CN106480507A - A kind of new technology of ardealite preparation low cost hemihydrate calcium sulfate crystal whisker - Google Patents
A kind of new technology of ardealite preparation low cost hemihydrate calcium sulfate crystal whisker Download PDFInfo
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- CN106480507A CN106480507A CN201611002654.3A CN201611002654A CN106480507A CN 106480507 A CN106480507 A CN 106480507A CN 201611002654 A CN201611002654 A CN 201611002654A CN 106480507 A CN106480507 A CN 106480507A
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
- C30B29/62—Whiskers or needles
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/46—Sulfur-, selenium- or tellurium-containing compounds
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/10—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by application of pressure, e.g. hydrothermal processes
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- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
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- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
A kind of new technology of ardealite preparation low cost hemihydrate calcium sulfate crystal whisker, comprises the steps：(1) adopt flotation desilication technology to remove quartz and partial impurities in ardealite, improve sulfate dihydrate calcium content >=92.0% in ardealite；In step（1）Its weight 0.5～2.0% dispersant, grinding 5～30min after mixing is added, it is standby that homogenizing process is prepared into solids content 5～12% in the upgrading ardealite obtaining；（3）Add its weight 0.1～5.0% crystal modifier and 1% sulphuric acid or hydrochloric acid in ardealite slurry, stir, proceed in pressure reaction still；（4）Crystal whisker of gypsum converts：120～140 DEG C of conversion temperature of setting, reacts temperature retention time 2.0h, after question response is complete, fast filtering, and dehydration, it is dried more than 80 DEG C of temperature, obtain final product hemihydrate calcium sulfate crystal whisker.Process is simple, low cost, gained Calcium Sulfate Whiskers are tiny, and draw ratio is high, and pattern is completely uniform.
Description
Technical field
The present invention relates to a kind of new technology of ardealite preparation low cost hemihydrate calcium sulfate crystal whisker.
Background technology is led
Ardealite is the by-product during Wet-process phosphoric acid (WPPA).With the continuous increasing to high-concentration phosphate compound fertilizerses demand both at home and abroad
Long, promote phosphoric acid by wet process industrial expansion, also create more ardealites.Therefore, the comprehensive resource profit to ardealite
With having critically important resource and Significance for Environment.
Calcium sulfate crystal whiskers, call crystal whisker of gypsum, also known as gypsum fiber, white fluffy solid, refer under certain condition with
The palpus shape monocrystal being shaped like chopped fiber of single crystal form growth, its intensity theoretical strength that valency is good for close between material atom.
Its main character is as follows：（1）There is excellent mechanical property：Its section mostly is hexagon, rhomboid, triangle or strip shape,
Different from the circular cross section of glass fibre etc., considerably increase draw ratio, increase plastics, fire-proof board draw ratio can be met
（30-100）Requirement；Tensile strength is 5-10 times of glass fibre；Temperature does not decompose softening when raising, and intensity is almost lossless
Lose, can be applicable to fire proofing material；No fatigue effect, be ground into powder, cut-out after, intensity is not also suffered a loss.（2）Have well
Stability and the compatibility, excellent flatness, regenerability is good.（3）Toxicity is low：Compared with other whiskers, toxicity is minimum.（4）Become
This is low：Calcium sulfate crystal whiskers internal price is 6-12 unit/kg, the only 1/300-1/200 of silicon carbide whisker.Building,
Medicine, plastics, rubber and field of environment protection have important purposes, are more used as composite reinforcing component at present.
Publication No. CN102115142A Chinese invention patent, discloses a kind of preparation method of industrial sulphuric acid calcium.The party
With ardealite as raw material, first washing removes soluble impurity to method, recycles excessive hydrochloric acid to remove insoluble phosphate with other not
Solubility impurity, last filtration separation purified after industrial sulphuric acid calcium.The method needs to remove dephosphorization stone using excessive hydrochloric acid
Silicon dioxide in cream, to improve the content of calcium sulphate dihydrate in ardealite.Publication No. CN104562180A Chinese invention is special
Profit, discloses a kind of method of use preparing calcium sulphate whiskers from ardealite.The method with ardealite breeze and diluted acid, in uniform temperature
Lower reaction, the calcium sulphate dihydrate in ardealite is completely dissolved in diluted acid, then makes the side of calcium sulphate dihydrate recrystallization by cooling
Method prepares calcium sulfate crystal whiskers.The method needs a large amount of Ore Leachings, and serious to equipment corrosion, the crystallization time is long, subsequently simultaneously
The product pH substantial amounts of fresh water (FW) of relatively low needs obtaining is washed, and has greater environmental impacts.
In sum, forefathers are made that fruitful work in terms of preparing calcium sulphate whiskers from ardealite, but remain work
The shortcomings of skill is complicated, crystal whisker products are unstable, production cost is high.
Content of the invention
It is an object of the invention to provide a kind of new technology of ardealite preparation low cost hemihydrate calcium sulfate crystal whisker, existing to solve
There is problem present in technology.
Technical scheme：
A kind of new technology of ardealite preparation low cost hemihydrate calcium sulfate crystal whisker, comprises the steps：
（1）, using quartz and partial impurities in ardealite, there is floatability, ardealite removed using flotation desilication technology
In quartz and partial impurities, improve ardealite in sulfate dihydrate calcium content >=92.0%；
（2）, in step（1）In the upgrading ardealite obtaining plus its weight 0.5～2.0% dispersant, grinding 5 after mixing～
30min, it is standby that homogenizing process is prepared into solids content 5～12% slurry；Preferably, homogenizing is processed is prepared into solids content 10%
Slurry；Described dispersant be one of technical grade sodium pyrophosphate, sodium hexameta phosphate, polyacrylamide or lignin sodium sulfonate or
Several mixing.
（3）, to step（2）It is obtained in ardealite slurry and add this slurry weight 0.1～5.0% crystal modifier and 1% industry
Level sulphuric acid or hydrochloric acid, and adjust pH value 2～5, stir to material uniformly, then proceed in pressure reaction still；
（4）Crystal whisker of gypsum converts：120～140 DEG C of conversion temperature of setting, reacts temperature retention time 2.0h, after question response is complete, quickly
Filter, dehydration, be dried more than 80 DEG C of temperature, obtain final product hemihydrate calcium sulfate crystal whisker.Wherein filtrate contains crystal modifier and sulphuric acid, returns step
Suddenly（2）Middle continuation recycles.
Described crystal modifier is inorganic salt or organic additive, wherein：Inorganic salt is sodium chloride, potassium chloride, zinc chloride, chlorination
One in magnesium, sodium sulfate, potassium sulfate, zinc sulfate, magnesium sulfate, aluminum sulfate, sodium phosphate, potassium phosphate, zinc phosphate, magnesium phosphate and aluminum phosphate
Plant or multiple combinations；Organic additive is cetyl trimethylammonium bromide, dodecylbenzene sodium sulfonate, hexadecyl hydrosulfate
The combination of one or more of sodium, Oleic acid and enuatrol；The aforementioned inorganic salt as crystal modifier or organic additive are work
Industry level commercial sources.
The hemihydrate calcium sulfate crystal whisker being obtained in aforementioned manners, sulfate hemihydrate calcium content >=92.00%（wt%）, whiteness is more than
92%, loose thickness:0.1～0.3g/cm3, whisker length：20～500um, diameter of whiskers：1～4um, draw ratio 10～100.
It is process is simple that the present invention prepares the maximum feature of hemihydrate calcium sulfate crystal whisker, low production cost, and prepared calcium sulfate crystal whiskers have
Diameter is tiny, and draw ratio is high, and pattern is completely uniform.Can as to whiteness require be not particularly harsh Colophonium, plastics, rubber,
The reinforcing material additive of the industry such as brake block and pottery, has broad application prospects.
The technical advantage of the present invention：Using gypsum grinding homogenizing treatment technology, increased Gypsum Fibrosum conversion ratio.Adopted by contrast
With homogenizing technology and the semi-hydrated gypsum whisker SEM spectrum being provided without uniform technology, result illustrates, solves Gypsum Fibrosum using this technology brilliant
The uneven technical problem of whisker in palpus preparation process, this technology has low cost and the uniform feature of slurry.
Brief description
Fig. 1 prepares sulfate hemihydrate whisker process chart for ardealite.
Specific embodiment
Example 1 is to prepare semi-hydrated gypsum whisker without the ardealite that homogenizing is processed：
Processing step is as follows：
（1）Remove quartz and the partial impurities in ardealite using common flotation desilication technology, improve sulfate dihydrate in ardealite
Calcium content >=92.0%.
（2）It is 5% slip that the ardealite of upgrading and water are prepared solid masses concentration, adds slurry weight 0.5% magnesium sulfate
Sulphuric acid with 1%, carries out hydro-thermal reaction 2.0h under the conditions of 120 DEG C～140 DEG C, after question response is complete, fast filtering, and dehydration,
It is dried, obtain final product hemihydrate calcium sulfate crystal whisker.Result shows, prepares semi-hydrated gypsum whisker, whisker without the ardealite that homogenizing is processed
There are unreacted impurity and speckle in product, whisker morphology is also uneven, have a strong impact on semi-hydrated gypsum crystal whisker products quality.
Example 2 prepares semi-hydrated gypsum whisker without the ardealite that homogenizing is processed：
Processing step is as follows：
（1）Remove quartz and the partial impurities in ardealite using common flotation desilication technology, improve sulfate dihydrate in ardealite
Calcium content >=92.0%.
（2）It is 12% slip that the ardealite of upgrading and water are prepared solid masses concentration, adds 1.5% sulfur based on its weight
Sour aluminum and 1% sulphuric acid, carry out hydro-thermal reaction 2.0h under the conditions of 120 DEG C～140 DEG C, after question response is complete, fast filtering, take off
Water, is dried, obtains final product hemihydrate calcium sulfate crystal whisker.Result shows, prepares semi-hydrated gypsum whisker without the ardealite that homogenizing is processed, brilliant
Must there are unreacted impurity and speckle, whisker morphology is also uneven, has a strong impact on semi-hydrated gypsum crystal whisker products quality in product.
Semi-hydrated gypsum whisker prepared by the ardealite that example 3 is processed through homogenizing：
Processing step is as follows：
（1）Remove quartz and the partial impurities in ardealite using common flotation desilication technology, improve sulfate dihydrate in ardealite
Calcium content >=92.0%.
（2）Upgrading ardealite is processed through grinding 10min homogenizing and is prepared into solids content 8% slip, standby；
（3）By solid masses concentration be 8% slip add based on its weight 2.0% iron sulfate and 1% sulphuric acid, 120 DEG C～140
Carry out hydro-thermal reaction 2.0h under the conditions of DEG C, after question response is complete, fast filtering, dehydration, it is dried, obtain final product hemihydrate calcium sulfate crystal whisker.
Result shows, semi-hydrated gypsum whisker prepared by the ardealite processing through homogenizing, and crystal whisker products pattern uniformly, has no speckle impurity,
Solve the problems, such as homogenizing in crystal whisker products production process.
Semi-hydrated gypsum whisker prepared by the ardealite that example 4 is processed through homogenizing：
Processing step is as follows：
（1）Remove quartz and the partial impurities in ardealite using common flotation desilication technology, improve sulfate dihydrate in ardealite
Calcium content >=92.0%.
（2）Upgrading ardealite is processed through grinding 30min homogenizing and is prepared into solids content 10% slip, standby；
（3）Solid masses concentration is that 10% slip adds its weight meter 4.0% aluminum phosphate and 1% sulphuric acid, 120 DEG C～140
Carry out hydro-thermal reaction 2.0h under the conditions of DEG C, after question response is complete, fast filtering, dehydration, it is dried, obtain final product hemihydrate calcium sulfate crystal whisker.
Result shows, semi-hydrated gypsum whisker prepared by the ardealite processing through homogenizing, and crystal whisker products pattern uniformly, has no speckle impurity,
Solve the problems, such as homogenizing in crystal whisker products production process.
Semi-hydrated gypsum whisker prepared by the ardealite that example 5 is processed through homogenizing：
Processing step is as follows：
（1）Remove quartz and the partial impurities in ardealite using common flotation desilication technology, improve sulfate dihydrate in ardealite
Calcium content >=92.0%.
（2）Upgrading ardealite is processed through grinding 5min homogenizing and is prepared into solids content 6% slip, standby；
（3）Solid masses concentration is added its weight meter 1.5% magnesium sulfate and 1% sulphuric acid for 6% slip, in 120 DEG C～140 DEG C bars
Carry out hydro-thermal reaction 2.0h under part, after question response is complete, fast filtering, dehydration, it is dried, obtain final product hemihydrate calcium sulfate crystal whisker.Result
Show, semi-hydrated gypsum whisker prepared by the ardealite processing through homogenizing, crystal whisker products pattern uniformly, has no speckle impurity, solve
Homogenizing problem in crystal whisker products production process.
Claims (6)
1. a kind of new technology of ardealite preparation low cost hemihydrate calcium sulfate crystal whisker is it is characterised in that comprise the steps：
（1）Using quartz and partial impurities in ardealite, there is floatability, ardealite is removed using flotation desilication technology
In quartz and partial impurities, improve ardealite in sulfate dihydrate calcium content >=92.0%；
（2）In step（1）Its weight 0.5～2.0% dispersant is added in the upgrading ardealite obtaining, grinding 5 after mixing～
30min, it is standby that homogenizing process is prepared into solids content 5～12%；
（3）To step（2）It is obtained in ardealite slurry and add this slurry weight 0.1～5.0% crystal modifier and 1% technical grade sulfuric acid
Or hydrochloric acid, and adjust pH value 2～5, stir to material uniformly, then proceed in pressure reaction still；
（4）Crystal whisker of gypsum converts：120～140 DEG C of conversion temperature of setting, reacts temperature retention time 2.0h, after question response is complete, quickly
Filter, dehydration, be dried more than 80 DEG C of temperature, obtain final product hemihydrate calcium sulfate crystal whisker.
2. the new technology of a kind of ardealite preparation low cost hemihydrate calcium sulfate crystal whisker according to claim 1, its feature exists
It is sodium chloride, potassium chloride, zinc chloride, magnesium chloride, sodium sulfate, potassium sulfate, zinc sulfate, sulphuric acid in the inorganic salt as crystal modifier
One or more of combination in magnesium, aluminum sulfate, sodium phosphate, potassium phosphate, zinc phosphate, magnesium phosphate and aluminum phosphate.
3. the new technology of a kind of ardealite preparation low cost hemihydrate calcium sulfate crystal whisker according to claim 1, its feature exists
It is cetyl trimethylammonium bromide, dodecylbenzene sodium sulfonate, hexadecyl hydrosulfate in the organic additive as crystal modifier
The combination of one or more of sodium, Oleic acid and enuatrol.
4. the new technology of the inexpensive hemihydrate calcium sulfate crystal whisker of a kind of ardealite preparation according to claim 1,2 or 3, it is special
Levy and be that the aforementioned inorganic salt as crystal modifier or organic additive are technical grade commercial sources.
5. the new technology of a kind of ardealite preparation low cost hemihydrate calcium sulfate crystal whisker according to claim 1, its feature exists
In step（2）Middle homogenizing processes and is prepared into solids content 10% slurry.
6. the new technology of a kind of ardealite preparation low cost hemihydrate calcium sulfate crystal whisker according to claim 1, its feature exists
In step（4）The filtrate being filtrated to get is back to step（2）In, continue cycling through use.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107190325A (en) * | 2017-05-09 | 2017-09-22 | 武汉理工大学 | A kind of method that utilization industrial by-product ardealite prepares anhydrous calcium sulfate whisker |
| CN108411369A (en) * | 2018-04-11 | 2018-08-17 | 中国计量大学 | A method of utilizing preparing alpha-hemihydrate gypsum with desulfurated gypsum whisker in alcohol-water system |
| CN109280959A (en) * | 2017-07-19 | 2019-01-29 | 北新集团建材股份有限公司 | A method of semi-hydrated gypsum fiber is prepared by desulfurized gypsum |
| CN109280979A (en) * | 2017-07-19 | 2019-01-29 | 北新集团建材股份有限公司 | A method of preparing semi-hydrated gypsum whisker |
| CN110205671A (en) * | 2019-07-04 | 2019-09-06 | 江苏一夫科技股份有限公司 | It is a kind of to prepare Dihydrate gypsum whiskers, the method for hemihydrate calcium sulfate crystal whisker and product as made from it |
| CN110699756A (en) * | 2019-10-31 | 2020-01-17 | 江西富达盐化有限公司 | Method for preparing alpha-type gypsum whisker by using ammonia-soda waste liquid |
| CN110835780A (en) * | 2019-10-28 | 2020-02-25 | 昆明理工大学 | Method for preparing nanometer α type calcium sulfate hemihydrate crystal whisker from phosphogypsum in reverse microemulsion system |
| CN111286788A (en) * | 2020-02-27 | 2020-06-16 | 武汉工程大学 | Method for preparing calcium sulfate whisker by phosphogypsum hydrothermal method |
| CN111560521A (en) * | 2020-06-22 | 2020-08-21 | 湖南科技大学 | Method for efficiently leaching valuable metal impurities in phosphogypsum and preparing high-added-value gypsum product |
| CN113830814A (en) * | 2021-09-16 | 2021-12-24 | 浙江钙宝新材料有限公司 | Method for preparing calcium sulfate nano-rods from industrial solid waste gypsum |
| CN114538840A (en) * | 2022-03-19 | 2022-05-27 | 青岛惠城环保科技股份有限公司 | Preparation method of high-strength anti-freezing foam concrete with in-situ generated whiskers |
| CN115872435A (en) * | 2022-09-20 | 2023-03-31 | 四川大学 | Method for preparing high-purity gypsum through crystal phase reconstruction |
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| CN104005086A (en) * | 2014-04-04 | 2014-08-27 | 贵阳中化开磷化肥有限公司 | Method for preparing calcium sulfate dihydrate crystal whisker from phosphorus gypsum |
| CN104562180A (en) * | 2015-01-07 | 2015-04-29 | 西南科技大学 | Method for preparing calcium sulfate whisker from phosphogypsum |
| CN105350066A (en) * | 2015-12-15 | 2016-02-24 | 云南省化工研究院 | Method for preparing calcium sulfate hemihydrate crystal whisker by ardealite |
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| CN101792932A (en) * | 2009-11-16 | 2010-08-04 | 瓮福（集团）有限责任公司 | Method for preparing ultra-fine calcium sulfate crystal whisker by using phosphogypsum |
| CN104005086A (en) * | 2014-04-04 | 2014-08-27 | 贵阳中化开磷化肥有限公司 | Method for preparing calcium sulfate dihydrate crystal whisker from phosphorus gypsum |
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Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107190325A (en) * | 2017-05-09 | 2017-09-22 | 武汉理工大学 | A kind of method that utilization industrial by-product ardealite prepares anhydrous calcium sulfate whisker |
| CN107190325B (en) * | 2017-05-09 | 2019-10-25 | 武汉理工大学 | A method of anhydrous calcium sulfate whisker is prepared using industrial by-product ardealite |
| CN109280959A (en) * | 2017-07-19 | 2019-01-29 | 北新集团建材股份有限公司 | A method of semi-hydrated gypsum fiber is prepared by desulfurized gypsum |
| CN109280979A (en) * | 2017-07-19 | 2019-01-29 | 北新集团建材股份有限公司 | A method of preparing semi-hydrated gypsum whisker |
| CN108411369A (en) * | 2018-04-11 | 2018-08-17 | 中国计量大学 | A method of utilizing preparing alpha-hemihydrate gypsum with desulfurated gypsum whisker in alcohol-water system |
| CN110205671A (en) * | 2019-07-04 | 2019-09-06 | 江苏一夫科技股份有限公司 | It is a kind of to prepare Dihydrate gypsum whiskers, the method for hemihydrate calcium sulfate crystal whisker and product as made from it |
| CN110835780B (en) * | 2019-10-28 | 2021-11-09 | 昆明理工大学 | Method for preparing nano-scale alpha type calcium sulfate hemihydrate crystal whisker from phosphogypsum in reverse microemulsion system |
| CN110835780A (en) * | 2019-10-28 | 2020-02-25 | 昆明理工大学 | Method for preparing nanometer α type calcium sulfate hemihydrate crystal whisker from phosphogypsum in reverse microemulsion system |
| CN110699756B (en) * | 2019-10-31 | 2021-06-25 | 江西富达盐化有限公司 | Method for preparing alpha-type gypsum whisker by using ammonia-soda waste liquid |
| CN110699756A (en) * | 2019-10-31 | 2020-01-17 | 江西富达盐化有限公司 | Method for preparing alpha-type gypsum whisker by using ammonia-soda waste liquid |
| CN111286788A (en) * | 2020-02-27 | 2020-06-16 | 武汉工程大学 | Method for preparing calcium sulfate whisker by phosphogypsum hydrothermal method |
| CN111560521A (en) * | 2020-06-22 | 2020-08-21 | 湖南科技大学 | Method for efficiently leaching valuable metal impurities in phosphogypsum and preparing high-added-value gypsum product |
| CN111560521B (en) * | 2020-06-22 | 2021-08-10 | 湖南科技大学 | Method for efficiently leaching valuable metal impurities in phosphogypsum and preparing high-added-value gypsum product |
| CN113830814A (en) * | 2021-09-16 | 2021-12-24 | 浙江钙宝新材料有限公司 | Method for preparing calcium sulfate nano-rods from industrial solid waste gypsum |
| CN114538840A (en) * | 2022-03-19 | 2022-05-27 | 青岛惠城环保科技股份有限公司 | Preparation method of high-strength anti-freezing foam concrete with in-situ generated whiskers |
| CN115872435A (en) * | 2022-09-20 | 2023-03-31 | 四川大学 | Method for preparing high-purity gypsum through crystal phase reconstruction |
| CN115872435B (en) * | 2022-09-20 | 2024-05-14 | 四川大学 | Method for preparing high-purity gypsum by crystal phase reconstruction |
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