CN107056115B - A kind of rush for ardealite based cementitious material coagulates type early strength agent and preparation method thereof - Google Patents

A kind of rush for ardealite based cementitious material coagulates type early strength agent and preparation method thereof Download PDF

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CN107056115B
CN107056115B CN201710300591.8A CN201710300591A CN107056115B CN 107056115 B CN107056115 B CN 107056115B CN 201710300591 A CN201710300591 A CN 201710300591A CN 107056115 B CN107056115 B CN 107056115B
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ardealite
rush
cementitious
early strength
component
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CN107056115A (en
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吴赤球
水中和
杨新峰
孙涛
吕伟
赵士豪
陈浩然
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HUBEI CHANG YAOXIN MATERIALS Ltd BY SHARE Ltd
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HUBEI CHANG YAOXIN MATERIALS Ltd BY SHARE Ltd
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    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B40/00Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/0028Aspects relating to the mixing step of the mortar preparation
    • C04B40/0039Premixtures of ingredients
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/10Accelerators; Activators
    • C04B2103/12Set accelerators

Abstract

The present invention provides a kind of rush for ardealite based cementitious material to coagulate type early strength agent and preparation method thereof, including the solidifying component of high-temperature calcination modified kraft, accelerating component and rush mixed;It is 50%~70% that high-temperature calcination modified kraft, which is wherein prepared, according to percentage, 1~3%, 1%~7% and 25%~40% takes ardealite respectively, granulated blast-furnace slag, alkali-activator and water wet-milling in the ball mill, it is aged again, obtain mixed slurry and alum, phosphorus slag, dolime is calcined in Muffle furnace, calcined product is dry grinded in the ball mill after cooling, it prepares accelerating component and passes through compounding anhydrous aluminium silicate, anhydrous calcium sulphoaluminate, aluminum sulfate and dicalcium silicate, the high-temperature calcination modified kraft that will be prepared, accelerating component and the solidifying component of rush mix to obtain a kind of solidifying type early strength agent of rush for ardealite based cementitious material.The invention discloses a kind of rush for ardealite based cementitious material to coagulate type early strength agent and preparation method thereof, effectively has cured the slow setting impurity in ardealite, improves early strength.

Description

A kind of rush for ardealite based cementitious material coagulates type early strength agent and preparation method thereof
Technical field
The present invention relates to technical field of concrete, and in particular to a kind of solidifying type of the rush for ardealite based cementitious material is early strong Agent and preparation method thereof.
Background technique
Ardealite is the byproduct of phosphorus chemical industry production, and domestic production capacity is superfluous at present, and the ardealite of bulk deposition is to China Environment cause considerable damage, while ardealite is a kind of again well using solid waste, main component sulphur, calcium There are a variety of potential uses with gypsum resource, and contain the radionuclides such as phosphorus, fluorine, organic matter, alkali metal element.With phosphorus stone The increase year by year of cream yield, the resource utilization of ardealite become domestic and international research emphasis, but since various regions produce phosphorus stone The problems such as cream technique, material quality, ardealite comprehensive utilization standards system is not perfect, only 15% phosphorus in worldwide Gypsum is recycled, and the ardealite resource utilization in China only has 20%, and at present, ardealite is mainly used for slow setting Agent, soil improvement agent, ammonium sulfate and potassium sulfate, calcium sulfate crystal whiskers, co-producing cement etc., but these ardealite Land use systems are small Scale, low dose of utilization, although ardealite, which is used to prepare building materials of gypsum, to be utilized with large dosage, plastering intensity is not Height is not suitable in building trade.Most of untreated ardealite is still used as solid waste stacking to handle, ardealite Bulk deposition causes serious pollution to soil, water source, air, using the physical and chemical performance of various solid waste, with phosphorus Gypsum performance combines, and prepares novel gelled material, is the effective way of ardealite comprehensive utilization.
Ardealite is used to prepare cementitious material, can largely utilize various solid waste, meets sustainable development war Slightly, both at home and abroad successively to gypsum-fly ashlime/cement, gypsum-slag-clinker/lime, gypsum-fly ashlime/steel Slag, gypsum-flyash-slag-lime, gypsum-slag-steel slag-lime, gypsum-fly ashlime, gypsum-slag-clinker- The systems such as lime, gypsum-slag-fly ash, gypsum-fly ashlime-cement are studied, and a series of gypsum are had developed Cementitious material, but hydraulicity gypsum plaster is less, and gypsum slag cement is more mature hydraulic stone cream base gelling material Material.As gypsum addition increases, gypsum slag cement morning epistasis can decline, and use influence of the ardealite to cement Early-age behavior Stronger, great amount of soluble P, F causes cementitious material setting time slow in ardealite, and early strength is low, using 300 DEG C~ 900 DEG C of high-temperature calcinations are activated ardealite, and activating cost greatly increases again, loses more than gain.
For the problems such as ardealite slag cements setting time is slow, early strength development is low, this patent passes through to phosphorus stone Cream carries out the modification of certain way, mixes other excitation components again and prepares the early strength agent for being suitble to ardealite slag cements, improves The above problem.
Summary of the invention
The problem to be solved in the present invention is provided a kind of for phosphorus stone for the above-mentioned deficiency in the presence of the prior art The rush of cream base cementitious material coagulates type early strength agent and preparation method thereof and effectively improves early strength.
To achieve the above object, present invention employs the following technical solutions: a kind of for ardealite based cementitious material Promote solidifying type early strength agent, including the solidifying component of modified kraft, accelerating component and rush mixed;Wherein modified kraft weight Percentage is 20%~70%, and accelerating component weight percent is 10%~60%, promote solidifying weight percentages of components be 10%~ 45%.
Further, the modified kraft includes ardealite, granulated blast-furnace slag, alkali-activator, alum, phosphorus slag, forges Calcined dolomite.
Further, by weight percentage, ardealite: granulated blast-furnace slag: alkali-activator: alum: phosphorus slag: calcining is white Marble=50%~70%:1~3%:1%~7%:25%~40%:0.5%~3%:0.5%~2%.
Further, the alkali-activator is Portland clinker and grinding steel slag mixture.
Further, CaSO in the ardealite4·2H2O content >=85%, P2O5、F-≤ 1.5%.
Further, the granulated blast-furnace slag is S95 grades, SiO2、Al2O3, CaO total content >=80%, specific surface area 400 ~450m2/kg。
The invention also includes a kind of methods for preparing the solidifying type early strength agent of rush for ardealite based cementitious material simultaneously, including Following steps:
1) it, prepares modified kraft: being respectively 50%~70%, 1~3%, 1%~7% and according to weight percent 25%~40% takes ardealite, granulated blast-furnace slag, alkali-activator and water wet-milling in the ball mill respectively, then is aged, and obtains mixed Slurry is closed, mixed slurry is dried into 1h~2h in 50 DEG C~60 DEG C baking ovens, then by the mixed slurry and alum, phosphorus after drying Slag, dolime are calcined in 110 DEG C~180 DEG C Muffle furnaces, calcined product are dry grinded in the ball mill after cooling, then Mill is sifted out into obtain modified kraft having divided after dry;
2), prepare accelerating component: by weight percentage 10%, 50%, 20% and 10% compound anhydrous aluminium silicate, anhydrous sulphur Calcium aluminate, aluminum sulfate and dicalcium silicate;
3), preparation promotees solidifying component: by weight percentage 50%~80% and 20%~50% nine water sodium metasilicate of compounding and hydrogen Sodium oxide molybdena is compounded by sodium sulphate, sodium carbonate, potassium sulfate, by weight percentage, sodium sulphate: sodium carbonate: potassium sulfate= 20%~70%:1%~30%:1%~20%;
4), by the modified kraft prepared, accelerating component and accelerating component mix a kind of ardealite base rubber that is used for is coagulated The rush of material coagulates type early strength agent.
Further, the mixed slurry after the drying is according to weight percent hundred with alum, phosphorus slag, dolime 97%, it 1%, 1% and 1% is calcined.
Further, the alkali-activator is compounded by Portland clinker and grinding steel slag, by weight percentage Meter, Portland clinker: grinding steel slag=5%~50%:50%~95%;The Portland clinker is through ball mill powder Mill, grinding time >=30min, specific surface area >=350m2/kg;The grinding steel slag is the high alkalinity steel slag of basicity > 2.5, than Surface area >=500m2/kg。
Compared with the prior art, the invention has the following beneficial effects:
The invention discloses a kind of rush for ardealite based cementitious material to coagulate type early strength agent and preparation method thereof, using few Amount slag and alkali-activator are modified ardealite, react soluble P, F in ardealite and generate Ca3(PO4)2Precipitating, The slow setting impurity in ardealite is effectively had cured, a small amount of hydrated product nucleus is formed simultaneously, due to nucleus inductive effect, aquation is produced The short-range order of object arranges, while having broken nucleation barrier, and glue material is added as early strength agent, and hydrated product surrounds nucleus growth, Improve early strength.
Above-mentioned modified product and alum, phosphorus slag, dolime are blended in low temperature calcination in Muffle furnace simultaneously, changed Property sulphate component, main component be β-CaSO4·1/2H2Ardealite calcining is prepared anhydrous sulphur compared at 300~900 DEG C by O Sour calcium greatly reduces activation temperature as sulphate activation agent, while exciting ardealite activity;By modified kraft component It compounds to obtain the early strength agent with accelerating component, the solidifying component of rush, the early stage that can increase substantially ardealite based cementitious material is strong Degree improves setting time.By weight percentage, the early strength agent totality volume accounts for the 3%~10% of cement quality, cost compared with Low, economical and practical, low-temperature activation is modified in ardealite use, and preparation method is simple, and energy consumption is smaller, and the accelerating component promotees to coagulate Component is common chemical products.
The rush of ardealite based cementitious material of the present invention is coagulated in type early strength agent, is promoted solidifying component and is dissolved in water rapidly, is formed strong Alkaline solution increases the pH of entire aquation system liquid phase medium, OH-Rapidly the surface of slag particle is started to corrode, be discharged Activity SiO in slag glass body2、A12O3, form C-S-H gel and hydrated calcium aluminate sulfate AFt, OH-Concentration is bigger, excitation effect Fruit is better, and early strength is also higher;Ardealite in ardealite slag cements plays sulphate activation effect, disintegrates with slag and discharges Active Al2O3Reaction generates hydrated calcium aluminate sulfate AFt, and the hydrated calcium aluminate sulfate AFt of early formation is in the form of a column, is mutually overlapped on Together, C-S-H gel plugs the gap, and provides early strength together, and the AFt quantity of formation is more, and early strength is higher, and early stage CaSO in the forming quantity and solution of AFt4·2H2The solubility of O is positively correlated, and modified kraft component is mainly β-CaSO4·1/ 2H2O, β-CaSO4·1/2H2The solubility of O is much larger than CaSO4·2H2The solubility of O, can be more in aquation early formation AFt;Accelerating component is aluminium-containing substance, and aquation not only generates AFt, but also generates AH3Gel, brilliant glue cooperation, makes AFt be evenly distributed on water In mudstone, Behavior of Hardened Cement Paste early strength and density are improved.
Further advantage, target and feature of the invention will be partially reflected by the following instructions, and part will also be by this The research and practice of invention and be understood by the person skilled in the art.
Specific embodiment
In order to make the present invention realize technological means, creation characteristic, reach purpose and effect more clearly and be apparent to, The present invention is further elaborated With reference to embodiment:
Embodiment 1
A kind of rush for ardealite based cementitious material coagulates type early strength agent, and wherein modified kraft weight percent is 20%, accelerating component weight percent is 60%, and promoting solidifying weight percentages of components is 20%.
Wherein, the modified kraft includes following components by weight percentage: ardealite: granulated blast-furnace slag: Alkali-activator: alum: phosphorus slag: dolime=60%:1.5%:3%:1%:0.5%:2%;The accelerating component by The anhydrous aluminium silicate of 10%:50%:20%:10%, anhydrous calcium sulphoaluminate, aluminum sulfate, dicalcium silicate compounding by weight percentage; The solidifying component of rush is compounded according to the nine water sodium metasilicate of 70:30 with sodium hydroxide.
Wherein, CaSO in the ardealite4·2H2O content >=85%, P2O5、F-≤ 1.5%, granulated blast-furnace slag is S95 Grade, SiO2、Al2O3, CaO total content >=80%, 400~450m of specific surface area2/ kg, the alkali-activator are portland cement Clinker and grinding steel slag mixture.Mixed slurry and alum, phosphorus slag, calcining white clouds as specific embodiment, after the drying Stone is calcined according to weight percent hundred for 97%, 1%, 1% and 1%.
As specific embodiment, the alkali-activator is compounded by Portland clinker and grinding steel slag, by weight Measure percentages, Portland clinker: grinding steel slag=5%~50%:50%~95%;The Portland clinker warp Ball mill grinding, grinding time >=30min, specific surface area >=350m2/kg;The grinding steel slag is the high alkalinity of basicity > 2.5 Steel slag, specific surface area >=500m2/kg。
As specific embodiment, the alum is that industrial aluminum sulphate potassium is dissolved in water, recrystallization preparation;The phosphorus slag partial size ≤ 60 μm, SiO2, CaO total content >=87%, P2O5Content≤3.2%;The dolime calcination temperature is 1100~1200 DEG C, burning quality loss late 45~48%.
The rush of the embodiment 1 coagulates type early strength agent the preparation method is as follows: weighing weight percent 60%:1.5%:3%:35% Ardealite, granulated blast-furnace slag, alkali-activator, water wet-milling 30min in the ball mill, ageing for 24 hours, obtains mixed slurry;It will Mixed slurry dries 1d in 60 DEG C of baking ovens, weighs mixed slurry after the drying of weight percent 97%:1%:1%:1%, bright Alum, phosphorus slag, dolime are calcined in 170 DEG C of Muffle furnaces, heating rate 8 DEG C/min, soaking time 2h, after being cooled to room temperature Calcined product is dry grinded 20min in the ball mill, the powder after dry grinding is crossed into 0.3mm square hole screen to get modified kraft component, Modified kraft component specific surface area >=400m2/kg;Alkali-activator by weight percentage the Portland clinker of 50:50, Grinding steel slag compounding;Accelerating component by weight percentage the anhydrous aluminium silicate of 10%:50%:20%:10, anhydrous calcium sulphoaluminate, Aluminum sulfate, dicalcium silicate compounding;The nine water sodium metasilicate for promoting solidifying component 70:30 by weight percentage are compounded with sodium hydroxide;It will change Property sulphate component, promote solidifying component, the mixing of the ratio of accelerating component 55%:10%:35% by weight percentage, mix ardealite The 8% of based cementitious material weight.Wherein the ratio of mud of ardealite based cementitious material mortar is 0.34, cement mortar rate 1:3, is added 0.5% polycarboxylate water-reducer, the results are shown in Table 1 for mortar experimental performance:
Table 1 implements the performance test results
Embodiment 2
A kind of rush for ardealite based cementitious material coagulates type early strength agent, and wherein modified kraft weight percent is 70%, accelerating component weight percent is 10%, and promoting solidifying weight percentages of components is 30%, wherein in 70% modified kraft Ardealite: granulated blast-furnace slag: alkali-activator: alum: phosphorus slag: dolime=60%:1.5%:3%:1%: 0.5%:2%, in accelerating component by weight percentage the anhydrous aluminium silicate of 10%:50%:20%:10%, anhydrous calcium sulphoaluminate, Aluminum sulfate, dicalcium silicate compounding;The solidifying component of rush compounded according to the nine water sodium metasilicate of 70:30 with sodium hydroxide.
The rush of embodiment 2 coagulate type early strength agent the preparation method is as follows:
Weigh the ardealite, granulated blast-furnace slag, alkali-activator, water of weight percent 60%:1.5%:3%:35% Wet-milling 20min in the ball mill, ageing for 24 hours, obtain mixed slurry;Mixed slurry is dried into 1d in 60 DEG C of baking ovens, weighs weight Mixed slurry, alum, phosphorus slag, dolime are calcined in 150 DEG C of Muffle furnaces after the drying of percentage 97:1:1:1, heating speed Rate 8 DEG C/min, soaking time 3h dry grind calcined product 30min after being cooled to room temperature, in the ball mill by the powder after dry grinding 0.3mm square hole screen is crossed to get modified kraft component, modified kraft component specific surface area >=400m2/kg;Alkali-activator The Portland clinker of 50%:50%, grinding steel slag compounding by weight percentage;Accelerating component 10:50 by weight percentage: The anhydrous aluminium silicate of 20:10, anhydrous calcium sulphoaluminate, aluminum sulfate, dicalcium silicate compounding;Promote solidifying component 70:30 by weight percentage Nine water sodium metasilicate compounded with sodium hydroxide;By modified kraft component, promote solidifying component, accelerating component by weight percentage The ratio of 55%:10%:35% mixes, and 5%, the 10% of incorporation ardealite based cementitious material weight.Wherein ardealite base rubber is solidifying The ratio of mud of material mortar is 0.34, cement mortar rate 1:3,0.5% polycarboxylate water-reducer is added, mortar experimental performance result is such as Shown in table 2:
Table 2 implements the performance test results
Other situations are same as Example 1.
Embodiment 3
A kind of rush for ardealite based cementitious material coagulates type early strength agent, and wherein modified kraft weight percent is 45%, accelerating component weight percent is 30%, and promoting solidifying weight percentages of components is 25%, phosphorus stone in modified kraft therein Cream: granulated blast-furnace slag: alkali-activator: alum: phosphorus slag: dolime=60%:1.5%:3%:1%:0.5%: 2%, the anhydrous aluminium silicate of 10%:50%:20%:10%, anhydrous calcium sulphoaluminate, sulfuric acid by weight percentage in accelerating component Aluminium, dicalcium silicate compounding;The solidifying component of rush compounded according to the nine water sodium metasilicate of 70:30 with sodium hydroxide.
The rush of embodiment 3 coagulate type early strength agent the preparation method is as follows:
Weigh the ardealite, granulated blast-furnace slag, alkali-activator, water of weight percent 60%:1.5%:3%:35% Wet-milling 20min in the ball mill, ageing for 24 hours, obtain mixed slurry;Mixed slurry is dried into 1d in 60 DEG C of baking ovens, weighs weight Mixed slurry, alum, phosphorus slag, dolime are calcined in 130 DEG C of Muffle furnaces after the drying of percentage 97:1:1:1, heating speed Rate 8 DEG C/min, soaking time 4h dry grind calcined product 30min after being cooled to room temperature, in the ball mill by the powder after dry grinding 0.3mm square hole screen is crossed to get modified kraft component, modified kraft component specific surface area >=400m2/kg;Alkali-activator The Portland clinker of 50%:50%, grinding steel slag compounding by weight percentage;Accelerating component 10:50 by weight percentage: The anhydrous aluminium silicate of 20:10, anhydrous calcium sulphoaluminate, aluminum sulfate, dicalcium silicate compounding;Promote solidifying component 70:30 by weight percentage Nine water sodium metasilicate compounded with sodium hydroxide;By modified kraft component, promote solidifying component, accelerating component by weight percentage The ratio of 40%:10%:50% mixes, and the 10% of incorporation ardealite based cementitious material weight.Carry out ardealite based cementitious material Concrete experiments, wherein water-binder ratio 0.24, polycarboxylate water-reducer volume 0.8%, sand coarse aggregate ratio 36%, concrete experiments performance The results are shown in Table 3.
Table 3 implements the performance test results
Other situations are same as Example 1.
Embodiment 4
A kind of rush for ardealite based cementitious material coagulates type early strength agent, and wherein modified kraft weight percent is 20%, accelerating component weight percent is 60%, and promoting solidifying weight percentages of components is 20%.
Wherein, the modified kraft includes following components by weight percentage: ardealite: granulated blast-furnace slag: Alkali-activator: alum: phosphorus slag: dolime=70%:3%:7%:16%:2.5%:1.5%;The accelerating component by The anhydrous aluminium silicate of 10%:50%:20%:10%, anhydrous calcium sulphoaluminate, aluminum sulfate, dicalcium silicate compounding by weight percentage; The solidifying component of rush is compounded according to the nine water sodium metasilicate of 70:30 with sodium hydroxide.
Ardealite, granulated blast-furnace slag, alkali-activator, the water for weighing weight percent 70%:3%:7%:35% exist Wet-milling 30min in ball mill, ageing for 24 hours, obtain mixed slurry;Mixed slurry is dried into 1d in 60 DEG C of baking ovens, weighs weight hundred Mixed slurry, alum, phosphorus slag, dolime are in 170 DEG C of Muffle furnaces after dividing the drying than 97%:16%:2.5%:1.5% Calcining, heating rate 8 DEG C/min, soaking time 2h dry grind calcined product 20min after being cooled to room temperature in the ball mill, will Powder after dry grinding crosses 0.3mm square hole screen to get modified kraft component, modified kraft component specific surface area >=400m2/ kg;The alkali-activator Portland clinker of 50:50, grinding steel slag compounding by weight percentage;Accelerating component by weight hundred Divide anhydrous aluminium silicate, anhydrous calcium sulphoaluminate, the aluminum sulfate, dicalcium silicate compounding than 10%:50%:20%:10;Promote solidifying component to press The nine water sodium metasilicate of weight percent 70:30 are compounded with sodium hydroxide;By modified kraft component, promote solidifying component, accelerating component The ratio of 55%:10%:35% by weight percentage mixes, and the 8% of incorporation ardealite based cementitious material weight.Wherein ardealite The ratio of mud of based cementitious material mortar is 0.34, cement mortar rate 1:3, and 0.5% polycarboxylate water-reducer, mortar experimental performance is added The results are shown in Table 4:
Table 4 implements the performance test results
Finally, it is stated that the above examples are only used to illustrate the technical scheme of the present invention and are not limiting, although referring to compared with Good embodiment describes the invention in detail, those skilled in the art should understand that, it can be to skill of the invention Art scheme is modified or replaced equivalently, and without departing from the objective and range of technical solution of the present invention, should all be covered at this In the scope of the claims of invention.

Claims (4)

1. a kind of rush for ardealite based cementitious material coagulates type early strength agent, it is characterised in that: forged by the high temperature mixed It burns modified kraft, accelerating component and promotees solidifying group and be grouped as;Wherein high-temperature calcination modified kraft weight percent be 20%~ 70%, accelerating component weight percent is 10%~60%, and promoting solidifying weight percentages of components is 10%~45%;High-temperature calcination changes Property sulfate the preparation method comprises the following steps: take ardealite, granulated blast-furnace slag, alkali-activator and water in ball respectively according to weight percent Wet-milling in grinding machine, then be aged, mixed slurry is obtained, mixed slurry is dried into 1h~2h in 50 DEG C~60 DEG C baking ovens, then will be dried Mixed slurry after dry is calcined in 110 DEG C~180 DEG C Muffle furnaces with alum, phosphorus slag, dolime, after cooling will calcining Product is dry grinded in the ball mill, and component of the mill after dry is then sifted out to obtain high-temperature calcination modified kraft;By weight percentage, Ardealite: granulated blast-furnace slag: alkali-activator: alum: phosphorus slag: dolime=50%~70%:1~3%:1%~ 7%:25%~40%:0.5%~3%:0.5%~2%.
2. a kind of rush for ardealite based cementitious material coagulates type early strength agent according to claim 1, it is characterised in that: described Alkali-activator is Portland clinker and grinding steel slag mixture.
3. a kind of rush for ardealite based cementitious material coagulates type early strength agent according to claim 1, it is characterised in that: described CaSO in ardealite4·2H2O content >=85%, P2O5、F-≤ 1.5%.
4. a kind of rush for ardealite based cementitious material coagulates type early strength agent according to claim 1, it is characterised in that: described Granulated blast-furnace slag is S95 grades, SiO2、Al2O3, CaO total content >=80%, 400~450m of specific surface area2/kg。
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CN104803651A (en) * 2015-04-28 2015-07-29 铜陵海源超微粉体有限公司 Gypsum-based cementing material
CN105384373A (en) * 2015-11-09 2016-03-09 铜陵化学工业集团有限公司 Phosphogypsum-based cement cementing material and coagulation accelerator thereof

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