility Cr6+The cement liquid additive of content, has good
Elimination Cr6+Ability, reasonable price, volume are less, little on cement performance impact simultaneously.
Summary of the invention
The invention provides a kind of reduction cement water-solubility Cr6+The cement liquid additive of content, mass percent forms
As follows: sodium borohydride 5%-10%, sodium sulfite 5%-10%, sodium nitrite 5%-10%, sodium formate 5%-10%, be polymerized sweet
Oil 1%-5%, hydramine 0-15%, NaOH 0.5%-1%, surplus is water, and described hydramine is triethanolamine, triisopropanolamine, second
At least one in glycol monoisopropanolamine, methyl diethanolamine, the pH value of described cement liquid additive is 10-14.
Preferably, described hydramine be triethanolamine, triisopropanolamine and ethylene glycol monoisopropanolamine by (1-2): 1: (1-2)
Mass ratio composition mixture.
Preferably, in described cement liquid additive, sodium borohydride, sodium sulfite, sodium nitrite, sodium formate and polymerization are sweet
The mass percent sum of oil is 30%-40%.
Polyglycerol be known can be as the material of cement additire, it is preferred that the molecular weight of described polyglycerol is
250-300。
Wherein, sodium borohydride, sodium sulfite, sodium nitrite and sodium formate are all reducing agents；Poly-and glycerol contains-OH and also has
There is certain reproducibility；Hydramine is the primary raw material of cement grinding aid, can mix as the case may be and become cementitious composite interpolation
Agent.
In order to ensure reducing power and the homogeneous stable performance of gained cement liquid additive of sodium borohydride as far as possible, excellent
Choosing, the preparation method of described cement liquid additive is: after NaOH is dissolved in water, adds remaining components mix homogeneously, obtains
Described cement liquid additive.
Cement liquid additive usage of the present invention, with the usage of traditional cements additive, adds when manufacture of cement,
Volume is the 0.03%-0.20% of cement quality, with specific reference to mixing before and after described cement liquid additive Cr in cement6+Content
Depending on Duo Shao.
Cement liquid additive of the present invention has good elimination Cr6+Ability, reasonable price, volume are relatively simultaneously
Little, cement performance (such as consumptive use of water normal consistence, intensity etc.) is affected little.
Detailed description of the invention
Explain below in conjunction with the embodiments.
Raw material used by following example is as follows:
Sodium borohydride, technical grade, Nantong Hongzhi Chemical Co., Ltd. produces；
Sodium sulfite, industry one-level, Suzhou dicyclo Chemical Industry Science Co., Ltd produces；
Sodium nitrite, technical grade, Zhong Xin Chemical Co., Ltd. of Xinxiang City produces；
Sodium formate, technical grade 98%, Zibo Puli Si Chemical Co., Ltd. produces；
Polyglycerol, 75%, molecular weight 250-300, Nanjing Shenhe New Materials Technology Co., Ltd. produces；
Triethanolamine, 85 grades, Shandong Hongyi Technology Co., Ltd. produces；
Triisopropanolamine, 85 grades, Nanjing red Pola group company produces；
Ethylene glycol monoisopropanolamine, 85 grades, Nanjing Rong Feng Environmental Protection Technology Co., Ltd produces；
Sheet alkali (NaOH), technical grade, jackshaft chemical plant, Linzhou City, Zibo, Shandong Province produces.
The mass percent composition of cement liquid additive described in embodiment 1-7 is as shown in table 1.Wherein: hydramine is three second
The mixture that hydramine, triisopropanolamine and ethylene glycol monoisopropanolamine are formed by the mass ratio of 2: 1: 1.
Table 1
Following Application Example and blank example cement testing as a comparison use the examination of unification of the motherland model SM500 × 500
Testing little mill, steel ball is abrasive media；Use following P.O 42.5 cement mixing ratio: grog 75%, dihydrate gypsum 5%, flyash
10%, chrome-bearing steel ferrum industrial residue 10%；Wherein, grog, Carnis Rapanae thomasianae Cement Group Chinese cement factory produces, 28 days intensity 58MPa；
Dihydrate gypsum, Nanjing Gypsum Mine produces；Flyash, Nanjing great Chang power plant of Huaneng Group group produces, two grades of ashes；Chrome-bearing steel ferrum Industry Waste
Slag, Ma'an Mountain's steel enterprise produces.Before entering mill, clinker, Gypsum Fibrosum and chrome-bearing steel ferrum industrial residue first carry out precrushing, make into
Grind materials granularity is less than 7mm.
Blank example
According to above-mentioned P.O 42.5 cement mixing ratio weigh treat the grog of grinding, Gypsum Fibrosum and respectively mix material (flyash, containing chromium
Steel and iron industry waste residue) it is total to 5Kg, tentatively mix.Excess material in mill body is removed clean, be subsequently poured into broken after load weighted
Compound.Closing grinding door, start is ground.The time of cement grinding discharging reaches 350m according to its specific surface area2/ kg determines.
Application Example 1-7
According to above-mentioned P.O 42.5 cement mixing ratio weigh treat the grog of grinding, Gypsum Fibrosum and respectively mix material (flyash, containing chromium
Steel and iron industry waste residue) it is total to 5Kg, mix cement additire by 0.10% (5g) of cement quality, tentatively mix to obtain compound.Will mill
Internal excess material is removed clean, is subsequently poured into described compound.Closing grinding door, start is ground.Grinding time and blank example phase
With.The cement additire added in Application Example 1-7 corresponds to embodiment 1-7 gained cement liquid additive respectively.Root
According to GB/T1346-2011 " cement setting time, consumptive use of water normal consistence, stability detection method "；GB175-2007 " general silicon
Acid salt cement "；" cement pressure steams stability examination for GB/T17671-1999 " cement mortar strength test method ", GB/T750-1992
Proved recipe method ", the standard testing cement performance such as GB31893-2015 " limitation of water soluble chromium (VI) and assay method in cement ", water
The concrete physical and chemical performance of mud is shown in Table 2.
As can be seen from Table 2, to the cement performance of the incorporation of cement liquid additive of the present invention not own produces bright
Development rings；Described cement liquid additive has under 0.10% volume and preferably subtracts chromium effect, water-solubility Cr6+Content is at cement
In with age extend the most stable.Certainly, in actual production, need (containing grog, to mix according to each raw material and equipment
Material, powder grinding medium and equipment, refractory brick is containing situations such as chromium) the concrete condition suitable additive volume of selection, it is ensured that water in cement
Dissolubility Cr6+Content controls at below 10ppm, and to meet national standard requirement, thus beneficially people are healthy.
Claims (5)
1. one kind is reduced cement water-solubility Cr6+The cement liquid additive of content, it is characterised in that mass percent forms such as
Under: sodium borohydride 5%-10%, sodium sulfite 5%-10%, sodium nitrite 5%-10%, sodium formate 5%-10%, polyglycerol
1%-5%, hydramine 0-15%, NaOH 0.5%-1%, surplus is water, and described hydramine is triethanolamine, triisopropanolamine, second two
At least one in alcohol monoisopropanolamine, methyl diethanolamine, the pH value of described cement liquid additive is 10-14.
2. cement liquid additive as claimed in claim 1, it is characterised in that described hydramine is triethanolamine, three isopropanols
Amine and ethylene glycol monoisopropanolamine are by (1-2): 1: the mixture of the mass ratio composition of (1-2).
3. cement liquid additive as claimed in claim 1 or 2, it is characterised in that the preparation of described cement liquid additive
Method is: after NaOH is dissolved in water, adds remaining components mix homogeneously, obtains described cement liquid additive.
4. cement liquid additive as claimed in claim 1 or 2, it is characterised in that the molecular weight of described polyglycerol is
250-300。
5. cement liquid additive as claimed in claim 1 or 2, it is characterised in that in described cement liquid additive, boron hydrogen
The mass percent sum changing sodium, sodium sulfite, sodium nitrite, sodium formate and polyglycerol is 30%-40%.
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| CN201610263643.4A CN105924029A (en) | 2016-04-21 | 2016-04-21 | Liquid cement additive for reducing content of water-soluble Cr<6+> in cement |
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| CN201610263643.4A CN105924029A (en) | 2016-04-21 | 2016-04-21 | Liquid cement additive for reducing content of water-soluble Cr<6+> in cement |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106673482A (en) * | 2016-12-16 | 2017-05-17 | 志成信（天津）科技有限公司 | Environment-friendly cement technological additive |
| CN106830725A (en) * | 2017-02-21 | 2017-06-13 | 辽宁天宝华瑞建材有限公司 | Cement Cr VI cuts down agent |
| CN108585597A (en) * | 2018-07-24 | 2018-09-28 | 青神鑫统领建材有限公司 | A kind of reduction of hexavalent chromium type grinding aid and preparation method thereof |
| CN113087428A (en) * | 2021-03-26 | 2021-07-09 | 唐山冀东水泥外加剂有限责任公司 | Chromium reducing agent, preparation method thereof and cement |
| CN113105140A (en) * | 2021-03-26 | 2021-07-13 | 唐山冀东水泥外加剂有限责任公司 | Chromium reducing agent and cement-based mixture using same |
| CN115093152A (en) * | 2022-06-13 | 2022-09-23 | 阳新娲石水泥有限公司 | Composite chromium-reducing grinding aid and preparation method thereof |
| CN115259739A (en) * | 2022-08-23 | 2022-11-01 | 青海新雨田化工有限公司 | Efficient cement chromium removing agent and preparation method thereof |
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| CN101282917A (en) * | 2005-08-12 | 2008-10-08 | 格雷斯公司 | Dosage efficient, storage stable compositions for reducing chromium (VI) in cement |
| CN102295933A (en) * | 2011-07-01 | 2011-12-28 | 浙江大学 | Special stabilizing agent for chromium polluted soil |
| CN103261116A (en) * | 2010-12-08 | 2013-08-21 | 电气化学工业株式会社 | Cement admixture, cement composition, and hexavalent chromium reduction method using same |
| CN104496251A (en) * | 2014-11-25 | 2015-04-08 | 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 |
| CN104496243A (en) * | 2014-11-06 | 2015-04-08 | 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 |
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Patent Citations (5)
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| CN101282917A (en) * | 2005-08-12 | 2008-10-08 | 格雷斯公司 | Dosage efficient, storage stable compositions for reducing chromium (VI) in cement |
| CN103261116A (en) * | 2010-12-08 | 2013-08-21 | 电气化学工业株式会社 | Cement admixture, cement composition, and hexavalent chromium reduction method using same |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106673482A (en) * | 2016-12-16 | 2017-05-17 | 志成信（天津）科技有限公司 | Environment-friendly cement technological additive |
| CN106830725A (en) * | 2017-02-21 | 2017-06-13 | 辽宁天宝华瑞建材有限公司 | Cement Cr VI cuts down agent |
| CN106830725B (en) * | 2017-02-21 | 2020-12-11 | 辽宁天宝华瑞建材有限公司 | Hexavalent chromium reducing agent for cement |
| CN108585597A (en) * | 2018-07-24 | 2018-09-28 | 青神鑫统领建材有限公司 | A kind of reduction of hexavalent chromium type grinding aid and preparation method thereof |
| CN108585597B (en) * | 2018-07-24 | 2020-10-27 | 青神鑫统领建材有限公司 | Reduced hexavalent chromium type grinding aid and preparation method thereof |
| CN113087428A (en) * | 2021-03-26 | 2021-07-09 | 唐山冀东水泥外加剂有限责任公司 | Chromium reducing agent, preparation method thereof and cement |
| CN113105140A (en) * | 2021-03-26 | 2021-07-13 | 唐山冀东水泥外加剂有限责任公司 | Chromium reducing agent and cement-based mixture using same |
| CN113087428B (en) * | 2021-03-26 | 2022-06-07 | 唐山冀东水泥外加剂有限责任公司 | Chromium reducing agent, preparation method thereof and cement |
| CN113105140B (en) * | 2021-03-26 | 2022-07-08 | 唐山冀东水泥外加剂有限责任公司 | Chromium reducing agent and cement-based mixture using same |
| CN115093152A (en) * | 2022-06-13 | 2022-09-23 | 阳新娲石水泥有限公司 | Composite chromium-reducing grinding aid and preparation method thereof |
| CN115259739A (en) * | 2022-08-23 | 2022-11-01 | 青海新雨田化工有限公司 | Efficient cement chromium removing agent and preparation method thereof |
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Application publication date: 20160907 |