CN104911688A - Preparation method of anhydrous calcium sulfate whisker - Google Patents
Preparation method of anhydrous calcium sulfate whisker Download PDFInfo
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- CN104911688A CN104911688A CN201510309296.XA CN201510309296A CN104911688A CN 104911688 A CN104911688 A CN 104911688A CN 201510309296 A CN201510309296 A CN 201510309296A CN 104911688 A CN104911688 A CN 104911688A
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- calcium sulfate
- anhydrous calcium
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- whisker
- sulfate whisker
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- 229940095564 anhydrous calcium sulfate Drugs 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000013078 crystal Substances 0.000 claims abstract description 53
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 37
- 239000007788 liquid Substances 0.000 claims abstract description 18
- 239000000725 suspension Substances 0.000 claims abstract description 16
- 239000002002 slurry Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000012065 filter cake Substances 0.000 claims abstract description 10
- 239000000706 filtrate Substances 0.000 claims abstract description 9
- 238000000926 separation method Methods 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- 239000007787 solid Substances 0.000 claims abstract description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 20
- 239000011505 plaster Substances 0.000 claims description 18
- 239000004575 stone Substances 0.000 claims description 17
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 6
- 238000013019 agitation Methods 0.000 claims description 5
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 3
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 3
- 239000001110 calcium chloride Substances 0.000 claims description 3
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 3
- 235000011148 calcium chloride Nutrition 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 3
- 235000011147 magnesium chloride Nutrition 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 27
- 238000003756 stirring Methods 0.000 abstract description 8
- 229910052602 gypsum Inorganic materials 0.000 abstract description 6
- 239000010440 gypsum Substances 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000005245 sintering Methods 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract 1
- 229940057306 hemihydrate calcium sulfate Drugs 0.000 description 19
- 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 description 18
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 11
- 239000000463 material Substances 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000000543 intermediate Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 229940095672 calcium sulfate Drugs 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229910052925 anhydrite Inorganic materials 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 150000004683 dihydrates Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical group Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 101100449785 Mus musculus Gsx2 gene Proteins 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000009970 fire resistant effect Effects 0.000 description 1
- 239000002783 friction material Substances 0.000 description 1
- 239000003630 growth substance Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- -1 papermaking Substances 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
Landscapes
- Crystals, And After-Treatments Of Crystals (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention belongs to the technical field of whisker preparation and particularly relates to a method for preparing anhydrous calcium sulfate whisker by a one-step hydrothermal process. The method comprises the following steps: (A) putting gypsum in water to prepare a first suspension, stirring and adding a crystal form controller to form slurry, wherein the liquid-solid mass ratio of the water to gypsum is (5.5-30):1, and the molar ratio of the crystal form controller to gypsum is (0.7-5):1; (B) transferring the slurry into a hydrothermal reaction kettle, and stirring for a hydrothermal reaction for 2-10h to obtain a second suspension, wherein the set temperature of the hydrothermal reaction kettle is 170-220 DEG C; and (C) performing solid-liquid separation on the second suspension to obtain a filter cake and filtrate, washing the filter cake and drying to obtain the anhydrous calcium sulfate whisker. According to the preparation method, the anhydrous calcium sulfate whisker can be prepared by a one-step hydrothermal process, and the method is simple; and meanwhile, the problem of low purity and the use of a high-temperature sintering process are avoided, and the production cost is lowered.
Description
Technical field
The invention belongs to whisker preparation technical field, specifically, relate to a kind of method that one step hydro thermal method prepares anhydrous calcium sulfate whisker.
Background technology
Calcium sulfate crystal whiskers, also known as crystal whisker of gypsum, has high strength, high-modulus, high tenacity, high-insulativity, abrasion performance, high temperature resistant, acid and alkali-resistance, anticorrosive, infrared reflectivity good, be easy to surface treatment, easily and polymkeric substance compound, the Wuli-Shili-Renli system approach of many excellences such as nontoxic and mechanical property.As new function material, it is widely used in making strengthening and toughening agent or functional type filler in plastics, rubber, caking agent, friction materials, papermaking, pitch, coating, paint, light building material and sealing material; Also can directly as the high insulating material of filtering material, lagging material, fire-resistant heat insulating material, infrared light reflecting material and covered electric cable.Calcium sulfate crystal whiskers is higher due to its cost performance, is the type material that a kind of Application Areas is comparatively wide, market outlook are very wide, be also receive much concern in the world at present, extremely rising inorganic carbon sources material.
Calcium sulfate crystal whiskers can be divided into Dihydrate gypsum whiskers (CaSO according to crystal water difference
42H
2o), hemihydrate calcium sulfate crystal whisker (CaSO
40.5H
2and anhydrous calcium sulfate whisker (CaSO O)
4).Wherein, anhydrous calcium sulfate whisker intensity is the highest; Dihydrate gypsum whiskers must use under lower than the condition of 110 DEG C, otherwise does not just have the enhancement of whisker, and therefore prospects for commercial application is little; Anhydrous calcium sulfate whisker and hemihydrate calcium sulfate crystal whisker then have higher intensity and use value.Can there is hydration reaction in hemihydrate calcium sulfate crystal whisker, destroy crystalline structure and performance in wet condition; Therefore, for keeping its stability hemihydrate calcium sulfate crystal whisker needs calcination process at 600 DEG C ~ 700 DEG C, generate insoluble anhydrous calcium sulfate whisker, this just causes the higher problem of industrial production cost.
Patent CN 201210452856.3 discloses a kind of method that low cost prepares calcium sulfate crystal whiskers, described method comprises following process: raw material water-ground limestone and anhydrite are pulverized, by pulverize after calcium carbonate mineral and anhydrite ore with after sulphuric acid soln process, add crystalline form growth substance and make mixed solution, generate the hemihydrate calcium sulfate crystal whisker had compared with high length-diameter ratio at high temperature under high pressure through hydrothermal synthesis method, hemihydrate calcium sulfate crystal whisker after filtration, washing, high temperature takes off crystal water step and namely obtain high-quality anhydrous calcium sulfate whisker product.Though calcination process at not needing 600 DEG C ~ 700 DEG C in this technique, still need the high temperature at 250 DEG C ~ 300 DEG C to take off crystal water in the process wherein changed to anhydrous calcium sulfate whisker by hemihydrate calcium sulfate crystal whisker and operate, therefore industrial cost is still higher.
Summary of the invention
For solving above-mentioned prior art Problems existing, the invention provides a kind of preparation method of anhydrous calcium sulfate whisker, this preparation method adopts one step hydro thermal method to prepare anhydrous calcium sulfate whisker, and method is simple, simplifies the preparation technology of anhydrous calcium sulfate whisker; Meanwhile, avoid the method using high temperature sintering, also significantly reduce production cost.
In order to reach foregoing invention object, present invention employs following technical scheme:
The preparation method of anhydrous calcium sulfate whisker, comprises step: A, plaster stone is placed in water, is mixed with the first suspension liquid, under agitation in described first suspension liquid, adds crystal control agent, forms slurry; Wherein, the liquid-solid mass ratio of described water and described plaster stone is 5.5 ~ 30:1; The mol ratio of described crystal control agent and described plaster stone is 0.7 ~ 5:1; B, described slurry to be transferred in hydrothermal reaction kettle, and under agitation to carry out hydro-thermal reaction 2h ~ 10h, obtain the second suspension liquid; Wherein, the set temperature of described hydrothermal reaction kettle is 170 DEG C ~ 220 DEG C; C, by described second suspension liquid solid-liquid separation, obtain filter cake and filtrate, described filter cake through washing, dry and obtain anhydrous calcium sulfate whisker.
Further, described crystal control agent is selected from any one in calcium chloride, ammonium chloride, magnesium chloride, ammonium sulfate.
Further, described filtrate is back in described steps A as crystal control agent Recycling.
Further, in described step C, described filter cake is dried through deionized water wash and at 80 DEG C and is obtained described anhydrous calcium sulfate whisker.
Further, in described step B, the compactedness of described slurry in described hydrothermal reaction kettle is 50% ~ 80%.
Further, described hydrothermal reaction kettle is magnetic force reactor or homogeneous reactor.
The present invention take plaster stone as raw material, and utilize the effect of crystal control agent, namely anhydrous calcium sulfate whisker has been synthesized by one step hydro thermal method, compared with the preparation method of anhydrous calcium sulfate whisker in prior art, avoid the process changed to anhydrous calcium sulfate whisker by hemihydrate calcium sulfate crystal whisker by pyroprocessing, significantly can reduce production cost; In addition, also have according to the preparation method of anhydrous calcium sulfate whisker of the present invention that technique is simple, the advantage of easy handling.
Accompanying drawing explanation
The following description carried out in conjunction with the drawings, feature and the advantage of the above-mentioned and other side of embodiments of the invention will become clearly, in accompanying drawing:
Fig. 1 is the flow chart of steps of the preparation method of anhydrous calcium sulfate whisker according to embodiments of the invention 1;
Fig. 2 is the XRD figure of the anhydrous calcium sulfate whisker according to embodiments of the invention 1;
Fig. 3 schemes according to the SEM of the anhydrous calcium sulfate whisker of embodiments of the invention 1;
Fig. 4 is the XRD figure of the anhydrous calcium sulfate whisker according to embodiments of the invention 4;
Fig. 5 schemes according to the SEM of the anhydrous calcium sulfate whisker of embodiments of the invention 4;
Fig. 6 is the XRD figure of the anhydrous calcium sulfate whisker according to embodiments of the invention 7;
Fig. 7 schemes according to the SEM of the anhydrous calcium sulfate whisker of embodiments of the invention 7;
Fig. 8 is the XRD figure of the anhydrous calcium sulfate whisker according to embodiments of the invention 8;
Fig. 9 schemes according to the SEM of the anhydrous calcium sulfate whisker of embodiments of the invention 8.
Embodiment
Below, embodiments of the invention are described in detail with reference to the accompanying drawings.But, the present invention can be implemented in many different forms, and the present invention should not be interpreted as being limited to the specific embodiment of setting forth here.On the contrary, provide these embodiments to be to explain principle of the present invention and practical application thereof, thus enable others skilled in the art understand various embodiment of the present invention and be suitable for the various amendments of certain expected application.
Will be appreciated that, although term " first ", " second " etc. can be used here to describe various intermediates, but these intermediates should not by the restriction of these terms, and these terms are only for making a distinction identical for chemical classes intermediates and another intermediates.
Fig. 1 is the flow chart of steps of the preparation method of anhydrous calcium sulfate whisker according to an embodiment of the invention.
With reference to Fig. 1, the preparation method of anhydrous calcium sulfate whisker comprises the steps: according to an embodiment of the invention
In step 110, plaster stone is placed in water, forms the first suspension liquid.Wherein, the liquid-solid mass ratio of water and plaster stone is 5.5 ~ 30:1.
In the step 120, in the first suspension liquid, add crystal control agent, stir and form white slurry.
Particularly, the mol ratio of crystal control agent and plaster stone is 0.7 ~ 5:1; Wherein, crystal control agent can be selected from any one in calcium chloride, ammonium chloride, magnesium chloride, ammonium sulfate.
In step 130, white slurry is moved in hydrothermal reaction kettle, allow white slurry carry out hydro-thermal reaction, obtain the second suspension liquid.
Particularly, the set temperature of hydrothermal reaction kettle is 170 DEG C ~ 220 DEG C, and the hydro-thermal reaction time is 2h ~ 10h.
What deserves to be explained is, above-mentioned hydro-thermal reaction should be carried out when stirring, and the equipment that hydro-thermal reaction adopts can be homogeneous reactor or magnetic force reactor, or other can realize the equipment of the hydro-thermal reaction under agitation condition simultaneously.
In step 140, by the second suspension liquid solid-liquid separation, obtain filter cake and filtrate, filter cake, after deionized water wash, is dried and is obtained anhydrous calcium sulfate whisker at 80 DEG C.
What deserves to be explained is, in step 140, the filtrate obtained through solid-liquid separation is capable of circulation as crystal control agent; That is, only in this filtrate, plaster stone need be added according to predetermined proportion, through stirring, can white slurry be formed, thus proceed hydro-thermal reaction; Or this filtrate is returned in step 110, mixes with the first suspension liquid, through stirring, can white slurry be formed, thus proceed hydro-thermal reaction.
Below, with reference to specific embodiment, the preparation method to anhydrous calcium sulfate whisker according to the present invention is described in detail, and for convenience of contrasting the experiment parameter of each embodiment, analyzes each embodiment of contrast in table form; Comparing result in embodiment 1-9 under different experiments parameter is as shown in table 1.
Table 1 contrasts according to the experiment parameter of embodiments of the invention 1-9
In Table 1, " mol ratio " refers to the ratio of crystal control agent and the amount of substance of plaster stone.
Wherein, the hydrothermal reaction kettle adopted in embodiment 1,2,4,5,6,7,8,9 refers to homogeneous reactor (model: JXF-8-200, producer: Pine Ridge, Yantai Chemical Equipment Co., Ltd.), wherein, the liner volume of the reactor in homogeneous reactor is 100mL, and the kettle speed of rotation of reactor is 28r/min, but the present invention is not particularly limited this, usually, when adopting this equipment, controlling kettle rotating speed is 14r/min ~ 28r/min; The hydrothermal reaction kettle adopted in embodiment 3 is magnetic force reactor (model: GSH-2/20, producer: Weihai Yuan Cheng Chemical Equipment Co., Ltd.), wherein, the volume of magnetic force reactor is 2L, its inner rotating speed of agitator is 600r/min, but the present invention is not also particularly limited this, usually, when adopting this equipment, the stirring velocity controlling inner stirring rake is 200r/min ~ 600r/min.
In above-described embodiment 1-9, in step 130, the compactedness of white slurry is about 50% ~ 80%, generally, controls to make above-mentioned hydro-thermal reaction carry out preferably within the scope of this compactedness.
Measure the anhydrous calcium sulfate whisker product that above-described embodiment 1-9 prepares, measurement result is as shown in table 2.
The measurement result of the anhydrous calcium sulfate whisker that table 2 prepares according to embodiments of the invention 1-9
| Pattern | Length/μm | Diameter/μm | |
| Embodiment 1 | Threadiness | 40～60 | 0.5～1.5 |
| Embodiment 2 | Threadiness | 40～100 | 0.5～1.0 |
| Embodiment 3 | Threadiness | 30～90 | 0.5～1.0 |
| Embodiment 4 | Threadiness | 30～60 | 0.5～3.0 |
| Embodiment 5 | Threadiness | 20～40 | 0.5～3.0 |
| Embodiment 6 | Threadiness | 30～50 | 0.5～2.0 |
| Embodiment 7 | Threadiness | 20～40 | 0.5～2.0 |
| Embodiment 8 | Threadiness | 20～30 | 1.0～2.0 |
| Embodiment 9 | Threadiness | 40～60 | 0.5～2.0 |
Wherein, SEM (scanning electron microscope) characterization result of anhydrous calcium sulfate whisker product that obtains of embodiment 1,4,7,8 is respectively as shown in Fig. 3, Fig. 5, Fig. 7 and Fig. 9; And XRD (X-ray diffraction) characterization result of the anhydrous calcium sulfate whisker product that embodiment 1,4,7,8 obtains is respectively as shown in Fig. 2, Fig. 4, Fig. 6 and Fig. 8.
It should be noted that in the prior art, with plaster stone (CaSO
42H
2o) be raw material, prepared the principle of hemihydrate calcium sulfate crystal whisker by hydrothermal method, be commonly considered as dissolution-crystallization mechanism.One, crystal control agent is by control CaSO
42H
2o and CaSO
40.5H
2the solubleness of O, thus the difference that result in system degree of supersaturation; Its two, hemihydrate calcium sulfate crystal whisker is hexagonal system, and crystal control agent is adsorbed on CaSO
40.5H
2on the different crystal faces of O, impel it to carry out one-dimensional growth, thus generate CaSO
40.5H
2o whisker.
In the preparation method of anhydrous calcium sulfate whisker according to an embodiment of the invention, with plaster stone (CaSO
42H
2o) be raw material, prepare anhydrous calcium sulfate whisker by hydrothermal method, its process and above-mentionedly there is larger difference.Specifically, on the one hand, in an embodiment according to the present invention, crystal control agent is to CaSO
42H
2o and CaSO
4solubleness impact, result in the difference of this system degree of supersaturation, thus to CaSO
4pattern controlled, obtain anhydrous calcium sulfate whisker; Skilled person will appreciate that, in the mixed system that many kinds of substance coexists, owing to there is the impact of the effect such as common-ion effcet and salting-out effect, the impact of same material on the solubleness of other materials is different, and at different temperatures, also present complex effects; On the other hand, anhydrous calcium sulfate whisker is rhombic system, and preparing in the process of anhydrous calcium sulfate whisker by plaster stone hydro-thermal, the crystal control agent in system is adsorbed on CaSO
4different crystal faces on, there is difference in the speed of growth controlling different crystal face, thus facilitates its one-dimensional growth, then forms anhydrous calcium sulfate whisker.Those skilled in the art also will be appreciated that it is at CaSO when same crystal control agent coexists from the material being in different crystallographic systems
40.5H
2o and CaSO
4the suction type on surface is different, and absorption crystal face is different, and therefore its crystal face process of growth caused is also by difference.Therefore, take plaster stone as raw material, prepare anhydrous calcium sulfate whisker with hydrothermal method and hemihydrate calcium sulfate crystal whisker is diverse two processes; And continue to prepare anhydrous calcium sulfate whisker with hemihydrate calcium sulfate crystal whisker, then need pyroprocessing, energy expenditure is comparatively large, significantly will improve production cost.
In prior art, the preparation of anhydrous calcium sulfate whisker generally adopts the preparation path of plaster stone-hemihydrate calcium sulfate crystal whisker-anhydrous calcium sulfate whisker, that is, take plaster stone as raw material, hemihydrate calcium sulfate crystal whisker is prepared through hydrothermal method, then pyroprocessing is carried out to hemihydrate calcium sulfate crystal whisker, obtain anhydrous calcium sulfate whisker; The shortcoming of the method is primarily of following two aspects, the hemihydrate calcium sulfate crystal whisker that the first obtains extent of hydration in the process of washing improves greatly, and the diameter of part whisker is thicker, generates the terra alba of sheet, then, after follow-up pyroprocessing, the purity of anhydrous calcium sulfate whisker is affected; It two is preparing in the process of anhydrous calcium sulfate whisker by hemihydrate calcium sulfate crystal whisker pyroprocessing, and energy expenditure is comparatively large, and this will cause cost significantly to improve.
Correspond ground, preparation method according to anhydrous calcium sulfate whisker of the present invention takes hydrothermal method to prepare equally, but without the pilot process of hemihydrate calcium sulfate crystal whisker, but namely one step hydro thermal method has prepared anhydrous calcium sulfate whisker product, thus can effectively avoid intermediates hemihydrate calcium sulfate crystal whisker because aquation is on the impact of anhydrous calcium sulfate whisker purity, in addition, also can avoid high-temperature calcination process, thus significantly reduce production cost.
Although illustrate and describe the present invention with reference to specific embodiment, but it should be appreciated by those skilled in the art that: when not departing from the spirit and scope of the present invention by claim and equivalents thereof, the various changes in form and details can be carried out at this.
Claims (6)
1. a preparation method for anhydrous calcium sulfate whisker, is characterized in that, comprises step:
A, plaster stone is placed in water, is mixed with the first suspension liquid, under agitation in described first suspension liquid, adds crystal control agent, form slurry; Wherein, the liquid-solid mass ratio of described water and described plaster stone is 5.5 ~ 30:1; The mol ratio of described crystal control agent and described plaster stone is 0.7 ~ 5:1;
B, described slurry to be transferred in hydrothermal reaction kettle, and under agitation to carry out hydro-thermal reaction 2h ~ 10h, obtain the second suspension liquid; Wherein, the set temperature of described hydrothermal reaction kettle is 170 DEG C ~ 220 DEG C;
C, described second suspension liquid is carried out solid-liquid separation, obtains filter cake and filtrate, described filter cake through washing, dry and obtain anhydrous calcium sulfate whisker.
2. preparation method according to claim 1, is characterized in that, described crystal control agent be selected from calcium chloride, ammonium chloride, magnesium chloride, ammonium sulfate any one.
3. preparation method according to claim 1, is characterized in that, described filtrate is back in described steps A as crystal control agent Recycling.
4. preparation method according to claim 1, is characterized in that, in described step C, described filter cake is dried through deionized water wash and at 80 DEG C and obtained described anhydrous calcium sulfate whisker.
5. preparation method according to claim 1, is characterized in that, in described step B, the compactedness of described slurry in described hydrothermal reaction kettle is 50% ~ 80%.
6. preparation method according to claim 1, is characterized in that, described hydrothermal reaction kettle is magnetic force reactor or homogeneous reactor.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105401219A (en) * | 2015-12-31 | 2016-03-16 | 中国科学院青海盐湖研究所 | Normal pressure acidification method for preparing anhydrous calcium sulfate whiskers |
| CN105668605A (en) * | 2016-01-09 | 2016-06-15 | 青岛科技大学 | Preparation method of nest-like mesoporous cerium oxide with high specific surface area |
| CN106365469A (en) * | 2016-08-31 | 2017-02-01 | 郭舒洋 | Preparation method of antifriction glass fiber reinforcement impregnating compound |
| CN108588839A (en) * | 2018-05-11 | 2018-09-28 | 武汉科技大学 | A method of using in shale vanadium extraction calcium sulfate crystal whiskers filler is prepared with slag |
| CN108893774A (en) * | 2018-07-27 | 2018-11-27 | 湖北工业大学 | A kind of preparation method of metal salt hydrotropy hydrothermal synthesis calcium sulfate crystal whiskers |
| 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 |
| CN111118606A (en) * | 2019-12-31 | 2020-05-08 | 浙江环耀环境建设有限公司 | Method for preparing calcium sulfate whiskers by using bone gelatin wastewater |
| CN111607827A (en) * | 2019-07-16 | 2020-09-01 | 北新集团建材股份有限公司 | Post-treatment method of calcium sulfate whisker |
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| EP0672634A2 (en) * | 1994-03-18 | 1995-09-20 | Salzgitter Anlagenbau Zweigniederlassung der Preussag Anlagenbau GmbH | Process for continuous production of alpha-calcium sulphate hemihydrate from calcium sulphate dihydrate |
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| CN104496237A (en) * | 2014-12-01 | 2015-04-08 | 路德环境科技股份有限公司 | Method for removing impurities from desulphurization gypsum of power plant |
| 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 |
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| CN1598083A (en) * | 2004-08-20 | 2005-03-23 | 东北大学 | Process for preparing calcium sulfate whisker |
| CN101550585A (en) * | 2009-04-16 | 2009-10-07 | 北京矿冶研究总院 | Preparation method of dehydrated calcium sulfate whisker |
| CN102534801A (en) * | 2012-02-23 | 2012-07-04 | 云南民族大学 | Method for improving quality of calcium sulfate whiskers |
| CN102794100A (en) * | 2012-07-25 | 2012-11-28 | 淮南市明月环保科技有限责任公司 | Technology of desulphurization by regenerated ammonia with combined production of calcium sulfate whisker |
| CN103014869A (en) * | 2012-12-28 | 2013-04-03 | 清华大学 | Controllable preparation method of ultrathin anhydrous calcium sulfate crystal whisker with high length-diameter ratio |
| CN104496237A (en) * | 2014-12-01 | 2015-04-08 | 路德环境科技股份有限公司 | Method for removing impurities from desulphurization gypsum of power plant |
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| CN105401219A (en) * | 2015-12-31 | 2016-03-16 | 中国科学院青海盐湖研究所 | Normal pressure acidification method for preparing anhydrous calcium sulfate whiskers |
| CN105401219B (en) * | 2015-12-31 | 2018-03-20 | 中国科学院青海盐湖研究所 | A kind of method that normal pressure acidization prepares anhydrous calcium sulfate whisker |
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| CN108893774A (en) * | 2018-07-27 | 2018-11-27 | 湖北工业大学 | A kind of preparation method of metal salt hydrotropy hydrothermal synthesis calcium sulfate crystal whiskers |
| 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 |
| CN111607827A (en) * | 2019-07-16 | 2020-09-01 | 北新集团建材股份有限公司 | Post-treatment method of calcium sulfate whisker |
| CN111607827B (en) * | 2019-07-16 | 2022-01-07 | 北新集团建材股份有限公司 | Post-treatment method of calcium sulfate whisker |
| CN111118606A (en) * | 2019-12-31 | 2020-05-08 | 浙江环耀环境建设有限公司 | Method for preparing calcium sulfate whiskers by using bone gelatin wastewater |
| CN111118606B (en) * | 2019-12-31 | 2021-12-21 | 浙江环耀环境建设有限公司 | Method for preparing calcium sulfate whiskers by using bone gelatin wastewater |
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