CN102531441A - Production method and product of cement retarder from ardealite - Google Patents
Production method and product of cement retarder from ardealite Download PDFInfo
- Publication number
- CN102531441A CN102531441A CN2012100475497A CN201210047549A CN102531441A CN 102531441 A CN102531441 A CN 102531441A CN 2012100475497 A CN2012100475497 A CN 2012100475497A CN 201210047549 A CN201210047549 A CN 201210047549A CN 102531441 A CN102531441 A CN 102531441A
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- phosphogypsum
- ardealite
- cement
- weight
- retardant
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Abstract
The invention relates to a novel cement retarder prepared from ardealite and a production method thereof. The production method comprises the following steps of: 1, analyzing the mass percentage content of fluorine and free phosphoric acid in the ardealite; 2, adding the weighed ardealite in a mixer, adding quick lime powder the weight of which is 3-8 times that of the ardealite, adding cement kiln ash the weight of which is 5-15% of the ardealite, and adding a grinding aid the weight of which is 5-10% of the ardealite; 3, controlling the mixing time of materials in the mixer to 10-30 minutes to obtain a mixed material; 4, feeding the mixed material into a smashing machine with a belt transportation machine for smashing the mixed material, and uniformly distributing the material layer by layer in a storeroom; 5, standing and curing the distributed material for 3-10 days in the storeroom to obtain the modified ardealite; and 6, continuously turning over the modified ardealite through a double-beam grab bucket crane and further naturally drying so as to obtain the cement retarder prepared from the ardealite. The obtained product is powdery and contains more than or equal to 38% of SO3, less than or equal to 0.1% of free phosphoric acid (based on P2O5), more than or equal to 15% of crystal water and less than or equal to 18% of adhered water.
Description
Technical field
The present invention relates to a kind of novel producing cement from phosphor retardant, and working method.
Background technology
Owing to contain fluorion and free phosphoric acid etc. to the deleterious impurity of cement in the phosphogypsum, can not need carry out modification directly as cement setting retarder.Simultaneously, phosphogypsum is a powdery, and is moisture 25 ~ 30%, and cement mill directly use can cause feed bin to stop up, and is difficult to control.General method of producing the phosphogypsum retardation setting agent is at first to add the properties-correcting agent lime powder in phosphogypsum, during the fluorion in the phosphogypsum and free phosphoric acid are carried out and modification.Phosphogypsum part (~ 30%) after the modification is taken off attached water wherein through calcining, simultaneously, and the staple terra alba (CaSO in the phosphogypsum
42H
2O) also taken off 1.5 its crystal water, become calcium sulphate hemihydrate (CaSO
40.5H
2O).Phosphogypsum after the calcining gets into tablets press with other 70% without the incinerating phosphogypsum, and at this, semi-hydrated gypsum absorbs water again and becomes dihydrate gypsum, in this process, has caused the granule of 10 ~ 40mm, is sold to the cement mill after the ageing.Because of it is granular, and moisture reduces therefore no longer stifled storehouse.Whole process needs calcining because of phosphogypsum, needs to consume a large amount of coals, general product consumption coal 50 ~ 80kg per ton; Calcine tail gas simultaneously and need pass through processing, cause secondary pollution again; Production process is complicated, the high enterprise of cost, and manufacturing cost surpasses 80 yuan/ton, causes price to surpass the desulfurated plaster price that use in the cement mill, can't big area promote.
The present domestic overwhelming majority's phosphogypsum retardation setting agent manufacturing enterprise all adopts traditional calcining technology, and its production technique is basic identical.Different according to calciner; Can be divided into following several kinds of technologies again: 1, single rotor hammer oven dry system retardant technology; This technology is that phosphogypsum is accomplished calcining generation semi-hydrated gypsum powder in single rotor hammer dryer; Carry out mixed ball and slaking again, finally obtain phosphogypsum retardation setting agent product, thermal source is from coal furnace.2, rotary drying system retardant technology, this technology are that phosphogypsum is accomplished dehydration in rotary dryer, and the semi-hydrated gypsum of generation is further processed balling-up and made retardant, and thermal source comes the spontaneous combustion coal fluidizing furnace.3, FC locellus calcination process retardant technology, this technology are that phosphogypsum is accomplished drying and dehydrating in FC locellus calcining compartment, make the ball ageing then and produce retardant, and thermal source also comes the spontaneous combustion coal fluidizing furnace.
Ardealite setting retarder for cement is as a kind of product innovation, and 2008, country announced national standard: GB/T21371-2008 " industry by-product gypsum that is used for cement ".To water-soluble P wherein
2O
5Content, mineral composition and attached water all have regulation, and its granularity is also had regulation, require product spherolite diameter 10～40mm.That is to say that present ardealite setting retarder for cement all must be a globular.
Summary of the invention
The object of the present invention is to provide a kind of working method of exempting from incinerating producing cement from phosphor retardant.
Another object of the present invention is to provide the resulting powdery producing cement from phosphor of this method retardant.
The working method of producing cement from phosphor retardant of the present invention is made up of following steps:
One, analyze the mass percentage content of fluorine in the phosphogypsum by Fluoride ion selective electrode method, press the mass percentage content that phospho-molybdic acid quinoline weighting method is analyzed free phosphoric acid in the phosphogypsum, method is analyzed the mass percentage content of attached water in the phosphogypsum by weight;
Two, phosphogypsum metering back is added in the mixing tank, according to the theory required CaO amount that neutralizes, add the calcium lime powder of 3 ~ 8 times of weight by the quality of resulting fluorion of analytical data and free phosphoric acid; The cement flue Dust that adds phosphogypsum weight 5 ~ 15%; Add the grinding aid of phosphogypsum weight 5 ~ 10%, described grinding aid is: tri-isopropanolamine 40 ~ 60%, trolamine 5 ~ 15%, carboxylic acid 10 ~ 25%, water 10 ~ 30%;
Three, the mixing time 10 ~ 30 minutes of material in the control mixing tank has obtained mixture;
Four, the material that mixes is sent in the beater with with fortune machine, mixture is broken up, and in storehouse uniform cloth in layer;
Five, the material that cloth is good static slaking 3 ~ 10 days in storehouse obtains the phosphogypsum after the modification;
Six, the phosphogypsum after the modification obtains the producing cement from phosphor retardant through the continuous turning of twin beams grab crane and continue seasoning.
Described calcium lime powder is to wear into 100 ~ 325 purpose powders with the unslaked lime of CaO >=90%; Described cement flue Dust is that cement mill kiln tail passes through 100 ~ 150 ℃ of the collected temperature of tornado dust collector, and water cut is grey less than 1% kiln.
Producing cement from phosphor retardant by aforesaid method production of the present invention is a powdery, trioxygen-containing sulphur S0
3>=38%, contain free phosphoric acid (with P
2O
5Meter)≤0.1%, contain crystal water>=15%, contain attached water≤18%.
The calcium lime powder that the present invention adds is a properties-correcting agent, and two effects are arranged, except in phosphogypsum in fluorine and free phosphoric acid, also, can reduce the moisture of product owing to become calcium hydroxide after its suction.The properties-correcting agent cement flue Dust that adopts, from the cement mill, cheap and easy to get; Harmless to manufacture of cement, because its temperature high (100 ~ 150 ℃) is not moisture basically; Can the moisture in the phosphogypsum directly be dropped near product standard after the adding; Through the mode of driving turning seasoning, the moisture in the product is finally dropped to standard-required again, thereby be able to omit calcining balling-up operation.The grinding aid that adopts mainly is in order to improve the grindability index of cement, to improve the later strength of cement.Whole energy saving technology environmental protection significantly reduces cost, and its manufacturing cost only accounts for 60% of calcining balling technique, and ton is manufacturing cost≤50 yuan/ton all.
Testing data:
Following with the phosphogypsum retardation setting agent and the desulfurated plaster correlation data of calcining balling-up:
Table 1 chemical analysis
| Sample number into spectrum | CaO | Cl - | MgO | SO 3 |
| #1 (P.S.A32.5) present embodiment 1 | 55.38 | 0.014 | 4.47 | 1.65 |
| #2 (P.S.A32.5) present embodiment 2 | 56.24 | 0.015 | 4.04 | 1.63 |
| #3 (P.S.A32.5) calcining balling-up phosphogypsum | 56.65 | 0.015 | 4.25 | 1.66 |
| #4 (P.S.A32.5) desulfurated plaster | 57.02 | 0.017 | 4.35 | 1.70 |
Table 2 Physical Test
Producing cement from phosphor retardant of the present invention adds in the cement clinker can play good delayed coagulation, and time of coagulation and ultimate compression strength are compared no significant difference with the desulfurated plaster retardant.Described production technique has avoided a large amount of employing fire coals to carry out the dry cost pressure that is brought of producing; It is relatively low, the moist not incinerating of product cost novel process in the current domestic same industry; Satisfy the present low-carbon economy of advocating simultaneously, and the properties-correcting agent raw material that is adopted is easy to get, with low cost; Method is simple, and modified effect is good.
Embodiment
Embodiment 1:
A, the mass percentage content of measuring fluorine (F) in the phosphogypsum by Fluoride ion selective electrode method are 0.1%; Press the phosphoric acid that dissociates in the phospho-molybdic acid quinoline gravimetric determination phosphogypsum (with P
2O
5Meter) mass percentage content is: 0.41%.Method is measured attached water (H in the phosphogypsum by weight
2O) mass percentage content is: 26.4%.
According to 100 tons of phosphogypsum meters, the fluorion amount is 0.1 ton, and the required CaO amount of theoretical neutralization is 0.295 ton, and calculating formula is:
100×0.1%×56/38?=?0.15。
According to 100 tons of phosphogypsum meters, free phosphoric acid is (with P
2O
5Meter) be 0.41 ton, the required CaO amount of theoretical neutralization is 0.49 ton, and calculating formula is:
100×0.41%×168/142?=?0.49。
B, in mixing tank, add 100 tons of phosphogypsums, add 5 tons of fineness, 100 purpose calcium lime powders more respectively, 10 tons of cement flue Dusts, 5 tons of grinding aids, described grinding aid is: tri-isopropanolamine 50%, trolamine 10%, carboxylic acid 10%, water 30%.
Mixing machine is a horizontal type structure; Constitute by feeding unit, riding wheel apparatus, rotating cylinder, transmission mechanism, holder latch device and discharge device; On the revolving drum body wall, pore is arranged; At the whole liner rubber plates of rotating cylinder inwall, rubber plate is fixed on the inwall of rotating cylinder through rubber pressing plate at interval.Described pore and the dislocation of rubber pressing plate are arranged, and can when rotating cylinder rotates, under gravity and self flexible effect, from the pore of rotating cylinder, suck air like this, under the effect of air, make the rubber plate recoverable deformation, reach self-cleaning function.
C, control mixing time 10 minutes have obtained the good material of a kind of modification.
D, the material that will react good are sent in the beater with with fortune machine, mixture is broken up, and in storehouse cloth uniformly in layer.
The static slaking 3 days in storehouse of the good material of E, cloth obtains the phosphogypsum after the modification;
Phosphogypsum after F, the modification is through the continuous turning of twin beams grab crane and continued seasoning 4 days, obtains final retardant product, wherein trioxygen-containing sulphur (S0
3): 38.28%, contain free phosphoric acid (with P
2O
5Meter): do not detect, contain crystal water: 16.6%, contain attached water: 17.2%.
Embodiment 2,
A, the mass percentage content of measuring fluorine (F) in the phosphogypsum by Fluoride ion selective electrode method are 0.15%; Press the phosphoric acid that dissociates in the phospho-molybdic acid quinoline gravimetric determination phosphogypsum (with P
2O
5Meter) mass percentage content is: 0.62%.Method is measured attached water (H in the phosphogypsum by weight
2O) mass percentage content is: 27.25%.
According to 100 tons of phosphogypsum meters, the fluorion amount is 0.15 ton, and the required CaO amount of theoretical neutralization is 0.22 ton, and according to 100 tons of phosphogypsum meters, free phosphoric acid is (with P
2O
5Meter) be 0.41 ton, the required CaO amount of theoretical neutralization is 0.73 ton.
B, in mixing tank, add 100 tons of phosphogypsums, add 6 tons of fineness, 100 purpose calcium lime powders more respectively, 15 tons of cement flue Dusts, 6 tons of grinding aids, described grinding aid is: tri-isopropanolamine 50%, trolamine 10%, carboxylic acid 10%, water 30%.
C, control mixing time 15 minutes have obtained the good material of a kind of modification.
D, the material that will react good are sent in the beater with with fortune machine, mixture is broken up, and in storehouse cloth uniformly in layer.
The static slaking 5 days in storehouse of the good material of E, cloth obtains the phosphogypsum after the modification;
Phosphogypsum after F, the modification is through the continuous turning of twin beams grab crane and continued seasoning 5 days, obtains final retardant product, wherein trioxygen-containing sulphur (S0
3): 38.01%, contain free phosphoric acid (with P
2O
5Meter): do not detect, contain crystal water: 16.2%, contain attached water: 16.0%.
Claims (3)
1. the working method of a producing cement from phosphor retardant is characterized in that being made up of following steps:
One, analyze the mass percentage content of fluorine in the phosphogypsum by Fluoride ion selective electrode method, press the mass percentage content that phospho-molybdic acid quinoline weighting method is analyzed free phosphoric acid in the phosphogypsum, method is analyzed the mass percentage content of attached water in the phosphogypsum by weight;
Two, phosphogypsum metering back is added in the mixing tank, according to the theory required CaO amount that neutralizes, add the calcium lime powder of 3 ~ 8 times of weight by the quality of resulting fluorion of analytical data and free phosphoric acid; The cement flue Dust that adds phosphogypsum weight 5 ~ 15%; Add the grinding aid of phosphogypsum weight 5 ~ 10%, described grinding aid is: tri-isopropanolamine 40 ~ 60%, trolamine 5 ~ 15%, carboxylic acid 10 ~ 25%, water 10 ~ 30%;
Three, the mixing time 10 ~ 30 minutes of material in the control mixing tank has obtained mixture;
Four, the material that mixes is sent in the beater with with fortune machine, mixture is broken up, and in storehouse uniform cloth in layer;
Five, the material that cloth is good static slaking 3 ~ 10 days in storehouse obtains the phosphogypsum after the modification;
Six, the phosphogypsum after the modification obtains the producing cement from phosphor retardant through the continuous turning of twin beams grab crane and continue seasoning.
2. the working method of producing cement from phosphor retardant as claimed in claim 1 is characterized in that described calcium lime powder is to wear into 100 ~ 325 purpose powders with the unslaked lime of CaO >=90%; Described cement flue Dust is that cement mill kiln tail passes through 100 ~ 150 ℃ of the collected temperature of tornado dust collector, and water cut is grey less than 1% kiln.
3. the product produced of according to claim 1 or claim 2 the working method of producing cement from phosphor retardant is characterized in that the producing cement from phosphor retardant of being produced by said method is a powdery, trioxygen-containing sulphur S0
3>=38%, contain free phosphoric acid with P
2O
5Meter≤0.1% contains crystal water>=15%, contains attached water≤18%.
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|---|---|---|---|
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|---|---|---|---|
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103833254A (en) * | 2014-03-25 | 2014-06-04 | 云南富民瑞呈饲料添加剂有限公司 | Modification method of ardealite applied as cement retarder |
| CN104310836A (en) * | 2014-09-28 | 2015-01-28 | 四川鑫统领建材科技有限公司 | Modified phosphogypsum as well as preparation method and use of modified phosphogypsum |
| CN105967615A (en) * | 2016-03-29 | 2016-09-28 | 蚌埠华东石膏有限公司 | Water-resistant self-cleaning insulation building gypsum powder and preparation method thereof |
| CN108609885A (en) * | 2018-05-28 | 2018-10-02 | 四川同庆南风有限责任公司 | A method of it solving mirabilite gypsum and feeds intake difficulty as cement retarder |
| CN109020286A (en) * | 2018-08-22 | 2018-12-18 | 曲靖市麒麟区鑫强商贸有限公司 | A kind of calcium sulphate retarder |
| CN109265040A (en) * | 2018-11-19 | 2019-01-25 | 广东鸿丰水泥有限公司 | A kind of application of industrial residue as cement retarder |
| CN113683321A (en) * | 2021-08-09 | 2021-11-23 | 山东汇泰再生资源有限公司 | Method for producing sulfate-resistant silicate cement by using phosphogypsum |
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| CN1453234A (en) * | 2002-04-27 | 2003-11-05 | 刘茂平 | Ardealite curing modification process |
| CN101792278A (en) * | 2010-04-06 | 2010-08-04 | 四川利森建材科技开发有限公司 | Method for producing cement retarder through phosphogypsum |
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2012
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Patent Citations (2)
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| CN1453234A (en) * | 2002-04-27 | 2003-11-05 | 刘茂平 | Ardealite curing modification process |
| CN101792278A (en) * | 2010-04-06 | 2010-08-04 | 四川利森建材科技开发有限公司 | Method for producing cement retarder through phosphogypsum |
Non-Patent Citations (1)
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| 罗代君等: "磷石膏作水泥缓凝剂试验", 《四川建材》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103833254A (en) * | 2014-03-25 | 2014-06-04 | 云南富民瑞呈饲料添加剂有限公司 | Modification method of ardealite applied as cement retarder |
| CN104310836A (en) * | 2014-09-28 | 2015-01-28 | 四川鑫统领建材科技有限公司 | Modified phosphogypsum as well as preparation method and use of modified phosphogypsum |
| CN105967615A (en) * | 2016-03-29 | 2016-09-28 | 蚌埠华东石膏有限公司 | Water-resistant self-cleaning insulation building gypsum powder and preparation method thereof |
| CN108609885A (en) * | 2018-05-28 | 2018-10-02 | 四川同庆南风有限责任公司 | A method of it solving mirabilite gypsum and feeds intake difficulty as cement retarder |
| CN108609885B (en) * | 2018-05-28 | 2021-03-30 | 四川同庆南风有限责任公司 | Method for solving feeding difficulty of mirabilite gypsum used as cement retarder |
| CN109020286A (en) * | 2018-08-22 | 2018-12-18 | 曲靖市麒麟区鑫强商贸有限公司 | A kind of calcium sulphate retarder |
| CN109265040A (en) * | 2018-11-19 | 2019-01-25 | 广东鸿丰水泥有限公司 | A kind of application of industrial residue as cement retarder |
| CN113683321A (en) * | 2021-08-09 | 2021-11-23 | 山东汇泰再生资源有限公司 | Method for producing sulfate-resistant silicate cement by using phosphogypsum |
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Application publication date: 20120704 |