CN1085879A - Producing cement from phosphor production is with strengthening gypsum sphere - Google Patents
Producing cement from phosphor production is with strengthening gypsum sphere Download PDFInfo
- Publication number
- CN1085879A CN1085879A CN 92112246 CN92112246A CN1085879A CN 1085879 A CN1085879 A CN 1085879A CN 92112246 CN92112246 CN 92112246 CN 92112246 A CN92112246 A CN 92112246A CN 1085879 A CN1085879 A CN 1085879A
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- CN
- China
- Prior art keywords
- cement
- phosphogypsum
- gypsum
- sphere
- manufacture
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Classifications
-
- 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
- C04B11/00—Calcium sulfate cements
- C04B11/26—Calcium sulfate cements strating from chemical gypsum; starting from phosphogypsum or from waste, e.g. purification products of smoke
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention provides a kind of is the enhancing gypsum sphere that main raw material is produced with the depleted phosphogypsum, is used as cement setting retarder to replace the plaster of paris in the manufacture of cement.Strengthen gypsum sphere by phosphogypsum slag and lime CaO, Ca (OH)
2Preparation.Drying moulding and making.The present invention is turned waste into wealth, be used for manufacture of cement, the quality and the ultimate compression strength of cement have been improved, simplified cement manufacture plant, the material cost and the production cost of manufacture of cement have been reduced, administered pollution and the harm of phosphogypsum slag effectively, had good benefits in environment, social benefit and economic benefit environment.
Description
The invention belongs to field of inorganic chemical engineering, relate to the phosphogypsum slag and produce the enhancing gypsum sphere, replace the plaster of paris in the manufacture of cement to be used as cement setting retarder.
The phosphogypsum slag is the by product that the chemical plant produces phosphamidon.Both at home and abroad at present methods that adopt the stockyard to stack more.According to statistics, the domestic phosphogypsum slag of storing up has reached 2,000 ten thousand tons, and the trend that rises is year by year arranged, and has occupied a large amount of useful soils.The stripping of the solubility Vanadium Pentoxide in FLAKES that contains in the phosphogypsum, fluorine, sulphur trioxide partly permeates the ground, and has influenced soil and underground water, and the slag ash flies upward after the phosphogypsum slag drying, and environment has been caused serious pollution and harm.
The plaster of paris is a kind of important raw and processed materials in the manufacture of cement, produces the cement mill of 1,000,000 tons of cement per year, needs to reach more than 50,000 ton as the plaster of paris of retardant.The phosphogypsum slag contains SO
3Amount is 42～43%, and the SO of the plaster of paris
3Content only 24～30% substitutes the plaster of paris with the phosphogypsum slag and is used for manufacture of cement, carries out utilization of waste material, not only helps reducing the manufacture of cement cost, and for the very important meaning of having curbed environmental pollution.But because phosphogypsum contains solubility P
2O
5, it to the influence of cement is: prolong cement setting time, concrete reinforcing bar is had corrosive nature.If with the solubility P in the phosphogypsum
2O
5Leach, can cause secondary pollution.Powdering after the phosphogypsum slag drying is also inapplicable to the tooling in existing cement mill in addition.
The object of the present invention is to provide a kind of with the phosphogypsum for the raw material substitution plaster of paris as cement setting retarder, that be applicable to existing cement industry equipment, and can improve the enhancing gypsum sphere of cement quality, refinforced cement intensity.
Technical scheme of the present invention is: with the phosphogypsum slag is main raw material, adds lime C
aO, C
a(OH)
2, at C
a(OH)
2Effect under, the solubility P in the phosphogypsum slag
2O
5Change insoluble calcium phosphate into, chemical reaction is as follows:
Insoluble calcium phosphate is again the binding agent that strengthens gypsum sphere.The incorporation of lime is that phosphogypsum slag ratio lime is that 100: 0.5～10(is heavy), optimal mixing amount is that phosphogypsum slag ratio lime is that 100: 0.5～2(is heavy).Draw the enhancing gypsum sphere that proportioning makes and still contain a spot of solubility P
2O
5, when making cement, this P
2O
5Can clear up free C
aO is useful to cement quality.The incorporation of lime is also looked the technology difference of manufacture of cement and is changed, and is used for rotary kiln cement production, because of free C in the cement clinker
aO content is low, and the incorporation that strengthens lime in the gypsum sphere can be phosphogypsum 1.0～2%(and weighs), be used for Vertical Kiln for Cement Production, because of free C in the cement clinker
aO content is low, and the incorporation that strengthens lime in the gypsum sphere can be 0.5～1.0%(weight of phosphogypsum).Used lime can be unslaked lime, slaked lime, and reasonable is slaked lime.
The preparation method who strengthens gypsum sphere is: phosphogypsum slag and lime are prepared burden by said ratio, add stirrer together, stir, make titanium pigment and C in the phosphogypsum
a(OH)
2Fully reaction and generate insoluble calcium phosphate, phosphogypsum after treatment enters dryer, in oven dry below 150 ℃, drying by the fire to water content is that 3～15%(is heavy).Baking back material enters shaper extruding balling-up.
Best bake out temperature is below 120 ℃, and the best water content of baking back material is 4～6%.
Bake out temperature is too high, gypsum dehydration, and dihydrate gypsum becomes semi-hydrated gypsum, can produce adverse influence to cement setting time.Baking back material water content is too high, low excessively, all can influence the balling ratio that strengthens gypsum sphere, and the intensity of ball.
The present invention compared with prior art has following advantage:
1. the enhancing gypsum sphere of the present invention preparation, SO
3Content is 42.5～43%, (the enhancing gypsum sphere of producing with the phosphogypsum in chemical plant, Xiangfan City is an example), the green stone cream SO in the plaster of paris such as yingcheng gypsum ore deposit
3Content is 24～30%, as seen, strengthens gypsum sphere SO
3Content is stable than the plaster of paris, strengthens the quality that gypsum sphere helps improving cement.
2. enhancing gypsum sphere of the present invention is stronger than the activation capacity of the plaster of paris, and being used for manufacture of cement has significant enhancement.
Test examples:
| Species of gypsum | Volume (%) | 28 days ultimate compression strength |
| The plaster of paris | 3.75% | 52.8MPa |
| Strengthen gypsum sphere | 3.75% | 57.0MPa |
3. the plaster of paris is irregular bulk, when the cement mill makes loading and unloading very inconvenient, the medium and small cement mill frock of all choosing is unloaded, large-scale cement factory then is equipped with special-purpose (fire) car machinery that unloads.For the gypsum of bulk being changed into the granularity that can prepare burden, also need a cover crushing system, crushing system mostly is secondary breaker and forms, use enhancing gypsum sphere of the present invention, can directly be used for preparing burden, complicated loading and unloading system, crushing system can save, and have reduced facility investment, reduce energy consumption, alleviated working strength of workers.
4. after enhancing gypsum sphere of the present invention is used for manufacture of cement, gypsum constitutes 1.75 yuan of/ton cement in the prediction cement total cost, the plaster of paris then is 3.3 yuan of/ton cement (in Xiangfan City's prices), cement per ton can reduce by 1.55 yuan of material cost, in 1,000,000 tons of cement, but 1,550,000 yuan of only this item incomes.
5. the present invention effectively utilizes phosphogypsum slag, turns waste into wealth, and has administered the pollution and the harm of phosphogypsum slag to environment effectively, has good benefits in environment, social benefit and economic benefit.
Embodiment 1: with the phosphogypsum slag with slaked lime by 100: 0.8 proportion ingredient and add stirrer and stir, churning time 8 minutes makes titanium pigment and C in the phosphogypsum slag
a(OH)
2Fully reaction, phosphogypsum slag after treatment enters dryer, dries by the fire to the moisture deal 5.0% of material at 120 ℃, and baking back material enters shaper extruding balling-up, must strengthen gypsum sphere A, balling ratio 90%, the intensity 10Kg of ball.
Embodiment 2: with the phosphogypsum slag with slaked lime by 100: 1.4(is heavy) proportion ingredient and add stirrer, stirred 10 minutes, to even, make titanium pigment and C in the phosphogypsum slag
a(OH)
2Fully reaction, phosphogypsum slag after treatment enters dryer, dries by the fire to water content 5.0% at 120 ℃, and baking back material enters shaper extruding balling-up, balling ratio 90%, the intensity 10Kg of ball must strengthen gypsum sphere B.
Embodiment 3: with the phosphogypsum slag with slaked lime by 100: 2(is heavy) proportion ingredient and add stirrer and stir, churning time 6 minutes makes titanium pigment and C in the phosphogypsum
a(OH)
2Fully reaction, phosphogypsum after treatment enters dryer, dries by the fire to water content 10% in 100 ℃, and baking back material enters shaper extruding balling-up, must strengthen gypsum sphere C, balling ratio 50%, the intensity 1.21Kg of ball.
Strengthen gypsum sphere A and contain solubility P
2O
5, strengthening gypsum sphere B, C does not almost have solubility P
2O
5, be used for the following table that the results are shown in of manufacture of cement:
| The cement clinker numbering | Free C in the cement clinker aO | Species of gypsum | Soundness of cement |
| Ⅰ | 4.5% | The plaster of paris | Bent (defective) |
| Strengthen gypsum sphere A | Stable (qualified) | ||
| Strengthen gypsum sphere B | Bent (defective) | ||
| Strengthen gypsum sphere C | Bent (defective) | ||
| Ⅱ | 1.5% | The plaster of paris | Stable (qualified) |
| Strengthen gypsum sphere A | Stable (qualified) | ||
| Strengthen gypsum sphere B | Stable (qualified) | ||
| Strengthen gypsum sphere C | Stable (qualified) |
As seen from the above table, according to the different workers of manufacture of cement, skill is what of free CaO in the cement clinker, and selects to strengthen the suitable ratio of components of phosphogypsum slag and lime in the gypsum sphere, can both reach satisfied effect.
Claims (4)
1, a kind of enhancing gypsum sphere that is used for manufacture of cement wherein contains CaSO
4, it is characterized in that it being by phosphogypsum and lime: CaO, Ca (OH)
2By the proportion ingredient of 100: 0.5～10 (weight), stir, in oven dry below 150 ℃, dry by the fire to material moisture be 3～10%, baking back material enters shaper, pushes balling-up, P in the phosphogypsum slag
2O
5With the reaction of lime be:
2, gypsum sphere as claimed in claim 1 is characterized in that the said phosphogypsum and the optimum proportion ratio of lime are 100: 0.5～2(weight).
3,, it is characterized in that said lime is preferably slaked lime as claim 1,2 described gypsum spheres.
4, gypsum sphere as claimed in claim 1 is characterized in that said compound method, and best bake out temperature is below 120 ℃, and baking back material optimum moisture content is 4～6%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92112246 CN1085879A (en) | 1992-10-16 | 1992-10-16 | Producing cement from phosphor production is with strengthening gypsum sphere |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92112246 CN1085879A (en) | 1992-10-16 | 1992-10-16 | Producing cement from phosphor production is with strengthening gypsum sphere |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1085879A true CN1085879A (en) | 1994-04-27 |
Family
ID=4945852
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 92112246 Pending CN1085879A (en) | 1992-10-16 | 1992-10-16 | Producing cement from phosphor production is with strengthening gypsum sphere |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1085879A (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1097568C (en) * | 2000-05-13 | 2003-01-01 | 吴帆 | Using gelating material-modified ardealite instead of natural gypsum as cement retardant |
| CN100351197C (en) * | 2002-09-25 | 2007-11-28 | 陈智丰 | Process for making quick hardening aluminosulfate cement |
| CN100371282C (en) * | 2005-10-01 | 2008-02-27 | 铜陵化学工业集团有限公司 | Production of cement retarder by chemical gypsum extrusion |
| US7585485B2 (en) | 2006-07-03 | 2009-09-08 | Tripoliven, C.A. | Process for the physiochemical conditioning of chemical gypsum or phospho-gypsum for use in formulation for cement and other construction materials |
| CN101152737B (en) * | 2006-09-26 | 2011-02-16 | 铜陵化学工业集团有限公司 | Method for squeezing to produce concrete retardation ball with chemical gypsum |
| CN101402515B (en) * | 2008-10-13 | 2011-07-20 | 葛洲坝集团试验检测有限公司 | Reinforced anti-split agent for materials such as lime and coal ash |
| CN102190451A (en) * | 2010-03-19 | 2011-09-21 | 贵州省建筑材料科学研究设计院 | Method for producing moderate heat portland cement |
| CN101376574B (en) * | 2008-09-23 | 2012-03-21 | 四川利森建材集团有限公司 | Process and apparatus for producing cement retarder using ardealite waste liquor |
| CN103011643A (en) * | 2012-12-25 | 2013-04-03 | 陶小勇 | Comprehensive utilization method of phosphogypsum and coal gangue |
| CN104072003A (en) * | 2014-07-15 | 2014-10-01 | 铜陵化学工业集团有限公司 | Method for preparing cement retarder through titanium gypsum |
| CN114907037A (en) * | 2022-04-11 | 2022-08-16 | 三峡大学 | Preparation method of phosphogypsum high-strength aggregate |
-
1992
- 1992-10-16 CN CN 92112246 patent/CN1085879A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1097568C (en) * | 2000-05-13 | 2003-01-01 | 吴帆 | Using gelating material-modified ardealite instead of natural gypsum as cement retardant |
| CN100351197C (en) * | 2002-09-25 | 2007-11-28 | 陈智丰 | Process for making quick hardening aluminosulfate cement |
| CN100371282C (en) * | 2005-10-01 | 2008-02-27 | 铜陵化学工业集团有限公司 | Production of cement retarder by chemical gypsum extrusion |
| US7585485B2 (en) | 2006-07-03 | 2009-09-08 | Tripoliven, C.A. | Process for the physiochemical conditioning of chemical gypsum or phospho-gypsum for use in formulation for cement and other construction materials |
| CN101152737B (en) * | 2006-09-26 | 2011-02-16 | 铜陵化学工业集团有限公司 | Method for squeezing to produce concrete retardation ball with chemical gypsum |
| CN101376574B (en) * | 2008-09-23 | 2012-03-21 | 四川利森建材集团有限公司 | Process and apparatus for producing cement retarder using ardealite waste liquor |
| CN101402515B (en) * | 2008-10-13 | 2011-07-20 | 葛洲坝集团试验检测有限公司 | Reinforced anti-split agent for materials such as lime and coal ash |
| CN102190451A (en) * | 2010-03-19 | 2011-09-21 | 贵州省建筑材料科学研究设计院 | Method for producing moderate heat portland cement |
| CN103011643A (en) * | 2012-12-25 | 2013-04-03 | 陶小勇 | Comprehensive utilization method of phosphogypsum and coal gangue |
| CN103011643B (en) * | 2012-12-25 | 2014-04-16 | 陶小勇 | Comprehensive utilization method of phosphogypsum and coal gangue |
| CN104072003A (en) * | 2014-07-15 | 2014-10-01 | 铜陵化学工业集团有限公司 | Method for preparing cement retarder through titanium gypsum |
| CN104072003B (en) * | 2014-07-15 | 2016-07-13 | 铜陵化学工业集团有限公司 | A kind of titanium gypsum prepares the method for cement retarder |
| CN114907037A (en) * | 2022-04-11 | 2022-08-16 | 三峡大学 | Preparation method of phosphogypsum high-strength aggregate |
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