CN104261716B - A kind of phosphogypsum base cement adjustable solidification agent and preparation method - Google Patents
A kind of phosphogypsum base cement adjustable solidification agent and preparation method Download PDFInfo
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- CN104261716B CN104261716B CN201410479353.4A CN201410479353A CN104261716B CN 104261716 B CN104261716 B CN 104261716B CN 201410479353 A CN201410479353 A CN 201410479353A CN 104261716 B CN104261716 B CN 104261716B
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- phosphogypsum
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Abstract
The invention discloses a kind of phosphogypsum base cement adjustable solidification agent and preparation method thereof.A kind of phosphogypsum base cement adjustable solidification agent, is made up of the material of following mass percent: phosphogypsum 92%-97%, properties-correcting agent 2.9%-7%, dispersion agent 0.1%-1%.Dispersion agent is evenly sprayed in the phosphogypsum and properties-correcting agent that mix by the preparation method of phosphogypsum base cement adjustable solidification agent of the present invention, and ageing is reacted, and dries, obtains phosphogypsum base cement adjustable solidification agent.Adjustable solidification agent of the present invention for raw material, not only solves the problem of environmental pollution of phosphogypsum with industrial residue-phosphogypsum, and prepares the cement adjustable solidification agent of excellent property, achieves and turns waste into wealth.Preparation method of the present invention is simple, and with low cost, process easy to use, the efficiency utilization tool for phosphogypsum is of great significance.
Description
Technical field
The present invention relates to material of construction production field, particularly a kind of phosphogypsum base cement adjustable solidification agent and preparation method thereof.
Background technology
Phosphogypsum is the waste residue of discharging when wet method manufactures phosphoric acid in phosphorous chemical industry, often produce 1 ton of phosphoric acid and discharge 5 tons of phosphogypsums, according to the data in 2011 " instruction that industrial information portion fully utilizes about industry by-product gypsum ", within 2009, Chinese phosphogypsum generation is about 5,000 ten thousand tons, and comprehensive utilization ratio only has 20%.The phosphogypsum amount that China discharges every year is about 7,000 ten thousand tons, and the phosphogypsum that accumulation is stored up, more than 2.5 hundred million tons, been has not only has been occupied a large amount of soil, also created the pollution of environment.Point out in " " 12 " energy-conserving and environment-protective industrial development planning ", strengthen the comprehensive utilization of large industrial solid castoffs such as phosphogypsum, encouragement industry by-product gypsum fully utilizes, industry Compact development, put forth effort to develop low cost, high-performance, environment-friendly type phosphogypsum purification technology, to the end of the year 2015, phosphogypsum comprehensive utilization ratio will strive bringing up to 40%, accelerate phosphogypsum recycling, become phosphorus chemical industry Sustainable development urgent problem.
Cement adjustable solidification agent is one of important composition material of cement, plays and regulates the effect of cement setting time, the conventional industry by-product gypsum etc. having gypsum, natural dihydrate gypsum and meet technical requirements.Phosphogypsum main chemical compositions and the plaster of paris are substantially identical, main with dihydrate gypsum, or semi-hydrated gypsum exists, but the reason due to industrial product process procedure causes in phosphogypsum containing a small amount of detrimental impurity such as phosphorus, fluorine, during untreated phosphogypsum making cement adjustable solidification agent, phosphorus wherein can and cement in the Ca of CaO reaction generation indissoluble
3(PO
4)
2be coated on C
3s, C
2s and gypsum surface, cause the solidifying effect of the tune of phosphogypsum unstable, limit the application of phosphogypsum.
Summary of the invention
The object of the present invention is to provide a kind of phosphogypsum base cement adjustable solidification agent, adjustable solidification agent of the present invention for raw material, not only solves the problem of environmental pollution of phosphogypsum with industrial residue-phosphogypsum, and prepares the cement adjustable solidification agent of excellent property, achieves and turns waste into wealth.
Present invention also offers a kind of preparation method of above-mentioned phosphogypsum base cement adjustable solidification agent, this preparation method is simple, with low cost, process easy to use, gained phosphogypsum base cement adjustable solidification agent not only has the effect of stable adjustment cement setting time, and have the effect of significantly gaining in strength, the efficiency utilization tool for phosphogypsum is of great significance.
A kind of phosphogypsum base cement adjustable solidification agent, is made up of the material of following mass percent: phosphogypsum 92%-97%, properties-correcting agent 2.9%-7%, dispersion agent 0.1%-1%; Described properties-correcting agent is made up of unslaked lime, calcined alunite and Starso; Described dispersion agent is made up of ethylene glycol, calcium lignin sulphonate and Tetramethylammonium iodide.
Described, in properties-correcting agent, the mass ratio of each material is unslaked lime: calcined alunite: Starso=1:0.5-1.5:0.5-1.2.
Preferably, in properties-correcting agent, the mass ratio of each material is unslaked lime: calcined alunite: Starso=1:1:1.Starso in properties-correcting agent can react with the fluorine in phosphogypsum the salt generating indissoluble, terra alba in unslaked lime and calcined alunite and phosphogypsum reacts, form the hydrated calcium aluminate sulfate class hydrated product that solubleness is lower, thus the impurity such as phosphorus, fluorine, organic matter on surface in fixing Phosphate Sorption gypsum, in elimination phosphogypsum, the impurity such as phosphorus, fluorine, organic matter is on the impact of general purpose portland cement time of coagulation.
Described, in dispersion agent, the mass ratio of each material is ethylene glycol: calcium lignin sulphonate: Tetramethylammonium iodide=1:0.5-2:0.2-0.8.
Preferably, in dispersion agent, the mass ratio of each material is ethylene glycol: calcium lignin sulphonate: Tetramethylammonium iodide=1:1:0.5.Material fluidity is subject to the impact of fine particle dispersion or coalescing state, determines primarily of particle and medium, particle and intergranular interaction.Using surfactivity class material as dispersion agent, when being adsorbed on powder granule surface, hydrophilic group aligns at powder surface, hydrophobic group is towards air, form monomolecular adsorption film at particle surface, the existence of this film, decrease direct contact surface between solid particulate and amass, as lubricant, reduce the friction between powder granule, make powder easily slide and improve liquidity.
A preparation method for phosphogypsum base cement adjustable solidification agent, comprises the following steps:
A. take phosphogypsum and properties-correcting agent, both mix, and obtain material 1;
B. take dispersion agent, and be added in the water of 40-80 times of dispersant weight and stir, obtain material 2;
C. be evenly sprayed in material 1 by material 2, ageing reaction 24h-48h, 30-100 DEG C of oven dry, obtains phosphogypsum base cement adjustable solidification agent.
The present invention's phosphogypsum used takes from chemical plant, Linyi, Shandong ardealite storage yard, canescence, and main component is terra alba (CaSO
4.2H
2o), specific surface area is 2750cm
2/ g, pH value is 2.5, is 20% containing free-water massfraction, its chemical group prejudice table 1.
The chemical constitution of table 1 phosphogypsum
| Composition | P 2O 5 | SiO 2 | Al 2O 3 | Fe 2O 3 | CaO | MgO | SO 3 | Loss on ignition |
| Massfraction/% | 1.13 | 3.52 | 0.67 | 0.38 | 32.57 | 0.59 | 46.89 | 13.89 |
Advantage of the present invention:
(1) adjustable solidification agent of the present invention is with industrial residue-phosphogypsum for raw material, and cost is low, not only solves the problem of environmental pollution of phosphogypsum, achieve the recycling of phosphogypsum, alleviate the processing pressure of industrial residue, and prepare the cement adjustable solidification agent of excellent property, achieve and turn waste into wealth.This cement adjustable solidification agent can not only replace natural dihydrate gypsum, effectively regulates time of coagulation, and has the effect of gaining in strength.
(2), in adjustable solidification agent of the present invention, to eliminate the adding of properties-correcting agent in phosphogypsum the impurity such as phosphorus, fluorine, organic matter to the impact of general purpose portland cement time of coagulation, make the performance of this adjustable solidification agent more stable.
(3) in adjustable solidification agent of the present invention, adding of dispersion agent increases intergranular oilness, reduces the friction between powder granule, powder is easily slided, efficiently solves the problem that phosphogypsum easily blocks blanking bin
(4) adjustable solidification agent preparation method of the present invention is simple, without the need to extruder grain, easy and simple to handle, is conducive to technical renovation and the transformation of Cement industry, has significant economic benefit and social benefit.
Embodiment
In order to understand the present invention further, below in conjunction with embodiment, the preferred embodiments of the invention are described, but should be appreciated that these describe just as further illustrating the features and advantages of the invention instead of the restriction to patent requirements of the present invention.
embodiment 1
92kg phosphogypsum is mixed with 2.6kg unslaked lime, 1.3kg calcined alunite, 3.1kg Starso, obtains material 1; 44g ethylene glycol, 22g calcium lignin sulphonate, 34g Tetramethylammonium iodide are added in 8kg water and stirs, obtain material 2; Material 2 is evenly sprayed on material 1, and ageing reaction 48h, 30 DEG C of oven dry, obtain phosphogypsum base cement adjustable solidification agent.
embodiment 2
94.5kg phosphogypsum is mixed with 1.6kg unslaked lime, 1.7kg calcined alunite, 1.7kg Starso, obtains material 1; 200g ethylene glycol, 200g calcium lignin sulphonate, 100g Tetramethylammonium iodide are added in 30kg water and stirs, obtain material 2; Material 2 is evenly sprayed on material 1, and ageing reaction 36h, 50 DEG C of oven dry, obtain phosphogypsum base cement adjustable solidification agent.
embodiment 3
97kg phosphogypsum is mixed with 1kg unslaked lime, 1.4kg calcined alunite, 0.5kg Starso, obtains material 1; 310g ethylene glycol, 630g calcium lignin sulphonate, 60g Tetramethylammonium iodide are added in 40kg water and stirs, obtain material 2; Material 2 is evenly sprayed on material 1, and ageing reaction 24h, 80 DEG C of oven dry, obtain phosphogypsum base cement adjustable solidification agent.
embodiment 4
95.5kg phosphogypsum, 1.4kg unslaked lime, 1.1kg calcined alunite, 1.2kg Starso, 276g ethylene glycol, 358g calcium lignin sulphonate and 166g Tetramethylammonium iodide are mixed; Evenly be sprayed on by 50kg water in the above-mentioned material mixed, ageing is reacted, and 100 DEG C of oven dry, obtain phosphogypsum base cement adjustable solidification agent.
effect example
The phosphogypsum base cement adjustable solidification agent selecting embodiment 1-4 obtained is as experimental example 1-4, with plaster of paris adjustable solidification agent for comparative example, experiment is divided into three groups, prepares burden respectively according to 97% grog+3% adjustable solidification agent, 47% grog+3% adjustable solidification agent+50% slag and 67% grog+3% adjustable solidification agent+30% flyash.Each batching in the little mill of φ 500 × 500mm grinding to specific surface area 360m
2/ kg, the grinding time of same batching is identical, according to the method test strength of cement mortar recorded in GB/T17671-1999 " Test method for strength of hydraulic cement mortar (ISO method) "; DBT-127 type Bo Shi ratio surface area instrument of breathing freely is adopted to detect Blain specific surface; Water consumption and the time of coagulation of cement normal consistency is detected according to the method recorded in GB1346-2001 " cement normal consistency water consumption, time of coagulation, the stability method of inspection ".Result is as shown in table 2.
Table 2 experimental result
As can be seen from Table 2, in three kinds of batching situations, cement adjustable solidification agent prepared by the present invention not only effectively can regulate time of coagulation, and has the effect of gaining in strength.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (4)
1. a phosphogypsum base cement adjustable solidification agent, is characterized in that, is made up of the material of following mass percent: phosphogypsum 92%-97%, properties-correcting agent 2.9%-7%, dispersion agent 0.1%-1%; Described properties-correcting agent is made up of unslaked lime, calcined alunite and Starso; Described dispersion agent is made up of ethylene glycol, calcium lignin sulphonate and Tetramethylammonium iodide;
The mass ratio of each material of described properties-correcting agent is unslaked lime: calcined alunite: Starso=1:0.5-1.5:0.5-1.2;
The mass ratio of each material of described dispersion agent is ethylene glycol: calcium lignin sulphonate: Tetramethylammonium iodide=1:0.5-2:0.2-0.8.
2. cement adjustable solidification agent according to claim 1, is characterized in that, in described properties-correcting agent, the mass ratio of each material is unslaked lime: calcined alunite: Starso=1:1:1.
3. cement adjustable solidification agent according to claim 1, is characterized in that, in described dispersion agent, the mass ratio of each material is ethylene glycol: calcium lignin sulphonate: Tetramethylammonium iodide=1:1:0.5.
4. a preparation method for phosphogypsum base cement adjustable solidification agent described in claim 1, comprises the following steps:
A. take phosphogypsum and properties-correcting agent, both mix, and obtain material 1;
B. take dispersion agent, and be added in the water of 40-80 times of dispersant weight and stir, obtain material 2;
C. be evenly sprayed in material 1 by material 2, ageing reaction 24h-48h, bake out temperature, obtains phosphogypsum base cement adjustable solidification agent.
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104628276A (en) * | 2015-02-02 | 2015-05-20 | 河南聚能新型建材有限公司 | Phosphogypsum treatment method |
| CN105331009B (en) * | 2015-11-29 | 2017-09-15 | 贵州开磷磷石膏综合利用有限公司 | A kind of powdery ardealite filler and its preparation |
| CN105967617A (en) * | 2016-03-29 | 2016-09-28 | 蚌埠华东石膏有限公司 | Insulation building gypsum powder with sound-absorption and noise-reduction function and preparation method thereof |
| CN105819795B (en) * | 2016-05-31 | 2017-09-19 | 山东宏德新材料有限公司 | A kind of insulation material of high-strength light and preparation method thereof |
| CN109455970A (en) * | 2018-12-19 | 2019-03-12 | 日照弗尔曼新材料科技有限公司 | A kind of concrete air-entrainer and preparation method thereof |
| CN116514450B (en) * | 2023-05-16 | 2024-02-06 | 山东诚港新材料科技有限公司 | Gypsum modifier for cement production |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1389421A (en) * | 2002-07-16 | 2003-01-08 | 武汉理工大学 | Denatured ardealite brick and its application as cement retardant |
| CN102285773A (en) * | 2010-06-18 | 2011-12-21 | 安徽金刀水泥有限公司 | Phosphogypsum-cement retarder and preparation method thereof |
| CN103482896A (en) * | 2013-09-09 | 2014-01-01 | 四川大学 | Phosphogypsum ball and preparation method and application thereof |
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2014
- 2014-09-19 CN CN201410479353.4A patent/CN104261716B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1389421A (en) * | 2002-07-16 | 2003-01-08 | 武汉理工大学 | Denatured ardealite brick and its application as cement retardant |
| CN102285773A (en) * | 2010-06-18 | 2011-12-21 | 安徽金刀水泥有限公司 | Phosphogypsum-cement retarder and preparation method thereof |
| CN103482896A (en) * | 2013-09-09 | 2014-01-01 | 四川大学 | Phosphogypsum ball and preparation method and application thereof |
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Address after: 276034 north of the intersection of Wenquan road and Fenghuang street, Fenghuangling sub district office, Hedong District, Linyi City, Shandong Province Patentee after: LINYI HONGYI TECHNOLOGY DEVELOPMENT Co.,Ltd. Address before: 276034 No. 369 Renmin Street, Hedong District, Shandong, Linyi Patentee before: SHANDONG HONGYI TECHNOLOGY Co.,Ltd. |
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Address after: 276000 north of the intersection of Wenquan road and Fenghuang street, Fenghuangling sub district office, Hedong, Linyi City, Shandong Province Patentee after: Linyi conch New Material Technology Co.,Ltd. Address before: 276034 north of the intersection of Wenquan road and Fenghuang street, Fenghuangling sub district office, Hedong District, Linyi City, Shandong Province Patentee before: LINYI HONGYI TECHNOLOGY DEVELOPMENT Co.,Ltd. |
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