CN1457937A - Phosphorous slag activation modifier - Google Patents
Phosphorous slag activation modifier Download PDFInfo
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- CN1457937A CN1457937A CN02114132A CN02114132A CN1457937A CN 1457937 A CN1457937 A CN 1457937A CN 02114132 A CN02114132 A CN 02114132A CN 02114132 A CN02114132 A CN 02114132A CN 1457937 A CN1457937 A CN 1457937A
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- slag
- chloride
- phosphorous slag
- phosphorous
- powder
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
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- Soil Conditioners And Soil-Stabilizing Materials (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The phosphorous slag activating modifier is precipitant comprising one or several kinds of oxide, hydroxide, chloride and nitrate of Ca, Mg and Ba, and prepared through crushing. It is added into phosphorous slag to convert the slowly coagulating components in phosphorous slag into insoluble precipitate as stuffing component. The present invention makes it possible to utilize phosphorous slag to produce high-quality and low-cost cement and other building material.
Description
Technical Field
The invention relates to a composition in a new technology for utilizing industrial waste residues, in particular to a composition which can effectively eliminate delayed coagulation and slow strength of phosphorus residues and has the functions of catalytic activation and grinding aid on the phosphorus residues in a new technology for utilizing phosphorus slag, namely phosphorus slag in an industrial electric furnace.
Background
The resource of phosphorite in China is rich, the phosphorite becomes the biggest industrial production base of phosphorization in Asia, such as Guizhou, Yunnan, Hubei, Sichuan and the like, the scale and the development potential of the phosphorization are huge, and the annual emission of phosphorus slag reaches million tons. Although the phosphorus slag contains a large amount of mineral substances such as calcium silicate, calcium aluminate, calcium aluminoferrite and the like, and is a very valuable industrial waste slag resource, and a large amount of application research is carried out by technical personnel at home and abroad, the slow setting and slow strengthening effects are very obvious, so that the phosphorus slag is still very limited in effective utilization amount so far, only a small amount of phosphorus slag is used as raw material ingredients of a cement plant, a small amount of phosphorus slag is used as a cement mixture, part of phosphorus slag is used as a paving filling base, a large amount of phosphorus slag still needs to be continuously searched for a field to be buried, the phosphorus slag becomes industrial garbage, occupies precious land, pollutes the environment and wastes valuable resources. From the data retrieval and the practical application conditions at home and abroad, no other effective technology for solving the slow coagulation and slow strengthening effects of the phosphorous slag exists at present. Nowadays, with the development of economy and the progress of society, environmental protection, energy conservation and consumption reduction become more concerned focuses of people. Therefore, how to effectively utilize the valuable phosphorus slag resources on a large scale, eliminate environmental pollution and change waste into valuables becomes a big problem influencing the sustainable development of the phosphating industry and the building material industry.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the retarding and strengthening effects of the phosphorus slag are eliminated, the gelled minerals such as calcium silicate, calcium aluminate and calcium aluminoferrite in the phosphorus slag are effectively utilized, the phosphorus slag is converted into a high-quality gelled material, the phosphorus slag is effectively utilized on a large scale, high-quality cement and building material products are produced at low cost, and the purposes of changing waste into valuables, protecting the environment, saving energy, reducing consumption and improving the economic benefits of enterprises are achieved.
The technical scheme adopted by the invention is as follows: the phosphorous slag activation modifier is prepared by taking a precipitator as a main component and crushing the precipitator into powder or granules, wherein the precipitator is added into phosphorous slag and uniformly mixed to convert a delayed coagulation component in the phosphorous slag into an insoluble precipitation to become a filler component.
The precipitator can be one or more of the following components: calcium oxide, calcium hydroxide, calcium chloride, calcium nitrate, magnesium oxide, magnesium hydroxide, magnesium chloride, magnesium nitrate, barium oxide, barium hydroxide, barium chloride, and barium nitrate. Such as quicklime, slaked lime, lime mud, carbide mud, etc.
The phosphorus slag activation modifier takes a precipitator as a main component, and can be added with filler, or added with filler and a catalyst activator, or added with filler, catalyst activator and grinding aid according to the functional requirements. Such as:
a-type phosphorous slag activation modifier: the composite material consists of a precipitator or a precipitator added with a filler, and the components are mixed according to the weight percentage: 15-100% of precipitant and 0-85% of filler.
B-type phosphorus slag activation modifier: the catalyst consists of a precipitator, a catalytic activator and a filler, wherein the components are prepared from the following components in percentage by weight: 20-80% of precipitator, 10-60% of catalytic activator and 0-80% of filler.
C-type phosphorus slag activation modifier: the composite material is composed of a precipitator, a catalyst activator, a grinding aid and a filler, wherein the components are mixed according to the weight percentage: 20-80% of precipitating agent, 10-60% of catalytic activator, 0.3-10% of grinding aid and 0-70% of filler.
The catalyst activator in the components can be one or more of red vitriol, alum, dried alum, water glass, chloride salt, thiocyanate, fluosilicate, nitrite, nitrate and sulfate, such as one or more of sodium sulfate, potassium sulfate, ferrous sulfate, calcium chloride, aluminum chloride, sodium chloride, ammonium chloride, stannous chloride, potassium chloride, alum and the like.
The grinding aid in the components can be OH-containing-、COOH-、-SO3-And surfactants of group-NH 2, such as ammonium salt of polycarboxylic acid, ammonium salt of acrylic acid copolymer, carboxylated acrylic acid copolymer, titanate, industrial naphthalene and methyl naphthalene sulfonate and formaldehyde polymer thereof, polycyclic aryl sulfonate and formaldehyde polymer thereof, calcium lignosulphonate, cellulose, melamine, monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine, diethylene glycol, octanol, etc.
The filler or carrier in the above components can be one or more selected from fly ash, bentonite, attapulgite powder, silica powder, slag powder, right ash slag powder, stone powder and coal slag.
The preparation process comprises the following steps: according to the actual application requirement, the components are selected, matched, crushed and uniformly mixed or crushed and ground and uniformly mixed, and then the grinding head is added.
The technical principle of the invention is as follows:
1. preferably considering the applicable resource conditions of the phosphorous slag building material, namely retarding coagulation of active components, retarding and strengthening components, filling components, normal-temperature activation environment, catalytic activation inducing factors and composite conditions;
2. eliminating phosphorus slag by precipitant in this kind of componentsThe slow setting and slow strengthening functions are realized by mixing the composition with phosphorus slag or phosphorus slag clinker and grinding, wherein the precipitator components are uniformly distributed in ground fine particles (such as modified phosphorus slag powder or cement), and when the modified phosphorus slag powder or the cement meets water, the precipitator rapidly and the slow setting components in the phosphorus slag react with each other to generate insoluble precipitate, and the insoluble precipitate is converted into filling components. (typical reactions are as follows ) So as to eliminate the adsorption of retarding component to cement and other minerals and shield the retarding action in the induction period of cement hydration, and the residual precipitant component can activate the phosphorus slag.
3. The B-type phosphorous slag activation modifier is assisted by a reinforced catalytic activation technology to promote the hydration activity reaction of silicon, aluminum, iron, calcium and the like, and utilizes the compatible catalytic activator component to activate or accelerate the potential active component in the phosphorous slag particles so as to ensure that the potential active component can exert the required gel strength within the required time.
4. The C-type phosphorous slag activation modifier neutralizes the static electricity of the grinding medium by utilizing the high-molecular surfactant group, eliminates the microcrack energy of the grinding material and the dispersion and adhesion resistance of the grinding material so as to improve the grinding efficiency and effectively reduce the power consumption.
The invention has the advantages and obvious effects that:
1. the retarding component is quickly converted into the filler without adsorption, shielding and retarding effects by utilizing chemical reaction, the retarding and strengthening effects of the phosphorous slag are effectively eliminated, and the method has the advantages of low cost, practicability and reliability;
2. the cementing component in the phosphorous slag can be effectively exerted, the phosphorous slag can be used in cement in a large mixing amount (the mixing amount can reach 80 percent), high-quality cement can be produced at low cost, the phosphorous slag can be ground into high-quality slag powder to be supplied to a concrete mixing plant and a construction site, the phosphorous slag can also be used as clinker-free cement, and reliable technical guarantee is provided for large-scale utilization of the phosphorous slag;
3. the grinding aid has good grinding-aiding effect, and can reduce the power consumption of grinding by 15-30%;
4. the phosphorus slag cement produced by the method has the characteristics of normal setting time, high early strength, stable increase of later strength, low hydration heat, good construction property, durability and corrosion resistance superior to those of common cement with the same grade, and the stability of the cement is obviously improved. The application performance of the phosphorous slag powder produced by the technology is superior to that of common slag powder, and the cement with less clinker or no clinker produced by the phosphorous slag has good physical and mechanical properties;
5. has good applicability to various concrete additives.
The test examples and the application effects of the invention are compared as follows:
1. the test manufacturer: a certain milling station in the Yichang area of Hubei: grinding the slag powder with a mill of phi 3.0 x 11.0 to obtain 32.5Mpa and 42.5Mpa cement, wherein the slag powder comprises 50% of phosphorus slag, 40% of coal slag, 40% of dry powder and 10% of gypsum and limestone. Before the technology of the invention is adopted, the cement mixture ratio of 32.5Mpa is 60% of clinker powder and 40% of slag powder, the initial setting time is about 8 hours, the delayed setting time is about 11 hours, the 3d strength is 10-12Mpa, and the 28d strength is as follows: 28-36Mpa, the user reaction coagulation time is too long, and the early strength is too low. After the technology of the invention is adopted, the proportion of 32.5Mpa cement is 46 percent of clinker powder and 54 percent of slag powder, the initial setting time is about 3 hours, the delayed setting time is about 4 hours, the 3d strength is 16-18Mpa, and the 28d strength is more than or equal to 34 Mpa.
2. The test manufacturer: a cement plant in Yichang areas of Hubei: before the technology of the invention is not adopted, the cement of 32.5Mpa is produced by a cement ring flow mill of phi 2.2 x 65m, the clinker dosage is 83 percent, the phosphorus slag doping amount is 14 percent, the gypsum is 3 percent, the mill output is 13T/h, the fineness is 4-7 percent, the initial setting time is 6: 15, final setting time 8: 30, 3d strength of 12-15Mpa and 28d strength of 20-38Mpa, after the technology of the invention is adopted, the phosphorus slag mixing amount is 35 percent, the yieldof a mill is 17T/h, the fineness is less than 4 percent, the initial setting time is 2: 45, final setting time 3: 50, 3d strength of 17-20Mpa, 28d strength of more than or equal to 35 Mpa.
The specific implementation mode is as follows:
example 1: the phosphorous slag activating modifier is prepared by selecting the precipitator of quicklime and carbide slag as the components of the invention, crushing the components by a hammer mill and mixing the components uniformly.
In the embodiment 2, 30% of lime slag and 20% of carbide slag are selected as a precipitator, 50% of coal slag is selected as a filler, the materials are ground and uniformly mixed by a ball mill, and the mixture is added into a grinding head, so that the A-type phosphorus slag activation modifier is prepared.
Example 3, 30% of slaked lime is selected as a precipitator, 20% of sodium sulfate and 10% of calcium chloride are selected as catalytic activators, 40% of fly ash is selected as filling powder, and the mixture is crushed and uniformly mixed to prepare the B-type phosphorous slag activation modifier.
Example 4, 40% of quicklime is used as a precipitator, 30% of alum is used as a catalytic activator, 10% of calcium lignosulfonate and cellulose are used as grinding aids, and 20% of bentonite is used as a filler, and the components are ground in a Raymond mill and uniformly mixed to prepare the C phosphorous slag activation modifier. When in use, the slow-setting and slow-strength components in the phosphorus slag are converted into insoluble precipitates by adding the phosphorus slag powder and mixing the phosphorus slag powder uniformly, and the insoluble precipitates become fillers to produce high-quality cement or building material products.
Claims (8)
1. A phosphorous slag activating modifier is characterized in that a precipitator is used as a main component, the precipitator is crushed into powder or particles to prepare the phosphorous slag activating modifier, the precipitator is added into phosphorous slag and mixed evenly, and delayed coagulation components in the phosphorous slag are converted into insoluble precipitates to become filler components.
2. The phosphorous slag activation modifier according to claim 1, wherein the precipitant is selected from one or more of the following components: calcium oxide, calcium hydroxide, calcium chloride, calcium nitrate, magnesium oxide, magnesium hydroxide, magnesium chloride, magnesium nitrate, barium oxide, barium hydroxide, barium chloride, and barium nitrate.
3. The phosphorous slag activation modifier according to claim 1, wherein a precipitant is used as a main component, and a filler is further added.
4. The phosphorous slag activation modifier according to claim 1, wherein a precipitant is used as a main component, and a filler and a catalyst activator are further added.
5. The phosphorus slag activation modifier as claimed in claim 1, wherein the main component is precipitator, and filler, catalyst activator and grinding aid can be added.
6. The phosphorous slag activation modifier according to claim 3, 4 or 5, wherein the filler is selected from one or more of fly ash, bentonite, attapulgite powder, silica powder, slag powder, lime slag powder, stone powder and coal slag.
7. The phosphorous slag activation modifier according to claim 4 or 5, wherein the catalyst activator is selected from one or more of arsenicum sablimatum, alum, dried alum, sodium silicate, chloride, thiocyanate, fluosilicate, nitrite, nitrate and sulfate, and one or more of sodium sulfate, potassium sulfate, ferrous sulfate, calcium chloride, aluminum chloride, sodium chloride, ammonium chloride, stannous chloride, potassium chloride and alum.
8. The phosphorous slag activation modifier as claimed in claim 5, wherein the grinding aid is selected from the group consisting of OH-containing grinding aids-、COOH-Surfactant of group, -SO3-, -NH2, etc., and one or more of polycarboxylic acid ammonium salt, acrylic acid copolymer ammonium salt, carboxylated acrylic acid copolymer, titanate, industrial naphthalene and methyl naphthalene sulfonate and formaldehyde polymer thereof, polycyclic aryl sulfonate and formaldehyde polymer thereof, calcium lignosulfonate, cellulose, melamine, monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine, diethylene glycol and octanol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021141320A CN1209202C (en) | 2002-05-16 | 2002-05-16 | Phosphorous slag activation modifier |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021141320A CN1209202C (en) | 2002-05-16 | 2002-05-16 | Phosphorous slag activation modifier |
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| Publication Number | Publication Date |
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| CN1457937A true CN1457937A (en) | 2003-11-26 |
| CN1209202C CN1209202C (en) | 2005-07-06 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB021141320A Expired - Fee Related CN1209202C (en) | 2002-05-16 | 2002-05-16 | Phosphorous slag activation modifier |
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102653460A (en) * | 2004-06-21 | 2012-09-05 | Sika技术股份公司 | Cement grinding aid |
| CN102964085A (en) * | 2012-11-08 | 2013-03-13 | 贵州环海澳蕾建材科技有限公司 | Special cement grinding aid for phosphorous slag |
| CN102965079A (en) * | 2012-12-01 | 2013-03-13 | 中化化肥有限公司重庆磷复肥工程技术研究中心 | Phosphate rock grinding aid and preparation method thereof |
| CN104496393A (en) * | 2014-11-28 | 2015-04-08 | 无锡晨驰环保科技股份有限公司 | Multipurpose concrete cementing agent and preparation method thereof |
| CN104724955A (en) * | 2014-11-25 | 2015-06-24 | 贵州大远混凝土有限公司 | Method for preparing high-activity composite phosphorus slag powder |
| CN105130216A (en) * | 2015-08-19 | 2015-12-09 | 安徽建筑大学 | Preparation method for phosphorus-slag micropowder applied to cement-based material |
| CN105293968A (en) * | 2015-11-30 | 2016-02-03 | 马鞍山泓宇材料科技有限公司 | Phosphorus slag compound modifying agent |
| CN105693119A (en) * | 2016-02-02 | 2016-06-22 | 武汉理工大学 | Modified phosphorus slag powder, and preparation method and application thereof |
| CN105820798A (en) * | 2016-04-18 | 2016-08-03 | 湖北富邦科技股份有限公司 | Phosphorite grinding aid, and preparation and application thereof |
| CN105948555A (en) * | 2016-06-27 | 2016-09-21 | 湖北鑫统领万象科技有限公司 | Special grinding aid for phosphorus slag cement |
| CN107188441A (en) * | 2017-06-23 | 2017-09-22 | 安徽科博建材科技有限公司 | A kind of composite gypsum |
| CN110171939A (en) * | 2019-04-11 | 2019-08-27 | 武汉理工大学 | A kind of sial phase chaotropic agent and its preparation method and application |
| CN111747672A (en) * | 2020-05-13 | 2020-10-09 | 武汉三源特种建材有限责任公司 | Superfine modified phosphorus slag powder and superfine composite admixture for concrete |
| CN112341026A (en) * | 2020-11-05 | 2021-02-09 | 安徽成弘建新材料有限公司 | Copper tailings modifier and preparation method and application thereof |
| CN115073025A (en) * | 2022-07-06 | 2022-09-20 | 中国水利水电第七工程局有限公司 | Low-slow-setting and high-initial-stage active phosphorus slag powder and preparation method thereof |
-
2002
- 2002-05-16 CN CNB021141320A patent/CN1209202C/en not_active Expired - Fee Related
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102653460A (en) * | 2004-06-21 | 2012-09-05 | Sika技术股份公司 | Cement grinding aid |
| CN102653460B (en) * | 2004-06-21 | 2016-04-13 | Sika技术股份公司 | The purposes of a kind of aqueous composition as cement agent and the method for manufacture cement |
| CN102964085A (en) * | 2012-11-08 | 2013-03-13 | 贵州环海澳蕾建材科技有限公司 | Special cement grinding aid for phosphorous slag |
| CN102964085B (en) * | 2012-11-08 | 2014-10-29 | 贵州环海澳蕾建材科技有限公司 | Special cement grinding aid for phosphorous slag |
| CN102965079A (en) * | 2012-12-01 | 2013-03-13 | 中化化肥有限公司重庆磷复肥工程技术研究中心 | Phosphate rock grinding aid and preparation method thereof |
| CN102965079B (en) * | 2012-12-01 | 2014-08-20 | 中化化肥有限公司重庆磷复肥工程技术研究中心 | Phosphate rock grinding aid and preparation method thereof |
| CN104724955A (en) * | 2014-11-25 | 2015-06-24 | 贵州大远混凝土有限公司 | Method for preparing high-activity composite phosphorus slag powder |
| CN104496393A (en) * | 2014-11-28 | 2015-04-08 | 无锡晨驰环保科技股份有限公司 | Multipurpose concrete cementing agent and preparation method thereof |
| CN105130216A (en) * | 2015-08-19 | 2015-12-09 | 安徽建筑大学 | Preparation method for phosphorus-slag micropowder applied to cement-based material |
| CN105293968A (en) * | 2015-11-30 | 2016-02-03 | 马鞍山泓宇材料科技有限公司 | Phosphorus slag compound modifying agent |
| CN105693119A (en) * | 2016-02-02 | 2016-06-22 | 武汉理工大学 | Modified phosphorus slag powder, and preparation method and application thereof |
| CN105693119B (en) * | 2016-02-02 | 2017-11-21 | 武汉理工大学 | A kind of modified phosphorous slag powder and its preparation method and application |
| CN105820798A (en) * | 2016-04-18 | 2016-08-03 | 湖北富邦科技股份有限公司 | Phosphorite grinding aid, and preparation and application thereof |
| CN105948555A (en) * | 2016-06-27 | 2016-09-21 | 湖北鑫统领万象科技有限公司 | Special grinding aid for phosphorus slag cement |
| CN107188441A (en) * | 2017-06-23 | 2017-09-22 | 安徽科博建材科技有限公司 | A kind of composite gypsum |
| CN110171939A (en) * | 2019-04-11 | 2019-08-27 | 武汉理工大学 | A kind of sial phase chaotropic agent and its preparation method and application |
| CN110171939B (en) * | 2019-04-11 | 2021-09-21 | 武汉理工大学 | Silicon-aluminum phase promoter and preparation method and application thereof |
| CN111747672A (en) * | 2020-05-13 | 2020-10-09 | 武汉三源特种建材有限责任公司 | Superfine modified phosphorus slag powder and superfine composite admixture for concrete |
| CN111747672B (en) * | 2020-05-13 | 2022-06-21 | 武汉三源特种建材有限责任公司 | Superfine modified phosphorus slag powder and superfine composite admixture for concrete |
| CN112341026A (en) * | 2020-11-05 | 2021-02-09 | 安徽成弘建新材料有限公司 | Copper tailings modifier and preparation method and application thereof |
| CN115073025A (en) * | 2022-07-06 | 2022-09-20 | 中国水利水电第七工程局有限公司 | Low-slow-setting and high-initial-stage active phosphorus slag powder and preparation method thereof |
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| Publication number | Publication date |
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| CN1209202C (en) | 2005-07-06 |
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