CN104176963A - Phosphorus gypsum cement retarder - Google Patents
Phosphorus gypsum cement retarder Download PDFInfo
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- CN104176963A CN104176963A CN201410382973.6A CN201410382973A CN104176963A CN 104176963 A CN104176963 A CN 104176963A CN 201410382973 A CN201410382973 A CN 201410382973A CN 104176963 A CN104176963 A CN 104176963A
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- waste
- phosphogypsum
- asphalt
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Abstract
The invention relates to a phosphorus gypsum cement retarder. The phosphorus gypsum cement retarder is prepared from the following raw materials of phosphorus gypsum, asphalt waste and lime in manners of evenly mixing and curing for over 11 hours, wherein the phosphorus gypsum is the waste generated in phosphoric acid production in phosphate fertilizer industry; and the asphalt waste is the waste produced in the asphalt production process. The phosphorus gypsum cement retarder does not need a high-energy calcination process, and the modification effect is obviously superior to those of traditional washing and limestone neutralization treatment processes. Compared with the phosphorus gypsum which is not subjected to modification treatment, the cement setting time is shortened by about an hour, and the water requirement of normal consistency and the setting time are roughly the same as those when a natural gypsum retarder is mixed. The phosphorus gypsum cement retarder is low in cost, simple in technical process, and easy to popularize and apply on a large scale, meanwhile, the dosage of cement admixtures such as coal ash and the like also can be saved, dual environmental pollution of the asphalt waste and the phosphorus gypsum is effectively reduced, a natural gypsum resource is saved, comprehensive utilization of industrial waste residues is achieved, and good economic and beneficial benefits are generated.
Description
Technical field
The present invention relates to renewable resource comprehensive utilization technique field, particularly a kind of ardealite setting retarder for cement and preparation method.
Background technology
Phosphogypsum is the waste material producing while producing phosphoric acid in Phosphate Fertilizer Industry, and 1 ton of phosphoric acid of every production can discharge about 5 tons of waste residues.Due to the quick growth development of phosphorous chemical industry industry, phosphogypsum waste material output is rapid growth also.Current, approximately 2. 8 hundred million tons of the annual discharges of global phosphogypsum slag, and China's quantity discharged accounts for 20%, and the demonstration of cut-off latest data, approximately there are 200,000,000 tons of phosphogypsum accumulation deposit in China.Phosphogypsum main chemical is dihydrate gypsum (CaSO
42H
2o), be similar to the plaster of paris, yet because phosphogypsum contains titanium pigment, fluorine and free acid and other impurity, arbitrarily discharge meeting causes severe contamination to environment.Therefore, production of phosphate fertilizer enterprise all needs to set up specially stockyard, and not only land occupation, and slag expense is high, and phosphogypsum store up for a long time can polluted water resources, ecotope is damaged.
Phosphogypsum substitutes the plaster of paris as cement setting retarder, not only saves a large amount of valuable gypsum resources, and turn waste into wealth, with low cost, there is important environment protection significance and economic implications, become one of main path of the comprehensive recycling of phosphogypsum waste.The main chemical of phosphogypsum is dihydrate gypsum (CaSO
42H
2o), quality is about 80%-98%, has a small amount of impurity to exist simultaneously.Because it contains residual H
3pO
4with HF and unreacted H
2sO
4, thereby phosphogypsum can show slightly acidic.Phosphogypsum is as a kind of important reclaimed gypsum resource, and purity is higher, conventionally SO
3mass percent be more than or equal to 40%, than the effective SO in the plaster of paris
3content is high.Leaching Properties of Soluble Phosphorus is topmost acidic impurities in phosphogypsum, derives from unreacted phosphoric acid salt and residual phosphoric acid, through after washing and filtering, still can partly be retained in phosphogypsum.While directly applying to industrial production cement, these impurity can extend cement setting time, cause product surface efflorescence simultaneously, affect cement surface smooth finish.Thereby need to, to phosphogypsum through suitable modification, could replace the plaster of paris for manufacture of cement.
Calcining process can make harmful phosphorus be transformed into the phosphate mineral of inertia, thereby can not affect time of coagulation and the intensity of cement.But calcining process energy consumption is large, and output is limited.WATER-WASHING METHOD is one of conventional pretreatment main technique of phosphogypsum.Soluble impurity in phosphogypsum is generally attached to the surface of terra alba crystal, comprises soluble phosphate, fluorine and free phosphoric acid etc., and these impurity will be removed after generally processing through washing substantially.But washing removal of impurities is limited in one's ability, so need repeated multiple times washing to process and can be effective; After washing, need large quantity of moisture evaporation to dry simultaneously, therefore not only cause a large amount of energy wastages, processing cost is high, and what be more mainly easily causes intermediate water resource severe contamination problem, is therefore difficult to large-scale popularization application.And lime neutralizing treatment needs a large amount of lime consumptions, generally need the lime of 10% content could effectively reduce Leaching Properties of Soluble Phosphorus content, and lime is expensive, so that the economic benefit degradation of enterprise.
Summary of the invention
For detrimental impurity content such as Leaching Properties of Soluble Phosphorus in effective reduction phosphogypsum, make cement setting time normal; The invention provides a kind of ardealite setting retarder for cement with low cost, simple to operate.
A kind of ardealite setting retarder for cement is comprised of the raw material of following weight: 1 ~ 10 part, phosphogypsum 50-80 part, asphalt waste 10-35 part and lime, and 1 ~ 5 part, water, mixes, and one-tenthization is more than 11 hours; Described phosphogypsum is the waste material producing while producing phosphoric acid in Phosphate Fertilizer Industry, and main chemical is dihydrate gypsum, and the content of dihydrate gypsum is 80%-98%;
Described asphalt waste is the waste material producing in asphalt production process, wherein silicon-dioxide (SiO
2) content be 49-50%, ferric oxide (Fe
2o
3) content be 5-7%, aluminium sesquioxide (Al
2o
3) content be that the content of 18-21%, calcium oxide (CaO) is that the content of 11-13%, magnesium oxide (MgO) is 2-4%, titanium dioxide (TiO
2) content be 0.5-1.5%, sulphur trioxide (SO
3) content be 1-2%.
The technical scheme of optimizing is: by 65 parts of phosphogypsums, 30 parts of asphalt waste, 3 parts, lime and 2 parts of mixing of water, stirs, then through the glomerate ardealite setting retarder for cement of nodulizer system, one-tenthization 12 hours.
Asphalt production enterprise produces a large amount of asphalt waste, often pile up idle, recycling not yet in effect also at present.Asphalt waste main component is silicon-dioxide (SiO
2), ferric oxide (Fe
2o
3), aluminium sesquioxide (Al
2o
3) etc., these are all the effective constituent that generates essential mineral tricalcium silicate, Dicalcium Phosphate (Feed Grade), sulfuric acid DFP and the tetracalcium aluminoferrite of hydrated cementitious.And current cement mixture and phosphogypsum modification agent adopt flyash as raw material and properties-correcting agent conventionally, as introduced a kind of preparation method of ardealite setting retarder for cement in patent CN1279219A, adopt flyash, calcareous material and activator as the property-modifying additive of phosphogypsum.But the current price of flyash is comparatively expensive, supply is more nervous.And the chemical composition of asphalt waste and flyash are more approaching, and calcium oxide (CaO) content is far superior to flyash, without adding in addition calcareous material, be expected further to improve strength of cement, and asphalt waste needs raw materials cost to drop into hardly, chemical composition, dust granules fineness are all suitable for as phosphogypsum modification additive.Therefore, novelty of the present invention adopts abundant raw material, asphalt waste with low cost as the properties-correcting agent of phosphogypsum, can solve the waste disposal problem of production of phosphate fertilizer enterprise and pitch enterprise, has good economic worth and environment protection significance.
From table 1, phosphogypsum is compared with the plaster of paris, its sulphur trioxide (SO
3) mass percent be greater than 40%, far above SO in the plaster of paris
3content.According to terra alba (CaSO in GBT23456-2009 phosphogypsum standard test phosphogypsum
42H
2o) content, surpasses 90%, reaches country-level standard (>=85%), can improve strength of cement, thereby ardealite setting retarder for cement of the present invention, mainly just measures the time of coagulation of its Leaching Properties of Soluble Phosphorus content and cement.
The present invention adopts cheap asphalt waste as properties-correcting agent, can shorten cement setting time, improves strength of cement, and the flyash consumption of reducing expenses and growing to even greater heights, and solves the disposal difficulties of asphalt waste and phosphogypsum, thereby has larger economic and social benefit.The main existence form of Leaching Properties of Soluble Phosphorus in phosphogypsum is HP0
4 2-, H
2p0
4-, H
3pO
4.The existence of Leaching Properties of Soluble Phosphorus, can cause that cement setting time is undesired, and cement performance and environment are had a strong impact on.The present invention selects abundant, the cheap and easy to get asphalt waste in source and a small amount of lime to carry out composite modified to phosphogypsum, the chemical composition that also can find asphalt waste and cement mixture flyash from table 1 is more approaching, and CaO content is far superior to flyash, so be expected further to improve strength of cement.And phosphogypsum is acid, the interpolation of lime can be reacted with the acidic substance in phosphogypsum, removes acidic impurities.Due to Ca in asphalt waste and lime
2+content is all very high, and a large amount of Ca are provided when composite modified
2+, make Leaching Properties of Soluble Phosphorus be converted into the calcium phosphate of indissoluble, can effectively reduce the Leaching Properties of Soluble Phosphorus content in phosphogypsum, make cement setting time normal.Meanwhile, high Ca raw material adds, and in mixing process, reacts with water, generates hydrated calcium silicate, drated calcium aluminate and calcium sulphoaluminate, makes product formation have some strength particle, is convenient to the balling-up of ardealite setting retarder for cement.
According to GBT23456-2009 phosphogypsum standard, in the present invention's experiment, adopt the Leaching Properties of Soluble Phosphorus content in quinoline molybdenum lemon ketone Precipitation Determination phosphogypsum.First the present invention has contrasted the affect rule of different treatment technique on phosphogypsum Leaching Properties of Soluble Phosphorus content.From table 2, sample number into spectrum is as follows: the PG0 plaster of paris; The untreated phosphogypsum of PG1; PG2 washes processing; PG3 lime neutralizing treatment; PG4 pitch, the composite modified processing of lime.As can be seen from Table 2, PG2 is processed in washing can remove portion Leaching Properties of Soluble Phosphorus, but cost is too high and very easily cause environmental pollution.Although lime treatment PG3 effect is remarkable, the phosphogypsum quality less stable of producing thus, after the composite modified technique of asphaltic limestone that the present invention proposes, compares with original state phosphogypsum, and in modified ardealite, the content of Leaching Properties of Soluble Phosphorus is close to zero.The composite modifying method of asphalt waste and lime compared with other modifications, has in all fields obvious advantage, so can effectively reduce the Leaching Properties of Soluble Phosphorus content in phosphogypsum.
The present invention adopts composite modifying method, and Leaching Properties of Soluble Phosphorus content, by untreated 0.28%, is significantly reduced to 0.007%; Obviously be better than 0.014% of 0.114% and lime neutralizing treatment that washing processes.And effective reduction of Leaching Properties of Soluble Phosphorus can make be tending towards normal the time of coagulation of cement.
According to GB/T1346-2001 cement normal consistency water consumption, time of coagulation national standard, the present invention has measured the impact of different treatment technique on cement setting time.From table 3, sample number into spectrum is as follows: the PG0 plaster of paris; The untreated phosphogypsum of PG1; PG2 washes processing; PG3 lime neutralizing treatment; PG4 pitch, the composite modified processing of lime.Tradition cement treated method, only shortened 10min the time of coagulation of cement, and the time of coagulation of shortening cement not yet in effect; Employing is lime modified separately, although make there has been shortening by a relatively large margin the time of coagulation of cement, lime price is also higher, and the final performance of cement is not very stable; Adopt the composite modified phosphogypsum of asphaltic limestone, cement setting time shortens 1 hour nearly, has obtained good modified effect, and is more or less the same the time of coagulation of the cement that is mixed with of the time of coagulation of finished cement and the plaster of paris, and cement performance is stablized.Therefore, the composite modified phosphogypsum of asphaltic limestone of the present invention, can replace the plaster of paris completely and make retardant and produce for Cement industry, has significantly reduced production cost, for enterprise has brought significant economic benefit.
Economic and Efficiency Analysis: the market value of modified ardealite is at 100 yuan/ton at present, and by annual 200000 tons of calculating, annual value of production is 2,000 ten thousand; Flyash market value is at 70 yuan/ton, and lime price is at 350 yuan/ton, adopts flyash modified 30 parts of calculating, 21 yuan/ton of cost-saved expenses, 4,200,000 yuan of year saving; Adopt lime modifiedly, 10 parts of calculating, need to add 7 parts more, cost-saved 24.5 yuan/ton, year save 4,900,000 yuan; Adopt calcining and lime treatment, by 8 parts of limings, calculate, cost-saved 25 yuan/part (17.5 yuan, 7.5 yuan+5 parts lime of calcining cost), can economize on the use of funds 5,000,000 yuan.
Embodiment
Below in conjunction with embodiment, the present invention is further described.
Embodiment 1
By 1 ton, 50 tons of phosphogypsums, 20 tons of asphalt waste, 1 ton, lime and water, mix, one-tenthization 11 hours, makes ardealite setting retarder for cement; Phosphogypsum is the waste material producing while producing phosphoric acid in Phosphate Fertilizer Industry, and main chemical is dihydrate gypsum, and the content of dihydrate gypsum is 80%;
Asphalt waste is the waste material producing in asphalt production process, and wherein the content of silicon-dioxide is 48%, the content of ferric oxide is 5%, the content of aluminium sesquioxide is 18%, the content of calcium oxide is 11%, magnesian content is 2%, the content of titanium dioxide is 0.5%, the content of sulphur trioxide is 1%.
Embodiment 2
By 65 tons of phosphogypsums, 30 tons of asphalt waste, 3 tons, lime and 2 tons of mixing of water, stir, then through the glomerate ardealite setting retarder for cement of nodulizer system, one-tenthization 12 hours; The other the same as in Example 1.
Embodiment 3
By 2 tons, 100 tons of phosphogypsums, 35 tons of asphalt waste, 5 tons, lime and water, mix one-tenthization 14 hours; Make ardealite setting retarder for cement; The other the same as in Example 1.
Claims (2)
1. an ardealite setting retarder for cement, is characterized in that being comprised of the raw material of following weight: 1 ~ 10 part of phosphogypsum 50-80 part, asphalt waste 10-35 part, lime, and 1 ~ 5 part, water, mixes, and one-tenthization is more than 11 hours naturally;
Described phosphogypsum is the waste material producing while producing phosphoric acid in Phosphate Fertilizer Industry, and main chemical is dihydrate gypsum, and the content of dihydrate gypsum is 80%-98%;
Described asphalt waste is the waste material producing in asphalt production process, and wherein the content of silicon-dioxide is that the content of 48-51%, ferric oxide is that the content of 5-7%, aluminium sesquioxide is that the content of 18-21%, calcium oxide is that 11-13%, magnesian content are that the content of 2-4%, titanium dioxide is that the content of 0.5-1.5%, sulphur trioxide is 1-2%.
2. a kind of ardealite setting retarder for cement according to claim 1, it is characterized in that being formed by the raw material of following weight: 65 parts of phosphogypsums, 30 parts of asphalt waste, 3 parts, lime and 2 parts of mixing of water, stir, through the glomerate ardealite setting retarder for cement of nodulizer system, one-tenthization is 12 hours naturally again.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410382973.6A CN104176963B (en) | 2014-08-06 | 2014-08-06 | A kind of ardealite setting retarder for cement |
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| CN201410382973.6A CN104176963B (en) | 2014-08-06 | 2014-08-06 | A kind of ardealite setting retarder for cement |
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| CN104176963B CN104176963B (en) | 2015-12-09 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105503007A (en) * | 2016-01-19 | 2016-04-20 | 温岭市创嘉信息科技有限公司 | Phosphogypsum-based cement retarder |
| CN105948671A (en) * | 2016-04-25 | 2016-09-21 | 贵州安凯达实业股份有限公司 | Thermal mortar and preparation method thereof |
| CN107082587A (en) * | 2017-05-18 | 2017-08-22 | 河北科技大学 | A kind of preparation method of calcium sulphate retarder |
| CN107382117A (en) * | 2017-01-05 | 2017-11-24 | 合肥工业大学 | A kind of composite modified ardealite setting retarder for cement of perlite and low cost cement |
| CN109563349A (en) * | 2016-04-14 | 2019-04-02 | 福斯弗格林有限公司 | Composite material comprising ardealite |
| CN112209640A (en) * | 2020-09-07 | 2021-01-12 | 黄山精强建材股份有限公司 | Method for controlling setting time of cement produced by desulfurized gypsum |
| CN112408896A (en) * | 2020-11-21 | 2021-02-26 | 湖北云海混凝土有限公司 | Super-retarding concrete and preparation method thereof |
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| CN1279219A (en) * | 1999-06-24 | 2001-01-10 | 武汉可锐思新材料科技有限公司 | Ardealite setting retarder for cement and its preparing process |
| CN1394823A (en) * | 2002-08-09 | 2003-02-05 | 孙国庆 | Modified phosphogypsum and its preparation |
| CN101306925A (en) * | 2008-07-04 | 2008-11-19 | 昆明理工大学 | Process for preparing modified ardealite by water-free calcining |
-
2014
- 2014-08-06 CN CN201410382973.6A patent/CN104176963B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1279219A (en) * | 1999-06-24 | 2001-01-10 | 武汉可锐思新材料科技有限公司 | Ardealite setting retarder for cement and its preparing process |
| CN1394823A (en) * | 2002-08-09 | 2003-02-05 | 孙国庆 | Modified phosphogypsum and its preparation |
| CN101306925A (en) * | 2008-07-04 | 2008-11-19 | 昆明理工大学 | Process for preparing modified ardealite by water-free calcining |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105503007A (en) * | 2016-01-19 | 2016-04-20 | 温岭市创嘉信息科技有限公司 | Phosphogypsum-based cement retarder |
| CN105503007B (en) * | 2016-01-19 | 2017-07-07 | 温岭市创嘉信息科技有限公司 | A kind of cement retarder based on ardealite |
| CN109563349A (en) * | 2016-04-14 | 2019-04-02 | 福斯弗格林有限公司 | Composite material comprising ardealite |
| CN105948671A (en) * | 2016-04-25 | 2016-09-21 | 贵州安凯达实业股份有限公司 | Thermal mortar and preparation method thereof |
| CN105948671B (en) * | 2016-04-25 | 2018-05-04 | 贵州安凯达实业股份有限公司 | A kind of thermal insulation mortar and preparation method thereof |
| CN107382117A (en) * | 2017-01-05 | 2017-11-24 | 合肥工业大学 | A kind of composite modified ardealite setting retarder for cement of perlite and low cost cement |
| CN107082587A (en) * | 2017-05-18 | 2017-08-22 | 河北科技大学 | A kind of preparation method of calcium sulphate retarder |
| CN107082587B (en) * | 2017-05-18 | 2019-04-19 | 河北科技大学 | A kind of preparation method of calcium sulphate retarder |
| CN112209640A (en) * | 2020-09-07 | 2021-01-12 | 黄山精强建材股份有限公司 | Method for controlling setting time of cement produced by desulfurized gypsum |
| CN112408896A (en) * | 2020-11-21 | 2021-02-26 | 湖北云海混凝土有限公司 | Super-retarding concrete and preparation method thereof |
| CN112408896B (en) * | 2020-11-21 | 2022-05-13 | 湖北云海混凝土有限公司 | Super-retarding concrete and preparation method thereof |
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|---|---|
| CN104176963B (en) | 2015-12-09 |
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