CN110563361B - Low-doping cement chromium-removing grinding aid and preparation method thereof - Google Patents
Low-doping cement chromium-removing grinding aid and preparation method thereof Download PDFInfo
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- CN110563361B CN110563361B CN201910871054.8A CN201910871054A CN110563361B CN 110563361 B CN110563361 B CN 110563361B CN 201910871054 A CN201910871054 A CN 201910871054A CN 110563361 B CN110563361 B CN 110563361B
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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
- C04B7/36—Manufacture of hydraulic cements in general
- C04B7/48—Clinker treatment
- C04B7/52—Grinding ; After-treatment of ground cement
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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
- C04B7/36—Manufacture of hydraulic cements in general
- C04B7/60—Methods for eliminating alkali metals or compounds thereof, e.g. from the raw materials or during the burning process; methods for eliminating other harmful components
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Abstract
The invention discloses a low-doping cement chromium-removing grinding aid and a preparation method thereof, belonging to the technical field of cement additives. The cement chromium-removing grinding aid is prepared from the following raw materials in parts by weight: 20-40 parts of alcohol amine substances, 20-40 parts of alcohol substances, 25-40 parts of antimony trichloride and 5-15 parts of ethanol. According to the invention, antimony trichloride is used as a hexavalent chromium reducing agent, so that good compatibility with main raw materials of the grinding aid, namely hydramine and alcohols can be realized, and the grinding aid and the hexavalent chromium reducing agent can be compounded for use. The invention skillfully utilizes antimony trichloride and alcamines to form acid-base complexes, thereby not only reserving Sb3+For Cr6+The reduction effect of the composite material, and the formed acid-base complex have better stability than antimony trichloride, have low doping amount, low production cost and convenient use, have double effects of chromium removal effect and grinding aid effect, and have better popularization and application values.
Description
Technical Field
The invention belongs to the technical field of cement additives, and particularly relates to a low-doping cement chromium-removing grinding aid and a preparation method thereof.
Background
The cement grinding is the most important link in the cement production process, and the power consumption in the grinding process accounts for 60-70% of the total power consumption of the cement production, wherein the grinding power consumption of the finished cement product accounts for 30-40% of the total power consumption. The grinding process of cement is a process that cement material particles are reduced from big to small, and is also an energy conversion process that electric energy is converted into mechanical energy and further converted into surface energy of cement powder, and the energy conversion efficiency determines the utilization rate of energy, so that the utilization rate of energy can be improved by improving the conversion efficiency of energy in the grinding process, and the cost is reduced. The grinding aid can prevent cracks from closing through adsorption in the grinding process so as to promote crack expansion and reduce grinding power consumption in the grinding process, and through dispersion in the powder selection process, the efficiency of the powder selection machine is improved, and qualified fine powder is prevented from returning to the grinding cycle, so that the effects of saving energy and reducing consumption are achieved.
In 9 months in 2015, China officially released national mandatory Standard GB31893-2015 limit and determination method for Water-soluble chromium (VI) in cement, and officially implemented from 10 months and 1 days in 2016, the limit of chromium (VI) in cement is required to be not more than 10 mg/kg. The method for eliminating hexavalent chromium is to reduce toxic hexavalent chromium into nontoxic trivalent chromium by using a reducing agent, the reducing agent is generally ferrous salt, stannous salt and the like, the reducing agent has poor compatibility with alkaline alcohol amine substances and large using amount, can not be compounded with the traditional grinding aid in use generally, is mostly used as a powder product form, has high use cost and is inconvenient to popularize. Based on the problems, the hexavalent chromium reducing material which can be well compatible with main raw materials of grinding aids such as alcamines, alcohols and the like is selected, so that a product which is low in mixing amount and has double effects of the grinding aids and hexavalent chromium reduction is developed.
Disclosure of Invention
In order to solve the problem of compatibility use of the grinding aid and a hexavalent chromium reducing agent, the invention uses antimony trichloride as the hexavalent chromium reducing agent, can realize good compatibility with main raw materials of the grinding aid, namely hydramine and alcohols, and realizes the compound use of the grinding aid and the hexavalent chromium reducing agent.
The invention adopts the following technical scheme:
a low-doping cement chromium-removing grinding aid is prepared from the following raw materials in parts by weight: 20-40 parts of alcohol amine substances, 20-40 parts of alcohol substances, 25-40 parts of antimony trichloride and 5-15 parts of ethanol.
The alcamines are one or two of triethanolamine or diethanol monoisopropanolamine.
The alcohol substance is ethylene glycol.
The triethanolamine is an industrial product with the content of 85 percent.
The diethanol monoisopropanolamine is an industrial product with the content of 85 percent.
The ethylene glycol is 95% of industrial products.
The ethanol is industrial ethanol with the content of 95 percent.
The grinding aid is added in an amount of 0.02-0.04% of the mass of the cement according to the content of hexavalent chromium in the cement.
The antimony trichloride is an industrial product with the content of 99.5 percent.
The preparation method of the low-doped cement chromium-removing grinding aid comprises the following steps:
(1) firstly, dissolving antimony trichloride with a formula amount in ethylene glycol to form a solution;
(2) adding an alcamines substance into the solution, and introducing cooling water into the reaction kettle; after the dropwise addition is finished and the temperature of the system is stable after the reaction is completed, heating to 60 ℃, and preserving the temperature for 30 minutes;
(3) and finally, adding ethanol to adjust the viscosity of the product, and uniformly stirring.
The invention has the beneficial effects that:
(1) the invention relates to a product which uses antimony trichloride as a hexavalent chromium reduction component, ingeniously utilizes the antimony trichloride and alcamines to form an acid-base complex, and not only Sb is reserved3+For Cr6+And form a reduction ofCompared with antimony trichloride, the acid-base complex has better stability. The compounded alcohol amine compound can also play a role in grinding and dispersing for cement production, and improve the physical properties of cement.
(2) The emulsion-type product provided by the invention has the advantages of low mixing amount, low production cost, convenience in use, dual effects of chromium removal and grinding aid, and good popularization and application values.
Detailed Description
For a further understanding of the invention, preferred embodiments of the invention are described below in conjunction with the examples, but it should be understood that these descriptions are included merely to further illustrate the features and advantages of the invention and are not intended to limit the invention to the claims.
Example 1
The low-doping cement chromium-removing grinding aid is prepared from the following raw materials in parts by weight: 20 parts of triethanolamine, 20 parts of ethylene glycol, 25 parts of antimony trichloride and 5 parts of ethanol.
The triethanolamine is an industrial product with the content of 85 percent;
the glycol is an industrial product with the content of 95 percent.
The antimony trichloride is 99.5 percent of industrial products.
The ethanol is industrial ethanol with the content of 95 percent.
A preparation method of a low-doping cement chromium-removing grinding aid comprises the following steps:
(1) dissolving a certain weight part of antimony trichloride in ethylene glycol to form a solution;
(2) and adding triethanolamine into the solution, and introducing cooling water into the reaction kettle. After the dropwise addition is finished and the temperature of the system is stable after the reaction is completed, the temperature is raised to 60 ℃ and the temperature is kept for 30 minutes.
(3) And finally, adding ethanol to adjust the viscosity of the product, and uniformly stirring.
Example 2
The low-doping cement chromium-removing grinding aid is prepared from the following raw materials in parts by weight: 30 parts of diethanol monoisopropanolamine, 30 parts of ethylene glycol, 35 parts of antimony trichloride and 10 parts of ethanol.
The diethanol monoisopropanolamine is an industrial product with the content of 85 percent:
the glycol is an industrial product with the content of 95 percent.
The antimony trichloride is 99.5 percent of industrial products.
The ethanol is industrial ethanol with the content of 95 percent.
A preparation method of a low-doping cement chromium-removing grinding aid comprises the following steps:
(1) dissolving a certain weight part of antimony trichloride in ethylene glycol to form a solution;
(2) adding diethanol monoisopropanolamine into the solution, and introducing cooling water into the reaction kettle. After the dropwise addition is finished and the temperature of the system is stable after the reaction is completed, the temperature is raised to 60 ℃ and the temperature is kept for 30 minutes.
(3) And finally, adding ethanol to adjust the viscosity of the product, and uniformly stirring.
Example 3
The low-doping cement chromium-removing grinding aid is prepared from the following raw materials in parts by weight: 40 parts of diethanol monoisopropanolamine, 20 parts of ethylene glycol, 40 parts of antimony trichloride and 15 parts of ethanol.
The diethanol monoisopropanolamine is an industrial product with the content of 85 percent:
the glycol is an industrial product with the content of 95 percent.
The antimony trichloride is 99.5 percent of industrial products.
The ethanol is industrial ethanol with the content of 95 percent.
A preparation method of a low-doping cement chromium-removing grinding aid comprises the following steps:
(1) dissolving a certain weight part of antimony trichloride in ethylene glycol to form a solution;
(2) adding alcamines into the solution, and introducing cooling water into the reaction kettle. After the dropwise addition is finished and the temperature of the system is stable after the reaction is completed, the temperature is raised to 60 ℃ and the temperature is kept for 30 minutes.
(3) And finally, adding ethanol to adjust the viscosity of the product, and uniformly stirring.
Test for chromium removal Effect
Proportioning cement materials: 80% of clinker, 5% of slag, 5% of fly ash, 5% of natural gypsum and 5% of limestone are selected. The cement material 5Kg is weighed in four test groups, and the cement material of examples 1-3 and the commercial ferrite reducing agent are respectively added according to the proportion and mixed evenly, and a blank comparative example is arranged, namely the chromium removing agent is not added. Respectively adding cement with the diameter of 500 x 500mm into a small experimental mill, grinding for 20 minutes, and then measuring the content of the water-soluble chromium (VI) in the cement according to the standard of GB31893-2015 limit and measuring method for the water-soluble chromium (VI) in the cement.
From experimental data of examples, the hexavalent chromium reducing agent has better hexavalent chromium reducing effect, and the blank Cr with the content of 16.9ppm can be reduced under the condition of extremely low doping amount6+The concentration is reduced to below 4 ppm. Compared with the commercial ferrous salt reducing agent, the grinding aid has better grinding aid and chromium removal effects. The content of the chromium (VI) is less than 10ppm which meets the standard requirement of GB31893-2015 limit and determination method for water-soluble chromium (VI) in cement. In addition, the physical properties of the cement show that the special grinding aid for hexavalent chromium cement has a certain grinding aid enhancing effect, the 3d and 28d strength of the cement is increased by about 2MPa and 4MPa compared with the blank, the 45um screen residue and the 80um screen residue are reduced, and the dual effects of chromium removal and grinding aid effects are reflected.
It should be noted that the above-mentioned embodiments are only some of the preferred modes for implementing the invention, and not all of them. Obviously, all other embodiments obtained by persons of ordinary skill in the art based on the above-mentioned embodiments of the present invention without any creative effort shall fall within the protection scope of the present invention.
Claims (7)
1. The low-doped cement chromium-removing grinding aid is characterized by being prepared from the following raw materials in parts by weight: 20-40 parts of alcohol amine substances, 20-40 parts of alcohol substances, 25-40 parts of antimony trichloride and 5-15 parts of ethanol; the alcamines are one or two of triethanolamine or diethanol monoisopropanolamine; the alcohol substance is ethylene glycol.
2. The low-doped cement chromium-removing grinding aid as claimed in claim 1, wherein the triethanolamine is an industrial product with a content of 85%.
3. The low-doped cement chromium-removing grinding aid as claimed in claim 1, wherein the diethanol monoisopropanolamine is an industrial product with a content of 85%.
4. The low-doped cement chromium-removing grinding aid as claimed in claim 1, wherein the ethanol is industrial ethanol with a content of 95%.
5. The low-doped cement chromium-removing grinding aid as claimed in claim 1, wherein the amount of the grinding aid added is 0.02-0.04% of the mass of the cement according to the content of hexavalent chromium in the cement.
6. The low-doped cement chromium-removing grinding aid as claimed in claim 1, wherein the antimony trichloride is industrial with a content of 99.5%.
7. A method for preparing a low-doped cement chromium-removing grinding aid as claimed in claim 1, which comprises the following steps: (1) firstly, dissolving antimony trichloride with a formula amount in ethylene glycol to form a solution;
(2) adding an alcamines substance into the solution, and introducing cooling water into the reaction kettle; after the dropwise addition is finished and the temperature of the system is stable after the reaction is completed, heating to 60 ℃, and preserving the temperature for 30 minutes;
(3) and finally, adding ethanol to adjust the viscosity of the product, and uniformly stirring.
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111517687B (en) * | 2020-06-15 | 2022-03-11 | 安徽海螺新材料科技有限公司 | Chromium-reducing cement grinding aid and preparation method thereof |
| CN111635160B (en) * | 2020-06-15 | 2022-03-11 | 安徽海螺新材料科技有限公司 | Composite chromium-reducing cement grinding aid and preparation method thereof |
| CN111635150B (en) * | 2020-06-15 | 2022-03-11 | 安徽海螺新材料科技有限公司 | Chromium-reducing cement and preparation method thereof |
| CN111875278A (en) * | 2020-07-13 | 2020-11-03 | 南京神仂建材科技有限公司 | Efficient cement chromium-removing grinding aid |
| CN112500014A (en) * | 2020-11-20 | 2021-03-16 | 华润水泥技术研发有限公司 | Preparation method of hexavalent chromium reducing agent for high-temperature-resistant cement |
| CN112500013A (en) * | 2020-11-20 | 2021-03-16 | 华润水泥技术研发有限公司 | Preparation method of nano-loaded hexavalent chromium reducing agent for cement |
| CN112745052A (en) * | 2020-12-24 | 2021-05-04 | 铜川声威建材有限责任公司榆林分公司 | Improved grinding aid |
| CN115417616B (en) * | 2022-10-08 | 2023-09-22 | 临沂海螺新材料科技有限公司 | Grinding aid for vertical mill cement and preparation method thereof |
| CN115490455B (en) * | 2022-10-09 | 2023-08-18 | 临沂海螺新材料科技有限公司 | Low-doping-amount enhanced cement grinding aid and preparation method thereof |
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| JP2017210398A (en) * | 2016-05-27 | 2017-11-30 | デンカ株式会社 | Cement grinding aid and method for producing cement composition using the same |
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Address after: 241000 No. 1-301, Area G, Construction Headquarters, Jiangbei New Area, Wuhu City, 150 meters south of Tongjiang Avenue, Jiangbei New Area, Wanjiang New Industry Cluster (except the trusteeship area), Wuhu City Patentee after: Anhui Conch Material Technology Co.,Ltd. Patentee after: Linyi conch New Material Technology Co.,Ltd. Address before: 241000 room 208, building 1, No.9, Wanjiang Avenue, Jiangbei industrial concentration area, Jiujiang District, Wuhu City, Anhui Province Patentee before: Anhui Conch New Materials Technology Co.,Ltd. Patentee before: Linyi conch New Material Technology Co.,Ltd. |