CN114540957A - Method for preparing calcium sulfate hemihydrate whiskers by using titanium white waste acid and titanium gypsum - Google Patents
Method for preparing calcium sulfate hemihydrate whiskers by using titanium white waste acid and titanium gypsum Download PDFInfo
- Publication number
- CN114540957A CN114540957A CN202210166438.1A CN202210166438A CN114540957A CN 114540957 A CN114540957 A CN 114540957A CN 202210166438 A CN202210166438 A CN 202210166438A CN 114540957 A CN114540957 A CN 114540957A
- Authority
- CN
- China
- Prior art keywords
- titanium
- gypsum
- calcium sulfate
- iron
- titanium gypsum
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000010440 gypsum Substances 0.000 title claims abstract description 80
- 229910052602 gypsum Inorganic materials 0.000 title claims abstract description 80
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 239000010936 titanium Substances 0.000 title claims abstract description 56
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 56
- ZOMBKNNSYQHRCA-UHFFFAOYSA-J calcium sulfate hemihydrate Chemical compound O.[Ca+2].[Ca+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZOMBKNNSYQHRCA-UHFFFAOYSA-J 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 34
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 235000010215 titanium dioxide Nutrition 0.000 title claims abstract description 25
- 239000002253 acid Substances 0.000 title claims abstract description 22
- 239000002699 waste material Substances 0.000 title claims abstract description 22
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 45
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000013078 crystal Substances 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000002002 slurry Substances 0.000 claims abstract description 19
- 229910052742 iron Inorganic materials 0.000 claims abstract description 17
- 238000005406 washing Methods 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 238000009835 boiling Methods 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 238000005070 sampling Methods 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 230000003287 optical effect Effects 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 15
- 239000000843 powder Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 238000001035 drying Methods 0.000 description 9
- 238000002156 mixing Methods 0.000 description 6
- 238000007873 sieving Methods 0.000 description 6
- 238000003828 vacuum filtration Methods 0.000 description 6
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 241000276425 Xiphophorus maculatus Species 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- GZHZKHYXEODHJF-UHFFFAOYSA-N acetic acid;azane Chemical compound N.N.N.CC(O)=O.CC(O)=O.CC(O)=O GZHZKHYXEODHJF-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000007952 growth promoter Substances 0.000 description 1
- 230000000887 hydrating effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Images
Classifications
-
- 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
-
- 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
-
- 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
- C30B7/14—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions the crystallising materials being formed by chemical reactions in the solution
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention discloses a method for preparing calcium sulfate hemihydrate whiskers by using titanium white waste acid and titanium gypsum, which comprises the following steps: removing iron in the titanium gypsum by using titanium white waste acid to prepare iron-removed titanium gypsum; adding a glycerol solution into the iron-removed titanium gypsum, transferring the iron-removed titanium gypsum into a three-necked flask, heating to 103-105 ℃, and keeping the temperature for 30min at a rotation speed of 400r/min until slurry caking occurs; and adding 75ml of boiling water into the slurry block, stirring until the block is completely dispersed, keeping the temperature for 60 mm, sampling under an optical microscope for observation, stopping reaction when all the plate-shaped gypsum crystals disappear, and filtering and washing to obtain the calcium sulfate hemihydrate crystal whisker. The length-diameter ratio of the calcium sulfate hemihydrate crystal whisker with the overlong length-diameter ratio can reach 90-180, so that the length-diameter ratio of the calcium sulfate hemihydrate crystal whisker is remarkably improved, and the application range is wider; and effectively improves the production efficiency and the production safety.
Description
Technical Field
The invention relates to the technical field of gypsum whisker preparation, in particular to a method for preparing calcium sulfate hemihydrate whiskers by using titanium white waste acid and titanium gypsum.
Background
Titanium gypsum and titanium white waste acid are common byproducts in the production process of titanium dioxide, titanium gypsum is generally subjected to accumulation treatment, which occupies space and pollutes the environment, and the method can recycle industrial byproducts, is beneficial to environmental management and improves the economic benefits of enterprises. For titanium gypsum, the most potential application is to prepare calcium sulfate hemihydrate whiskers (gypsum whiskers), and the gypsum whiskers with ultrahigh length-diameter ratio can be used in paper industry, cement, rubber and the like. However, the impurity iron is a major obstacle to the preparation of gypsum whiskers, and studies have shown that the presence of iron reduces the aspect ratio of calcium sulfate whiskers. Therefore, before the titanium gypsum is used for preparing the calcium sulfate whisker, the reddish brown titanium gypsum needs to be subjected to iron removal to obtain white iron-removed titanium gypsum.
Ganyanle et al use titanium white waste acid and lime as raw materials to prepare titanium white gypsum, then use titanium white gypsum as raw materials to prepare calcium sulfate whisker by hydrothermal synthesis, and investigate the influence of factors such as reaction temperature, reaction time, stirring speed, slurry concentration and the like on the appearance of the calcium sulfate whisker, and experimental results show that the product prepared by the method has good appearance under the conditions that the reaction temperature is 120 ℃, the reaction time is 60min, the stirring speed is 70rpm and the slurry concentration is 4%. The method needs to be completed at higher temperature or pressure, has higher energy consumption and has higher requirements on the aspects of the tightness of a reaction device and the like.
Yang et al at 3% K2SO4And (mass fraction) reacting in the solution for 60min to prepare the HH crystal whisker with the diameter of 1-5 mu m and the length-diameter ratio of 50-80. At present, the normal pressure salt solution method is adoptedThe method does not need to be carried out under high-pressure equipment, but has the disadvantages of complex preparation process and difficult control of the process, and the salts are mainly selected from chloride and sulfate and can generate great corrosivity on reaction equipment.
And the patent No. CN112342624 is to dissolve calcium sulfate dihydrate at the temperature of 60-80 ℃, filter, cool and crystallize filtrate, wash and dry to obtain the calcium sulfate dihydrate crystal whisker. The method comprises adding 0.12-0.21 mol of calcium sulfate dihydrate into each liter of hydrochloric acid. And adding a crystallization promoter in the dissolving process, wherein the crystallization promoter comprises magnesium chloride, and the addition amount of the magnesium chloride is 0.01-0.02 mol per liter of hydrochloric acid. Calcium sulfate dihydrate is prepared by removing free water from titanium gypsum. The performance of the calcium sulfate dihydrate crystal whisker prepared by the method is inferior to that of the hemihydrate.
In the purification of titanium gypsum, patent No. CN109161971A is dissolved by 1-5 mol of L-1 hydrochloric acid, and the solution is filtered, the pH value of the solution is adjusted, and pure white titanium gypsum is precipitated. The hydrothermal reaction time is 6-12 hours, and the temperature is 120-130 ℃. The length-diameter ratio of the obtained calcium sulfate whisker is 40-60. The preferable components are as follows: the mass fraction of the pure white titanium gypsum slurry is 2.5-5%. The additive is glycerol, and the volume of the glycerol is 10-30% of the volume of the slurry. The crystal growth promoter is magnesium sulfonate with the molar concentration of 0.01-0.1 mol/l. The method has the advantages of overlong hydrothermal time, overhigh temperature, high energy consumption and short length-diameter ratio of the prepared crystal whisker.
In patent No. CN111270312A, titanium gypsum is purified by concentrated hydrochloric acid, then PH is adjusted to 7 by shell slaked lime, clear liquid 1 is obtained by filtration, mixed crystal modifier (3g sodium sulfate +4ml ammonium triacetate +4ml glycerol) is added, and the mixed liquid is sealed in a vacuum drying oven (140 ℃, 4h) with the length-diameter ratio of 40-90. The method uses concentrated hydrochloric acid for purification and a complex-component crystal transformation agent.
The existing method has complex operation steps and higher requirements on reaction conditions such as temperature, pressure and the like, and the prepared gypsum whisker has shorter length and diameter.
Disclosure of Invention
The invention aims to solve the problems in the prior art, and provides a method for preparing calcium sulfate hemihydrate whiskers by using titanium white waste acid and titanium gypsum, which is simple in steps and can prepare the calcium sulfate hemihydrate whiskers with the length-diameter ratio of 90-180 only by reacting for 1-2 hours under normal pressure.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: a method for preparing calcium sulfate hemihydrate whiskers by using titanium white waste acid and titanium gypsum comprises the following steps:
s1, removing iron in the titanium gypsum by using titanium white waste acid to prepare iron-removed titanium gypsum;
s2, adding a glycerol solution into the iron-removed titanium gypsum, transferring the mixture into a three-necked flask, heating to 103-105 ℃, and keeping the temperature for 30min at a rotation speed of 400r/min until slurry caking occurs;
and S3, adding 75ml of boiling water into the slurry block, stirring until the block is completely dispersed, keeping the temperature for 60 mm, sampling, observing under an optical microscope, stopping the reaction when the plate-shaped gypsum crystals completely disappear, and filtering and washing to obtain the calcium sulfate hemihydrate crystal whisker.
Preferably, in the S1, titanium white waste acid is added into a three-neck flask, preheated to 70 ℃ in a water bath, added with titanium gypsum with the particle size of 75-150 microns, uniformly mixed, reacted for 1-2h, vacuum filtered, washed by boiling water until the washing liquid is colorless, fixed by absolute ethyl alcohol, and dried for 12h to obtain the iron-removed titanium gypsum.
Preferably, in the S1, the mass ratio of the titanium gypsum to the titanium white waste acid is 1: 5.
Preferably, the iron-removed titanium gypsum prepared in S1 is white, and the iron content in the iron-removed titanium gypsum is less than 4%.
Preferably, the liquid-solid ratio of the glycerol solution to the iron-removed titanium gypsum in S2 is 9: 1.
More preferably, the concentration of the glycerol solution in S2 is 40 wt% to 50 wt%.
Further preferably, the temperature increase rate in S2 is 6 ℃/min.
More preferably, the length-diameter ratio of the calcium sulfate hemihydrate crystal whisker prepared in S3 is 90-180.
The invention has the following beneficial effects:
firstly), removing iron in titanium gypsum by using titanium white waste acid, preparing calcium sulfate hemihydrate crystal whiskers by using an alcohol-water method, washing away redundant alcohol by using boiling water, and preventing the calcium sulfate hemihydrate crystal whiskers from hydrating, so that the calcium sulfate hemihydrate crystal whiskers with an ultra-long length-diameter ratio can be prepared, the length-diameter ratio of the calcium sulfate hemihydrate crystal whiskers can reach 90-180, the length-diameter ratio of the calcium sulfate hemihydrate crystal whiskers is remarkably improved, and the application range is wider;
secondly), the preparation process is simple in steps, mild in reaction conditions, free of high-pressure conditions, and capable of preparing the calcium sulfate hemihydrate crystal whisker with the length-diameter ratio of 90-180 only by reacting for 1-2 hours under normal pressure, so that the production efficiency and the production safety are effectively improved, and energy is saved.
Drawings
FIG. 1 is a flow chart of the steps of the present invention for preparing calcium sulfate hemihydrate whiskers;
FIG. 2 is a topographical view of calcium sulfate hemihydrate whiskers prepared in example 1 of the present invention;
FIG. 3 is a topographical view of calcium sulfate hemihydrate whiskers prepared in example 2 of the present invention;
FIG. 4 is a topographical view of calcium sulfate hemihydrate whiskers prepared in example 3 of the present invention;
FIG. 5 is a graphical representation of the gypsum prepared in comparative example 1 of the present invention;
FIG. 6 is a graphical representation of the gypsum prepared in comparative example 2 of the present invention;
fig. 7 is a comparison of the slurry of comparative example 2 and the slurry of example 1 in the present invention (fig. 7-a is a diagram of the slurry of comparative example 2 and fig. 7-B is a diagram of the slurry of example 1).
Detailed Description
The invention is further described with reference to the following figures and specific embodiments.
Example 1
As shown in attached figure 1, the method comprises the steps of carrying out drying, crushing and sieving pretreatment on reddish brown titanium gypsum to obtain titanium gypsum powder with the particle size of 75 microns, adding 400g of titanium white waste acid into a three-neck flask, preheating to 70 ℃ in a water bath kettle, adding 80g of titanium gypsum powder, uniformly mixing, reacting for 2 hours, carrying out vacuum filtration, washing with boiling water until washing liquor is colorless, fixing with absolute ethyl alcohol, drying for 12 hours, grinding and sieving to obtain iron-removed titanium gypsum powder with the iron content of 3.83%.
Putting 11g of the iron-titanium-removed gypsum powder and 100g of 40 wt% glycerol solution into a three-necked flask, and fully mixing, wherein the particle size of the iron-titanium-removed gypsum is 100 meshes; heating to 103 ℃ in 20 minutes, preserving heat for 30 minutes at the rotating speed of 400r/min, and generating slurry agglomeration; adding 75ml of boiling water into a three-neck flask, stirring until the blocks are completely dispersed into a uniform slurry (shown in figure 7-B), and keeping the temperature for 60 minutes; sampling and observing by using an electron microscope, and stopping the reaction when the platy gypsum is completely converted into the whiskers (as shown in figure 2); and (4) carrying out vacuum filtration, washing with absolute ethyl alcohol, and then placing in a constant-temperature drying oven for 12 hours to obtain the calcium sulfate hemihydrate crystal whisker.
Example 2
As shown in attached figure 1, the method comprises the steps of carrying out drying, crushing and sieving pretreatment on reddish brown titanium gypsum to obtain titanium gypsum powder with the particle size of 150 microns, adding 400g of titanium white waste acid into a three-neck flask, preheating to 70 ℃ in a water bath kettle, adding 80g of titanium gypsum powder, uniformly mixing, reacting for 1h, carrying out vacuum filtration, washing with boiling water until washing liquor is colorless, fixing with absolute ethyl alcohol, drying for 12h, grinding and sieving to obtain iron-removed titanium gypsum powder with the iron content of 3.22%.
Putting 11g of the iron-titanium-removed gypsum powder and 100g of 50 wt% glycerol solution into a three-necked flask, and fully mixing, wherein the particle size of the iron-titanium-removed gypsum is 100 meshes; heating to 105 ℃ in 20 minutes, preserving heat for 30 minutes, and enabling the rotation speed to be 400r/min to generate slurry caking; adding 75ml of boiling water into the three-neck flask, stirring until the agglomeration is completely dispersed, and continuously preserving the heat for 60 minutes; taking a sample by an electron microscope for observation, and stopping the reaction when the platy gypsum is completely converted into the whisker (shown in figure 3); and (4) carrying out vacuum filtration, washing with absolute ethyl alcohol, and then placing in a constant-temperature drying oven for 12 hours to obtain the calcium sulfate hemihydrate crystal whisker.
Example 3
As shown in attached figure 1, the method comprises the steps of carrying out drying, crushing and sieving pretreatment on reddish brown titanium gypsum to obtain titanium gypsum powder with the particle size of 100 microns, adding 400g of titanium white waste acid into a three-necked flask, preheating to 70 ℃ in a water bath kettle, adding 80g of titanium gypsum powder, uniformly mixing, reacting for 1.5 hours, carrying out vacuum filtration, washing with boiling water until washing liquor is colorless, fixing with absolute ethyl alcohol, drying for 12 hours, and then grinding and sieving to obtain iron-removed titanium gypsum powder with the iron content of 3.64%.
Putting 11g of the iron-titanium-removed gypsum powder and 100g of 45 wt% glycerol solution into a three-necked flask, and fully mixing, wherein the particle size of the iron-titanium-removed gypsum is 100 meshes; heating to 104 ℃ in 20 minutes, preserving heat for 30 minutes, and enabling the rotation speed to be 400r/min to generate slurry caking; adding 75ml of boiling water into the three-neck flask, stirring until the agglomeration is completely dispersed, and continuously preserving the heat for 60 minutes; taking a sample by an electron microscope for observation, and stopping the reaction when the platy gypsum is completely converted into the whisker (shown in figure 4); and (4) carrying out vacuum filtration, washing with absolute ethyl alcohol, and then placing in a constant-temperature drying oven for 12 hours to obtain the calcium sulfate hemihydrate crystal whisker.
Comparative example 1
The method comprises the steps of taking the gypsum without removing iron and titanium as a raw material, adding a glycerol solution with a liquid-solid ratio of 9, reacting for 2 hours at 105 ℃, sampling and observing under an electron microscope, wherein calcium sulfate hemihydrate whiskers do not appear (as shown in figure 5).
Comparative example 2
Taking the iron titanium-removed gypsum as an example, adding a glycerol solution with a liquid-solid ratio of 9, reacting at 105 ℃ for 30min, wherein the slurry is seriously caked (as shown in figure 7-A), and like evaporating water, sampling and observing under an electron microscope, the blocky gypsum is not completely converted into whiskers (as shown in figure 6), but cannot be reacted further.
TABLE 1 comparison of length to diameter ratio data for calcium sulfate hemihydrate whiskers prepared in accordance with the present invention and comparative examples
| Grouping | Aspect ratio |
| Example 1 | 90-150 |
| Example 2 | 95-180 |
| Example 3 | 95-180 |
| Comparative example 1 | Whisker free formation |
| Comparative example 2 | Agglomeration of |
TABLE 2 data table of iron removal rate of titanium white waste acid in the invention
The data in Table 2 show that the titanium white waste acid can be used for efficiently removing iron in the titanium gypsum to obtain the titanium gypsum with the iron content of less than 4%; on the basis, the calcium sulfate hemihydrate crystal whisker with the length-diameter ratio of 90-180 is prepared by taking iron-titanium-removed gypsum as a raw material and utilizing an alcohol-water method (as shown in table 1, figure 2, figure 3 and figure 4). Compared with the prior art, the comparative example 1 and the comparative example 2 adopt the same alcohol-water method, but the calcium sulfate hemihydrate crystal whisker with the length-diameter ratio of 90-180 cannot be effectively obtained, so the method can effectively prepare the calcium sulfate hemihydrate crystal whisker with the overlong length-diameter ratio, has mild reaction conditions, does not need high pressure conditions, can be prepared by reacting for 1-2h under normal pressure, obviously improves the production efficiency and the production safety, and is very suitable for industrial large-scale production.
The present specification and figures are to be regarded as illustrative rather than restrictive, and it is intended that all such alterations and modifications that fall within the true spirit and scope of the invention, and that all such modifications and variations are included within the scope of the invention as determined by the appended claims without the use of inventive faculty.
Claims (8)
1. A method for preparing calcium sulfate hemihydrate whiskers by using titanium white waste acid and titanium gypsum is characterized by comprising the following steps:
s1, removing iron in the titanium gypsum by using titanium white waste acid to prepare iron-removed titanium gypsum;
s2, adding a glycerol solution into the iron-removed titanium gypsum, transferring the mixture into a three-necked flask, heating to 103-105 ℃, and keeping the temperature for 30min at a rotation speed of 400r/min until slurry caking occurs;
and S3, adding 75ml of boiling water into the slurry block, stirring until the block is completely dispersed, keeping the temperature for 60 mm, sampling, observing under an optical microscope, stopping the reaction when all the plate-shaped gypsum crystals disappear, and filtering and washing to obtain the calcium sulfate hemihydrate crystal whisker.
2. The method according to claim 1, wherein in the step S1, titanium white waste acid is added into a three-necked flask, preheated to 70 ℃ in a water bath kettle, added with titanium gypsum with the particle size of 75-150 μm, uniformly mixed, reacted for 1-2h, vacuum filtered, washed with boiling water until the washing liquid is colorless, fixed with absolute ethyl alcohol, and dried for 12h to obtain the iron-removed titanium gypsum.
3. The method according to claim 1 or 2, wherein in S1, the mass ratio of titanium gypsum to titanium white waste acid is 1: 5.
4. The method as claimed in claim 1, wherein the de-ferred titanium gypsum obtained in S1 is white, and the content of iron in the de-ferred titanium gypsum is less than 4%.
5. The method as claimed in claim 1, wherein the liquid-solid ratio of the glycerol solution to the iron-removed titanium gypsum in S2 is 9: 1.
6. The method according to claim 1, wherein the concentration of the glycerol solution in S2 is 40 wt% to 50 wt%.
7. The method according to claim 1, wherein the temperature increase rate in S2 is 6 ℃/min.
8. The method of claim 1, wherein the aspect ratio of the calcium sulfate hemihydrate whiskers prepared in S3 is 90-180.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210166438.1A CN114540957A (en) | 2022-02-23 | 2022-02-23 | Method for preparing calcium sulfate hemihydrate whiskers by using titanium white waste acid and titanium gypsum |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210166438.1A CN114540957A (en) | 2022-02-23 | 2022-02-23 | Method for preparing calcium sulfate hemihydrate whiskers by using titanium white waste acid and titanium gypsum |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114540957A true CN114540957A (en) | 2022-05-27 |
Family
ID=81677126
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210166438.1A Pending CN114540957A (en) | 2022-02-23 | 2022-02-23 | Method for preparing calcium sulfate hemihydrate whiskers by using titanium white waste acid and titanium gypsum |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114540957A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116876069A (en) * | 2023-07-18 | 2023-10-13 | 湖北大学 | Method for directly preparing alpha semi-hydrated gypsum whisker from titanium white waste acid |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008081329A (en) * | 2006-09-26 | 2008-04-10 | Taiheiyo Cement Corp | Method for manufacturing gypsum dihydrate having large particle size |
| CN103086624A (en) * | 2013-01-22 | 2013-05-08 | 武汉理工大学 | Method for preparing alpha-semi-hydrated gypsum from titanium gypsum |
| CN109161971A (en) * | 2018-10-11 | 2019-01-08 | 西昌学院 | A method of calcium sulfate crystal whiskers are prepared by titanium gypsum |
-
2022
- 2022-02-23 CN CN202210166438.1A patent/CN114540957A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008081329A (en) * | 2006-09-26 | 2008-04-10 | Taiheiyo Cement Corp | Method for manufacturing gypsum dihydrate having large particle size |
| CN103086624A (en) * | 2013-01-22 | 2013-05-08 | 武汉理工大学 | Method for preparing alpha-semi-hydrated gypsum from titanium gypsum |
| CN109161971A (en) * | 2018-10-11 | 2019-01-08 | 西昌学院 | A method of calcium sulfate crystal whiskers are prepared by titanium gypsum |
Non-Patent Citations (2)
| Title |
|---|
| 吴叶 ET AL.: "脱硫石膏制备纳米级硫酸钙晶须的试验研究", 《新型建筑材料》 * |
| 孟华 ET AL.: "利用钛白废酸浸出钛石膏铁杂质及技术经济分析", 《化工矿工与加工》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116876069A (en) * | 2023-07-18 | 2023-10-13 | 湖北大学 | Method for directly preparing alpha semi-hydrated gypsum whisker from titanium white waste acid |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104846440B (en) | A kind of method that metallurgical gas desulfuration gypsum recrystallization method prepares high-purity Dihydrate gypsum whiskers | |
| CN102677177B (en) | A kind of preparation method of high length-diameter ratio hemihydrate calcium sulfate crystal whisker | |
| CN104532339B (en) | A kind of method that calcium sulfate crystal whiskers are prepared using low grade natural gypsum or gypsum mine | |
| CN103951297A (en) | Preparation method of alpha type gypsum with ultrahigh strength | |
| CN102092749A (en) | Preparation method of boehmite | |
| CN105271347A (en) | Method for preparing high-purity barium salt by using witherite-barytocalcite industrial waste residues | |
| CN106315605B (en) | Method for preparing 1.1nm tobermorite from low-grade attapulgite clay | |
| CN114540957A (en) | Method for preparing calcium sulfate hemihydrate whiskers by using titanium white waste acid and titanium gypsum | |
| CN114921851A (en) | Calcium carbonate whisker prepared by carbide slag carbonization and preparation method thereof | |
| CN102851739B (en) | Preparation process of calcium sulfate whisker | |
| CN114540959A (en) | Calcium sulfate whisker and preparation process of raw material calcium sulfate thereof | |
| CN104030331B (en) | A kind of method utilizing aluminous fly-ash to produce aluminium oxide | |
| CN109133690B (en) | Method for preparing high-strength alpha-titanium gypsum by using industrial waste titanium dioxide waste residue | |
| CN112694098A (en) | Method for recovering and synthesizing molecular sieve ZSM-5X from silicon-containing sewage | |
| CN101319382B (en) | Calcium sulphate crystal whisker preparation method with sea water bittern as raw material | |
| CN1974412A (en) | Process of preparing high purity ferric oxide | |
| CN110304850A (en) | A method of alpha semi-hydrated gypsum is produced based on titanium gypsum | |
| CN105271290A (en) | Method for preparing analcite through high-alumina fly ash | |
| CN115716721A (en) | Method for directly preparing anhydrous gypsum by using phosphogypsum | |
| CN101700913B (en) | Method for preparing high-purity cobalt nitrate by utilizing alumina-supported cobalt-based spent catalyst for Fischer-Tropsch synthesis | |
| CN110156054B (en) | Preparation method of rhombohedral anhydrous magnesium carbonate | |
| CN111286788A (en) | Method for preparing calcium sulfate whisker by phosphogypsum hydrothermal method | |
| CN104860344A (en) | Preparation method of spherical strontium carbonate | |
| CN115872435B (en) | Method for preparing high-purity gypsum by crystal phase reconstruction | |
| CN111170324A (en) | Method for preparing light high-whiteness calcium silicate micro powder by using rice hull ash |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220527 |
|
| RJ01 | Rejection of invention patent application after publication |