CN103074667A - Method for preparing calcium sulfate whisker through recrystallization - Google Patents
Method for preparing calcium sulfate whisker through recrystallization Download PDFInfo
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- CN103074667A CN103074667A CN2013100366352A CN201310036635A CN103074667A CN 103074667 A CN103074667 A CN 103074667A CN 2013100366352 A CN2013100366352 A CN 2013100366352A CN 201310036635 A CN201310036635 A CN 201310036635A CN 103074667 A CN103074667 A CN 103074667A
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Abstract
The invention discloses a method for preparing a calcium sulfate whisker through recrystallization. The method is characterized in that the method comprises the steps of (1), conducting program control on heating and dissolution courses: putting a raw material with a main ingredient of calcium sulfate into a sulphuric acid solution for stirring, heating simultaneously, heating a mixture to 60-95 DEG C at a certain rate with the adoption of the program control, dissolving for 20min-1h, (2), conducting the program control on cooling and recrystallization courses: using the program control to cool a suspension obtained by dissolution to 10-30 DEG C, ageing for 20min-2h, (3), conducting separating and washing courses: conducting solid-liquid separation on the suspension, washing a separated solid-phase product, and (4), conducting a drying course: drying the washed solid-phase product at a certain temperature, and obtaining the calcium sulphate dihydrate whisker. The calcium sulfate whisker is prepared by utilizing a recrystallization principle under an ordinary-pressure mild condition, and a relatively economical technological approach can be provided for the resource utilization of industrial by-products such as desulfurization gypsum and phosphogypsum.
Description
Technical field
The invention belongs to calcium sulfate inorganic mineral whisker preparing technical field, be specifically related to a kind of under the normal pressure mild conditions, utilize the recrystallization principle to realize the calcium sulfate crystal whiskers preparation, the technological approaches of less expensive can be provided for the recycling of the industrial by-products such as desulfurated plaster, phosphogypsum.
Background technology
Calcium sulfate crystal whiskers refers under the certain condition the similar staple fibre of shape with the growth of monocrystalline form, and (diameter is generally between 0.01 ~ 10 μ m; length-to-diameter ratio reaches 5 ~ 1000) must shape single crystal; it is a kind of environmental protection inorganic material; at building, medicine, plastics, rubber and field of environment protection important purposes is arranged, at present more as the matrix material reinforcing component.The main method of disclosed preparation calcium sulfate crystal whiskers can be divided into the hot method of hydraulic pressure and normal pressure acidization.
The hot method of hydraulic pressure is that the dihydrate gypsum suspension with the certain mass mark is added in the hydrothermal reaction kettle, depresses reaction at saturation steam, makes the calcium sulfate crystal whiskers of tiny needle-like.These class methods have the advantages such as the high and technique of transformation efficiency is simple, but the general requirement temperature is high to the requirement of hydro-thermal reaction device at 100-200 ℃, and one-time investment greatly, production cost is higher, and industrial applications is subject to certain limitation.Wherein some method also need add a certain proportion of crystal seed and additive, and process complexity and cost increase, and regulate and control more loaded down with trivial details.As, published patented technology CN101230483A namely " produces the method for crystal whisker of gypsum " with citrate of lime, and reaction needed is 120 ~ 130 ℃ of reactions of holding temperature in the 0.27MPa autoclave.And for example, patent CN101311337A disclosed " utilizing desulfurized gesso of flue gas to prepare the method for calcium sulfate crystal whiskers ", require adding inhibitor control pH value is 2 ~ 6, then being controlled at temperature and being 110 ~ 200 ℃, pressure is to react under 0.2 ~ 1.2MPa condition.It is more that these class methods propose, and sees that notification number is the patent application of CN101544385, CN1477242, CN102002756A, CN102605430A, CN102212884A, CN101994153A, CN101550602.
The normal pressure acidization refers to high density dihydrate gypsum suspension is placed acidic solution under the certain temperature, by regulation and control acidity (pH value) and temperature of reaction, makes it to change into needle-like or fibrous hemihydrate calcium sulfate crystal whisker.Compare with the hot method of hydraulic pressure,, this method does not need high temperature, high-pressure reactor, and cost decreases.But disclosed a lot of normal pressure acidization technique still exists operation too much, controls complicated problem, so that industrial prospect is affected.Such as, patent CN1584130 disclosed " making the method for crystal whisker of gypsum in phosphoric acid ", it is characterized by: using excessive concentration is that 30 ~ 40% phosphoric acid and phosphorus ore leach chemical reaction; The control temperature is 50 ~ 95 ℃, through 2 ~ 4 hours reaction, tells liquid phase and is also filtered, and obtains containing H
3PO
43 ~ 4mol/L, Ca
2+0.8 the phosphoric acid leaching liquid of ~ 1.2mol/L; And then gradually it to be added concentration be that stirring reaction 120 ~ 150min under 50 ~ 100 ℃ of conditions can obtain Dihydrate gypsum whiskers in 30 ~ 35% the sulphuric acid soln.The forming process of this technology crystal whisker of gypsum need to have simultaneously high-concentration phosphoric acid and sulfuric acid just can be finished, and is only applicable to the phosphoric acid production commercial run or the region of phosphorus ore is arranged.And for example, patent CN101311355 discloses a kind of method of preparing calcium sulphate whiskers from ardealite, be raw material with the solid slag phosphogypsum, preparing diameter of whiskers through synthetic reaction, filtration, heating for dissolving, heat filtering and crystallisation by cooling is 1～4 μ m, length 50～200 μ m, the calcium sulfate crystal whiskers product that diameter and length are controlled.The method need to add the pH adjusting agent, and to make the potential of hydrogen of solution be 7.5～12, also adds the magnesium nitrate powder as the crystalline form growth substance, and pre-treatment step is many, and temperature has increased regulation and control difficulty and cost all more than 100 ℃.Similarly normal pressure acidization processing method is seen the patent applications such as notification number CN102303852A, CN102352528A, CN1796285, CN101092734, CN102534801A, CN102634843A.
In addition, the method that also has the more complicated slurries system of utilization to prepare whisker is suggested, as utilize the organism such as methyl alcohol, ethanol as reaction medium, the auxiliary various crystal control agents etc. that add in the process, solution system composition and additive that these methods adopt are more, more complicated, follow-up regulation and control with separate loaded down with trivial details, cause inevitably industrialization investment and cost to increase, also may bring secondary pollution, and be unfavorable for using chemical gypsum in enormous quantities as raw material realizing its resource utilization (further reducing the whisker cost), thereby limited industrial applications.
The preparation process of calcium sulfate crystal whiskers meets the growth mechanism of general crystal, comprises that nucleus forms and two processes of crystal growth, can keep certain degree of supersaturation but its precondition is solution.The forming process of calcium sulfate crystal whiskers in solution be from the macroscopic view process that to be crystal-solution interface pass to the solution, is to form the process that the particle of crystal is arranged by the space lattice structure from microcosmic.Morphology is subjected to the impact of the factors such as crystalline structure, surface energy, each crystal face relative growth rate and envrionment conditions.Under the hydrothermal condition, temperature of reaction, temperature rise rate, pressure, medium pH, additive types and quantity etc. all can exert an influence to each face family growth velocity of nucleation, growth and crystal of crystal and make crystal present certain pattern.For preparing whisker, must keep certain degree of supersaturation and reduce the inhibition that crystal C direction of principal axis crystal face is grown, make calcium sulphate crystal continue growth along the C direction of principal axis.
Find by the systematic study to sulfuric acid-calcium sulphate soln system, interval in certain temperature, the solubleness of calcium sulfate presents certain Changing Pattern, under the condition of not introducing other conditioning agents, can realize the flexible regulation and control of system calcium sulfate degree of supersaturation realizing that calcium sulphate crystal is along the axial dominant growth of C by the control of temperature changing process accurately.
Summary of the invention
The object of the invention is to for the existing high-temperature and high-pressure conditions cost of existing calcium sulfate crystal whiskers technology of preparing high, and the regulation and control complexity causes the industrial application hard problem, a kind of succinct efficiently recrystallization calcium sulphate crystal whisker preparation method is provided, the method is the least possible introducing interfering substance and simplification regulatory factor in system, utilize and dissolve---the recrystallization principle prepares calcium sulfate crystal whiskers, under condition of normal pressure, select industrial sulphuric acid soln commonly used as reaction medium, according to calcium sulfate solubleness variation with temperature rule in the sulphuric acid soln of different concns, utilize temperature variation and regulation and control to realize the dissolve-repreparation process, and grow into the crystal whisker-shaped Dihydrate gypsum whiskers, further can be processed into half water and anhydrous calcium sulfate whisker.
Recrystallization of the present invention prepares the method for calcium sulfate crystal whiskers, comprises the step of following order:
(1) time variable control rising temperature for dissolving process: be that the raw material of calcium sulfate drops in the sulphuric acid soln and stirs with main component, simultaneously heating adopts time variable control with given pace mixture to be warming up to 60 ~ 95 ℃ and dissolve 20min ~ 1h;
(2) time variable control cooling recrystallization process: the suspension that will dissolve gained adopts time variable control to be cooled to 10 ~ 30 ℃ with given pace, and ageing 20min ~ 2h;
(3) separation, washing process: suspension is carried out solid-liquid separation, and the isolated solid product of institute is washed;
(4) drying process: the washed solid product of institute is dry at a certain temperature, namely obtain Dihydrate gypsum whiskers.
More particularly, in the described raw material of step (1), the mass percent of calcium sulfate 〉=50%, raw material particle size is below 30mm.Raw material sources of the present invention are extensive, be not limited to wet containing of calcium salt and sulfate liquor reaction product or dry solid materials, also can be used as raw material such as calcium sulfate reagent, plaster of paris ore deposit and the industrial by-products such as desulfurated plaster, phosphogypsum and fluorgypsum, this is that utilization of waste material, the cost that reduces whisker are laid a good foundation.
More particularly, in the step (1), the mass concentration of described sulphuric acid soln is 1.8% ~ 45.0%, is preferably 15% ~ 35%; The quality of described adding raw material is 0.2% ~ 35% of total mass after mixing; Describedly with given pace mixture is warming up to 60 ~ 95 ℃ and refers to mixture is increased to 60 ~ 95 ℃ with the speed of 0.5K/min ~ 5K/min, be preferably 70-85 ℃.
More particularly, the described suspension of step (2) is the supernatant liquor of taking from step (1) gained solution, its solid holdup≤2%.
More particularly, be cooled to 10 ~ 30 ℃ with given pace described in the step (2) and refer to supernatant liquor is placed on that the mean rate with 0.2K/min ~ 15K/min is cooled to 10 ~ 30 ℃ in the crystallization reactor with chuck; Can adopt indirect cooling water, refrigerating fulid or cold air as the cooling medium.
More particularly, the described time variable control cooling of step (2) refers to, by adopting programmable logic controller (PLC), electric thermo-couple temperature to detect and the integrated automatic control technology of intelligent PID (proportional-integral-differential) controller, cryogenic media flow and temperature in the crystallization reactor chuck are regulated, and then realization is to the control of crystallization reactor rate of temperature fall.
More particularly, the described ageing 20min ~ 2h of step (2) refers to that constant temperature keeps 20min ~ 2h under the temperature when cooling stops, reaches stable until grow the crystal whisker-shaped product, is preferably ageing 30min ~ 1.0h.
More particularly, the described at a certain temperature drying of step (4) refers to solid product is being obtained Dihydrate gypsum whiskers behind dry 0.5 ~ 3h under 50 ~ 110 ℃ the temperature, and when temperature was high, the corresponding time can suitably shorten.On this basis, can further Dihydrate gypsum whiskers be obtained hemihydrate calcium sulfate crystal whisker at 110 ~ 200 ℃ of lower dry 0.5 ~ 3h, can obtain anhydrous calcium sulfate whisker at 200 ~ 800 ℃ of lower calcining 0.5 ~ 3h.
Wherein, the solid-liquid separation in the above-mentioned steps (3) can adopt the modes such as industry centrifugal, press filtration commonly used or vacuum filtration to carry out, simultaneously with the clear water cleaning product to conforming to quality requirements.The recyclable dissolution process that is used further to of isolated sulphuric acid soln reclaims after the washing water by precipitation and uses a part, regularly discharges a part, and solid phase then is used for next step dry or calcining.
The prepared calcium sulfate crystal whiskers matter of the inventive method is white, pattern is even, and diameter can be controlled in 0.1 μ m ~ 15 μ m, and length is controlled in 10 ~ 800 mu m ranges.The present invention has following beneficial effect:
(1) the inventive method principle is reliable and stable, and the technology operation is succinct, only need control emphatically temperature variation, easy handling.
(2) carry out crystallization under the normal pressure, integrated industrial reactor commonly used and control techniques, investment and running cost are lower.
(3) energy consumption is lower, the waste heat of plant of can suiting measures to local conditions to utilize.
(4) be easy to realize continuous production, and can be the recycling that starting material are realized industrial waste with chemical gypsum.
Description of drawings
Fig. 1 is process flow sheet of the present invention.
Fig. 2 embodiment of the invention is the optical microscope image of the Dihydrate gypsum whiskers product of raw material preparation with the chemical reagent terra alba.
Fig. 3 is that embodiment of the invention desulfurated plaster is the optical microscope image of the Dihydrate gypsum whiskers product of raw material preparation.
Embodiment
The present invention is described in further detail below in conjunction with drawings and Examples.Equipment used and raw material are the conventional dose of general-purpose equipment among the embodiment.
Embodiment 1:
It is to stir in 14% the sulphuric acid soln that 110g sulfate dihydrate calcon is joined the 1L mass percent concentration, speed with 1.5K/min is heated to 85 ℃ of dissolvings simultaneously, then leave standstill, regulate the flow of chuck freezing air by the PID Controlling System, make suspension temperature be down to 20 ℃ with the mean rate of 0.5K/min, and keep this temperature ageing 0.5h, product is filtered and wash with clear water, again at 60 ℃ of lower dry 1h, obtain length-to-diameter ratio and be 50 ~ 110 Dihydrate gypsum whiskers.
Embodiment 2:
The Gypsum Mine (calcium sulphate content 〉=70%) of 6kg particle diameter≤3cm joined to fill the 200L mass percent concentration be to stir in 25% the sulphuric acid soln groove, be heated to the speed of 2.0K/min simultaneously and reduce stirring intensity after 90 ℃ of dissolvings or leave standstill; To stir in the top suspension suction crystallization reactor, the flow by PID Controlling System adjusting chuck cold air makes suspension temperature be down to 20 ℃ with the mean rate of 1.0K/min, and keeps this temperature ageing 1h; With product by vacuum filtration, and with clear water washing to conforming to quality requirements; The solid product that separates is put into baking oven, at 60 ℃ of lower dry 1h, obtain length-to-diameter ratio and be 50 ~ 110 Dihydrate gypsum whiskers.
Embodiment 3:
The 1kg desulfurated plaster joined to fill the 100L mass percent concentration be to stir in 35% the sulphuric acid soln groove, leave standstill after being heated to 75 ℃ of dissolvings with the speed of 0.5K/min simultaneously; To stir in the top suspension suction crystallization reactor, regulate the flow of chuck cold water by the PID Controlling System, make suspension temperature be down to 20 ℃ with the mean rate of 1.5K/min, and keep this temperature ageing 0.5h, product is filtered and wash with clear water, again at 60 ℃ of lower dry 1h, obtain length-to-diameter ratio and be 50 ~ 180 Dihydrate gypsum whiskers.
Embodiment 4:
It is to stir in 30% the sulphuric acid soln that 5.0g sulfate dihydrate calcon is joined the 1L mass percent concentration, speed with 3.0K/min is heated to 85 ℃ of dissolvings simultaneously, then leave standstill, regulate the flow of chuck cold water by the PID Controlling System, make suspension temperature be down to 20 ℃ with the mean rate of 2.5K/min, and keep this temperature ageing 0.5h, product is filtered and wash with clear water, again at 60 ℃ of lower dry 0.5h, obtain length-to-diameter ratio and be 50 ~ 110 Dihydrate gypsum whiskers, further at 150 ℃ of lower dry 1h, obtain hemihydrate calcium sulfate crystal whisker; At 600 ℃ of lower calcining 1h, obtain anhydrous calcium sulfate whisker.
Embodiment 5:
It is to stir in 38% the sulphuric acid soln that 14g sulfate dihydrate calcon is joined the 1L mass percent concentration, speed with 5.0K/min is heated to 80 ℃ of dissolvings simultaneously, then leave standstill, regulate the flow of chuck cold water by the PID Controlling System, make suspension temperature be down to 20 ℃ with the mean rate of 5K/min, and keep this temperature ageing 0.5h, product is filtered and wash with clear water, again at 60 ℃ of lower dry 1h, obtain length-to-diameter ratio and be 50 ~ 110 Dihydrate gypsum whiskers.
Embodiment 6:
The Gypsum Mine (calcium sulphate content 〉=80%) of 5kg joined to fill the 100L mass percent concentration be to stir in 40% the sulphuric acid soln groove, leave standstill after being heated to 92 ℃ of dissolvings with the speed of 4.0K/min simultaneously; To stir in the top suspension suction crystallization reactor, the flow by PID Controlling System adjusting chuck cold water makes suspension temperature be down to 20 ℃ with the mean rate of 10K/min, and keeps this temperature ageing 1.5h; With product centrifuging, and with clear water washing to conforming to quality requirements; The solid product that separates is put into baking oven, at 60 ℃ of lower dry 2h, obtain length-to-diameter ratio and be 50 ~ 110 Dihydrate gypsum whiskers.
Embodiment 7:
(size≤3cm) joins and fills the 1000L mass percent concentration is to stir in 32% the sulphuric acid soln groove, leaves standstill after being heated to 88 ℃ of dissolvings with the speed of 2.5K/min simultaneously with the 50kg phosphogypsum; To stir in the top suspension suction crystallization reactor, the flow by PID Controlling System adjusting chuck cold water makes suspension temperature be down to 20 ℃ with the mean rate of 15K/min, and keeps this temperature ageing 2h; The product press filtration is separated, and wash to conforming to quality requirements with clear water; The solid product that separates is put into baking oven, at 100 ℃ of lower dry 1.5h, obtain length-to-diameter ratio and be 50 ~ 110 Dihydrate gypsum whiskers.
Embodiment 8:
It is to stir in 30% the sulphuric acid soln that 92g sulfate dihydrate calcon is joined the 10L mass percent concentration, speed with 1.0K/min is heated to 82 ℃ of dissolvings simultaneously, then leave standstill, regulate the flow of chuck liquid nitrogen by the PID Controlling System, make suspension temperature be down to 10 ℃ with the mean rate of 15K/min, and keep this temperature ageing 1h, product is filtered and wash with clear water, again at 60 ℃ of lower dry 0.5h, obtain length-to-diameter ratio and be 30 ~ 90 Dihydrate gypsum whiskers.
Embodiment 9:
The 1kg desulfurated plaster joined to fill the 100L mass percent concentration be to stir in 35% the sulphuric acid soln groove, leave standstill after being heated to 86 ℃ of dissolvings with the speed of 1.2K/min simultaneously; To stir in the top suspension suction crystallization reactor, regulate the flow of chuck cold water by the PID Controlling System, make suspension temperature be down to 18 ℃ with the mean rate of 2.5K/min, and keep this temperature ageing 0.5h, product is filtered, and with the clear water washing, again at 95 ℃ of lower dry 1h, obtain length-to-diameter ratio and be 60 ~ 150 Dihydrate gypsum whiskers, its optical microscope image is seen Fig. 3; Product further at 150 ℃ of lower dry 1.5h, is obtained hemihydrate calcium sulfate crystal whisker; At 700 ℃ of lower calcining 1.5h, obtain anhydrous calcium sulfate whisker.
Embodiment 10:
The 200kg desulfurated plaster joined to fill the 1000L mass percent concentration be to stir in 32% the sulphuric acid soln groove, leave standstill after being heated to 78 ℃ of dissolvings with the speed of 0.5K/min simultaneously; To stir in the top suspension suction crystallization reactor, the flow by PID Controlling System adjusting chuck cold water makes suspension temperature be down to 20 ℃ with the mean rate of 4.0K/min, and keeps this temperature ageing 0.5h; Product is filtered, and acid solution is returned the dissolving tank recycling, and solid product washs to conforming to quality requirements with clear water; Solid phase after the washing at 100 ℃ of lower dry 1h, is obtained length-to-diameter ratio and is 40 ~ 120 Dihydrate gypsum whiskers.
Embodiment 11:
It is to stir in 33% the sulphuric acid soln that 5g sulfate dihydrate calcon is joined the 1L mass percent concentration, and the speed with 0.5K/min is heated to 78 ℃ of dissolvings simultaneously, then leaves standstill; Utilize freezing air to make suspension temperature be down to 30 ℃ with the mean rate of 0.5K/min, and keep this temperature ageing 0.5h; Product filtered and with the clear water washing, again at 60 ℃ of lower dry 0.5h, obtain length-to-diameter ratio and be 30 ~ 60 Dihydrate gypsum whiskers.
Embodiment 12:
It is to stir in 30% the sulphuric acid soln that 140g sulfate dihydrate calcon is joined the 1L mass percent concentration, and the speed with 1.5K/min is heated to 88 ℃ of dissolvings simultaneously; Flow by PID Controlling System adjusting chuck cold water makes suspension temperature be down to 15 ℃ with the mean rate of 1.5K/min, and keeps this temperature ageing 1.5h; Product filtered and with the clear water washing, again at 70 ℃ of lower dry 1h, obtain length-to-diameter ratio and be 50 ~ 120 Dihydrate gypsum whiskers, its optical microscope image is seen Fig. 2; 110 ℃ of calcinings, obtain hemihydrate calcium sulfate crystal whisker; 500 ℃ of calcinings, obtain anhydrous calcium sulfate whisker.
Claims (9)
1. a recrystallization prepares the method for calcium sulfate crystal whiskers, it is characterized in that comprising the step of following order:
(1) time variable control rising temperature for dissolving process: be that the raw material of calcium sulfate drops in the sulphuric acid soln and stirs with main component, simultaneously heating adopts time variable control with given pace mixture to be warming up to 60 ~ 95 ℃ and dissolve 20min ~ 1h;
(2) time variable control cooling recrystallization process: the suspension that will dissolve gained adopts time variable control to be cooled to 10 ~ 30 ℃ with given pace, and ageing 20min ~ 2h;
(3) separation, washing process: suspension is carried out solid-liquid separation, and the isolated solid product of institute is washed;
(4) drying process: the washed solid product of institute is dry at a certain temperature, namely obtain Dihydrate gypsum whiskers.
2. described recrystallization prepares the method for calcium sulfate crystal whiskers according to claim 1, it is characterized in that: in the described raw material of step (1), and the mass percent of calcium sulfate 〉=50%, raw material particle size is below 30mm.
3. described recrystallization prepares the method for calcium sulfate crystal whiskers according to claim 2, and it is characterized in that: in the step (1), the mass concentration of described sulphuric acid soln is 1.8% ~ 45.0%, is preferably 15% ~ 35%; The quality of described adding raw material is 0.2% ~ 35% of total mass after mixing.
4. described recrystallization prepares the method for calcium sulfate crystal whiskers according to claim 3, it is characterized in that: with given pace mixture is warming up to 60 ~ 95 ℃ described in the step (1) and refers to mixture is increased to 60 ~ 95 ℃ with the speed of 0.5K/min ~ 5K/min, be preferably 70-85 ℃.
5. described recrystallization prepares the method for calcium sulfate crystal whiskers according to claim 1, and it is characterized in that: the described suspension of step (2) is the supernatant liquor of taking from step (1) gained solution, its solid holdup≤2%.
6. described recrystallization prepares the method for calcium sulfate crystal whiskers according to claim 5, it is characterized in that: be cooled to 10 ~ 30 ℃ with given pace described in the step (2) and refer to supernatant liquor is placed on that the mean rate with 0.2K/min ~ 15K/min is cooled to 10 ~ 30 ℃ in the crystallization reactor with chuck.
7. described recrystallization prepares the method for calcium sulfate crystal whiskers according to claim 6, it is characterized in that: the described time variable control cooling of step (2) refers to, by adopting programmable logic controller, electric thermo-couple temperature to detect and the integrated automatic control technology of intelligent PID controller, cryogenic media flow and temperature in the crystallization reactor chuck are regulated, and then realization is to the control of crystallization reactor rate of temperature fall.
8. described recrystallization prepares the method for calcium sulfate crystal whiskers according to claim 7, it is characterized in that: the described ageing 20min ~ 2h of step (2) refers to that constant temperature keeps 20min ~ 2h under the temperature of supernatant liquor when cooling stops, reach stable until grow the crystal whisker-shaped product, be preferably ageing 30min ~ 1.0h.
9. described recrystallization prepares the method for calcium sulfate crystal whiskers according to claim 1, it is characterized in that: the described at a certain temperature drying of step (4) refers to solid product dry 0.5 ~ 3h under 50 ~ 110 ℃ temperature.
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| CN103526277A (en) * | 2012-10-26 | 2014-01-22 | 青岛科技大学 | Method for manufacturing gypsum whisker with hexagonal cross section and low phosphorus content |
| CN103540993A (en) * | 2013-10-31 | 2014-01-29 | 洛阳氟钾科技有限公司 | Method for preparing calcium sulfate whiskers by use of potassium feldspar decomposition residue |
| CN103628142A (en) * | 2013-11-01 | 2014-03-12 | 贵州开磷（集团）有限责任公司 | Method for preparing phosphogypsum whiskers by secondary crystallization |
| CN104532339A (en) * | 2014-12-16 | 2015-04-22 | 青海博川矿业开发有限公司 | Method for preparing calcium sulfate whisker from low-grade natural gypsum or gypsum tailings |
| CN104528798A (en) * | 2014-12-16 | 2015-04-22 | 中国科学院青海盐湖研究所 | Method for purifying low-grade natural gypsum or gypsum tailings by recrystallization |
| CN104562180A (en) * | 2015-01-07 | 2015-04-29 | 西南科技大学 | Method for preparing calcium sulfate whisker from phosphogypsum |
| CN104651944A (en) * | 2015-02-12 | 2015-05-27 | 湘潭大学 | Preparation method of calcium-sulfate-based calcium sulfate crystal whisker |
| CN104846440A (en) * | 2015-05-29 | 2015-08-19 | 昆明冶金研究院 | Method for preparing high-purity calcium sulfate dihydrate crystal whisker by using metallurgic flue gas desulfurization gypsum recrystallization process |
| CN106801259A (en) * | 2017-01-17 | 2017-06-06 | 辽宁工程技术大学 | A kind of method that mechanical force activating desulfurated plaster prepares calcium sulfate crystal whiskers |
| CN107557870A (en) * | 2017-09-08 | 2018-01-09 | 云南磷化集团有限公司 | A kind of method with preparing calcium sulphate whiskers from ardealite |
| CN108394981A (en) * | 2018-03-29 | 2018-08-14 | 德淮半导体有限公司 | Treatment liquid and preparation method thereof containing phosphorus waste liquid |
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| CN110205679A (en) * | 2019-06-25 | 2019-09-06 | 湖南迈辉环保材料有限公司 | The manufacturing method of wgrg high strength crystal whisker gypsum |
| CN110453286A (en) * | 2019-09-18 | 2019-11-15 | 云南凝创环保科技有限公司 | A kind of method of semi-transparent embrane method production Dihydrate gypsum whiskers |
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