CN105040105A - Method for preparing calcium sulfate whiskers with oyster shells - Google Patents
Method for preparing calcium sulfate whiskers with oyster shells Download PDFInfo
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- CN105040105A CN105040105A CN201510306235.8A CN201510306235A CN105040105A CN 105040105 A CN105040105 A CN 105040105A CN 201510306235 A CN201510306235 A CN 201510306235A CN 105040105 A CN105040105 A CN 105040105A
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- calcium sulfate
- oyster shells
- sulfate crystal
- calcium
- crystal whiskers
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- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 title claims abstract description 97
- 241000237502 Ostreidae Species 0.000 title claims abstract description 43
- 235000020636 oyster Nutrition 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 41
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 17
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 239000002440 industrial waste Substances 0.000 claims abstract description 10
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 8
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 8
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 8
- 239000013078 crystal Substances 0.000 claims description 43
- 229940095672 calcium sulfate Drugs 0.000 claims description 40
- 239000000843 powder Substances 0.000 claims description 15
- 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 claims description 14
- 229940057306 hemihydrate calcium sulfate Drugs 0.000 claims description 12
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 11
- 239000000725 suspension Substances 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 5
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000007669 thermal treatment Methods 0.000 claims description 5
- 239000002699 waste material Substances 0.000 claims description 5
- 238000010298 pulverizing process Methods 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 239000002002 slurry Substances 0.000 abstract description 2
- 239000000126 substance Substances 0.000 description 11
- 239000000654 additive Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 239000011505 plaster Substances 0.000 description 4
- 239000004575 stone Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 241000237852 Mollusca Species 0.000 description 2
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 2
- 230000000274 adsorptive effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011507 gypsum plaster Substances 0.000 description 2
- 238000010335 hydrothermal treatment Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 235000014102 seafood Nutrition 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 241000237509 Patinopecten sp. Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 229910052925 anhydrite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- NEEHYRZPVYRGPP-IYEMJOQQSA-L calcium gluconate Chemical compound [Ca+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O NEEHYRZPVYRGPP-IYEMJOQQSA-L 0.000 description 1
- IKRMZAOEXULJQX-UHFFFAOYSA-N calcium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Ca+2].O1B([O-])OB2OB([O-])OB1O2 IKRMZAOEXULJQX-UHFFFAOYSA-N 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000007764 o/w emulsion Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 235000020637 scallop Nutrition 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 210000000434 stratum corneum Anatomy 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
Landscapes
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The invention relates to a preparation method of calcium sulfate whiskers. The method is characterized by using oyster shells, industrial waste hydrochloric acid and sodium sulfate as raw materials, firstly grinding the oyster shells and then reacting the ground oyster shells with the industrial waste hydrochloric acid to prepare a calcium chloride solution, then adding sodium sulfate to obtain calcium sulfate slurry, and preparing the calcium sulfate whiskers after hydrothermal reaction. The method can achieve the effects of preparing the calcium sulfate whiskers with high added values and high yields, expanding the application range of the oyster shells and also improving the production capacity of the calcium sulfate whiskers.
Description
[technical field]
The present invention relates to a kind of preparation method of calcium sulfate crystal whiskers, be specifically related to a kind of method being prepared calcium sulfate crystal whiskers by oyster shells, belong to calcium sulfate crystal whiskers preparation field.
[background technology]
China shoreline is very long, the Mollusca Resources such as oyster are very abundant, but at present its edible portion is mainly processed to the exploitation of the Mollusca Resources such as oyster, a large amount of sea-food shells then goes out of use as rubbish, organism residual in these discarded sea-food shells is in long-term process of stacking, and corruption is smelly causes severe contamination to environment.How fully, utilize oyster resource to high level, being the huge opportunity that oyster industry faces, is also the severe challenge that oyster industry faces.
Oyster shells is made up of stratum corneum, prismatic layer, nacreous layer, and major portion is prismatic layer, and distribute a large amount of micropore, has stronger adsorptive power.On composition, oyster shells is primarily of mineral substance and the organism such as protein, polysaccharide composition, and mineral substance is then based on calcium constituent, and its calcium carbonate content is up to 90%.At present two aspects are mainly divided into the higher value application of oyster shells, one is the extraction utilizing the adsorptive power of oyster shells to use it for textile printing heavy metals in industrial wastewater ion, phosphorus etc., specifically see Chinese patent application CN103551119A, CN103585990A, CN103962104A, CN104174362A etc.Two is the high-value-uses of calcium constituent in oyster shells, bibliographical information is such as had to prepare the method for citrate of lime, calglucon or calcium carbonate by oyster shells and scallop shell, but these method stepss are simple, the quality product produced is general, and generally not there is the crystal formation of expectation, only can be used in basic industrial application, also not have the report utilizing oyster shells to prepare calcium sulfate crystal whiskers at present.
Calcium sulfate crystal whiskers is a kind of microdenier staple, aerated density is minimum, specific surface area is huge, there is good toughness, electrical insulating property be good, intensity is high, high temperature resistant, the advantage such as resist chemical, acid and alkali-resistance, can be used as strongthener for fields such as urethane, plastics, rubber, cement, pottery, papermaking, sizing agent, friction materialss, also can be used as absorption and the material filtered, for waste water decoloring, except oil in water emulsion, remove detrimental impurity (as lead ion).Current calcium sulfate crystal whiskers is adopt the plaster of paris or industrial residue gypsum to be raw material mostly, adopts hydrothermal method or the preparation of normal pressure acidization.
Normal pressure acidization is at a certain temperature, and high density terra alba suspension changes needle-like or fibrous hemihydrate calcium sulfate crystal whisker in an acidic solution into.This method does not need high top pressure operation, and raw materials quality mark is higher, and product cost can significantly reduce in theory, is easy to suitability for industrialized production.But carry out because it is prepared in strong acid media, serious to equipment corrosion, operate and control more difficult, equipment requirements is higher, produces a large amount of acid-bearing wastewater, causes serious problem of environmental pollution simultaneously.
Hydrothermal method is generally by the terra alba suspension of certain mass mark in airtight reactor, by heating, creates the reaction environment of a high temperature, high pressure, make its by dissolving and recrystallization is converted into needle-like or fibrous hemihydrate calcium sulfate crystal whisker.Although this method is acidization less pollution comparatively, but the material concentration of the document employing of report is all lower at present, such as, (the inorganic chemicals industry such as Yang Ronghua, 2010,42 (1): 44-47) prepare in the research of calcium sulfate crystal whiskers with the plaster of paris, the pulp quality mark adopted is 5%; Chinese patent CN102965721A describes a kind of method being raw water thermal synthesis hemihydrate calcium sulfate crystal whisker with water-ground limestone and anhydrite, and the slurry concentration that the method adopts is up to 10%; It take plaster stone as the method that calcium sulfate crystal whiskers prepared by raw material that Chinese patent CN100334264C describes a kind of, and the pulp density that the method adopts is 14%.However, current hydrothermal method prepares the restriction of calcium sulfate crystal whiskers due to pulp density, and production efficiency is relatively low, and throughput is less, cause energy consumption and cost higher.
As can be seen here, prior art is produced in the method for calcium sulfate crystal whiskers exists above drawback, is badly in need of a kind of production efficiency high, with low cost, and the preparation method of the calcium sulfate crystal whiskers of good quality of product.
[summary of the invention]
[technical problem that will solve]
The object of this invention is to provide a kind of preparation method of calcium sulfate crystal whiskers.
Another object of the present invention is to provide described method and is preparing the purposes in calcium sulfate crystal whiskers.
[technical scheme]
Present situation and calcium sulfate crystal whiskers technology of preparing defect is utilized according to current oyster shells, the object of the invention is to find a kind of is main raw material with oyster shells, prepare the method for high added value, high yield kraft calcium pyroborate, expand the range of application of oyster shells, improve the throughput of calcium sulfate crystal whiskers simultaneously.
The present invention is achieved through the following technical solutions.
A kind of method preparing calcium sulfate crystal whiskers, it is characterized in that the method with oyster shells, Industry Waste hydrochloric acid and sodium sulfate for raw material, first rear for oyster shells pulverizing and industrial waste salt acid-respons are prepared calcium chloride solution, then sodium sulfate is added, obtain calcium sulfate slip, obtained calcium sulfate crystal whiskers after hydro-thermal reaction.
According to another kind of preferred implementation of the present invention, it is characterized in that the method comprises the steps:
(1), after being soaked in rare Industry Waste hydrochloric acid by oyster shells, cleaning, drying, is broken into powder with pulverizer by the oyster shell powder after oven dry for subsequent use, obtained oyster shells powder and industrial waste salt acid-respons is obtained the calcium chloride solution of concentration 0.1 ~ 3.0mol/L;
(2) under the condition of temperature 20 ~ 80 DEG C, while stirring the metabisulfite solution of concentration 0.1 ~ 3.0mol/L is joined in the calcium chloride solution obtained by step (1), reaction 10 ~ 90min is continued after reinforced, obtain the calcium sulfate slip that concentration is 18% ~ 30%, this slip is added hydrothermal reaction kettle, at temperature 100 ~ 200 DEG C of Water Under thermal treatment 1 ~ 10h;
(3) by the suspension filtered after step (2) hydro-thermal reaction, products obtained therefrom is dry 2 ~ 10h under 100 DEG C of conditions, obtained hemihydrate calcium sulfate crystal whisker.
According to another kind of preferred implementation of the present invention, it is characterized in that in step (1), calcium chloride solution concentration is 1.0 ~ 2.5mol/L.
According to another kind of preferred implementation of the present invention, it is characterized in that in step (2), calcium sulfate pulp density is 25% ~ 30%.
According to another kind of preferred implementation of the present invention, it is characterized in that preparing length 30 ~ 200 μm, the hemihydrate calcium sulfate crystal whisker that diameter is 0.5 ~ 8 μm, product yield is 90% ~ 97%, and length-to-diameter ratio is 100 ~ 300.
The inventive method comprises the steps: with oyster shells, Industry Waste hydrochloric acid and sodium sulfate as raw material, first rear for oyster shells pulverizing and industrial waste salt acid-respons are prepared calcium chloride solution, then add sodium sulfate, obtain calcium sulfate slip, obtained calcium sulfate crystal whiskers after hydro-thermal reaction.Its FB(flow block) is shown in accompanying drawing 2.
The oyster shells composition that the present invention adopts is based on inorganics, and except calcium carbonate, also plant trace and trace elements containing more than 20 in inorganics, table 1 lists the content of Partial Elements.Be that raw material is prepared in the water-heat process of calcium sulfate crystal whiskers by oyster shells, the metal ions such as the magnesium in oyster shells, potassium, manganese, iron play certain regulating and controlling effect as the growth of chemical additives to whisker.In addition, generate a large amount of sodium-chlor in the method system, sodium-chlor carries out coordinated regulation as chemical additives to the growth of whisker together with other metal ion.Because the effect of coordinated regulation, the pulp density that the present invention allows is far away higher than traditional method, compared with the synthetic method of traditional interpolation chemical additives, present method does not need to add chemical additives in addition, and regulating effect is better than traditional method, the regular appearance of gained whisker, length-to-diameter ratio is comparatively large, describes the performance index of the calcium sulfate crystal whiskers of gained in table 2.
The chemical composition of table 1 oyster shells
Table 2 whisker performance index
[beneficial effect]
Technical scheme of the present invention can obtain following technique effect:
(1) method raw material of the present invention is cheap, can obtain high value-added product.The yield of product is high simultaneously, and product yield is 90% ~ 97%, is a kind of range of application that can expand oyster shells, improves the method for the throughput of calcium sulfate crystal whiskers simultaneously.
(2) the calcium sulfate pulp density of the present invention's permission is far away higher than traditional method, compared with the synthetic method of traditional interpolation chemical additives, present method does not need to add chemical additives in addition, and regulating effect is better than traditional method, the regular appearance of gained whisker, length-to-diameter ratio is larger.
[accompanying drawing explanation]
Fig. 1 the application prepares calcium sulfate crystal whiskers SEM and schemes;
Fig. 2 the application prepares the schema of calcium sulfate crystal whiskers.
[embodiment]
Embodiment 1
By oyster shells after soaking in dilute hydrochloric acid, cleaning, drying, is broken into powder with high speed Universalpulverizer by the oyster shell powder after oven dry for subsequent use.Obtained oyster shells powder and industrial waste salt acid-respons are obtained the calcium chloride solution of concentration 2.2mol/L.Under the condition of temperature 60 C, while stirring the metabisulfite solution of concentration 0.1 ~ 3.0mol/L is joined in obtained calcium chloride solution, continue reaction 60min after reinforced, obtain the calcium sulfate slip that concentration is 20%.This slip is added hydrothermal reaction kettle, at temperature 150 DEG C of Water Under thermal treatment 5h.By the suspension filtered after hydro-thermal reaction, products obtained therefrom is dry 8h under 100 DEG C of conditions, and obtain mean length 120 μm, the hemihydrate calcium sulfate crystal whisker that mean diameter is 0.5 μm, product yield is 90%, and length-to-diameter ratio is about 240.
Embodiment 2
By oyster shells after soaking in dilute hydrochloric acid, cleaning, drying, is broken into powder with high speed Universalpulverizer by the oyster shell powder after oven dry for subsequent use.Obtained oyster shells powder and industrial waste salt acid-respons are obtained the calcium chloride solution of concentration 2.4mol/L.Under the condition of temperature 55 DEG C, while stirring the metabisulfite solution of concentration 0.1 ~ 3.0mol/L is joined in obtained calcium chloride solution, continue reaction 55min after reinforced, obtain the calcium sulfate slip that concentration is 22%.This slip is added hydrothermal reaction kettle, at temperature 185 DEG C of Water Under thermal treatment 6h.By the suspension filtered after hydro-thermal reaction, products obtained therefrom is dry 7h under 100 DEG C of conditions, and obtain mean length 150 μm, the hemihydrate calcium sulfate crystal whisker that mean diameter is 0.7 μm, product yield is 92%, and length-to-diameter ratio is about 210.
Embodiment 3
By oyster shells after soaking in dilute hydrochloric acid, cleaning, drying, is broken into powder with high speed Universalpulverizer by the oyster shell powder after oven dry for subsequent use.Obtained oyster shells powder and industrial waste salt acid-respons are obtained the calcium chloride solution of concentration 2.9mol/L.Under the condition of temperature 75 DEG C, while stirring the metabisulfite solution of concentration 0.1 ~ 3.0mol/L is joined in obtained calcium chloride solution, continue reaction 80min after reinforced, obtain the calcium sulfate slip that concentration is 26%.This slip is added hydrothermal reaction kettle, at temperature 145 DEG C of Water Under thermal treatment 4h.By the suspension filtered after hydro-thermal reaction, products obtained therefrom is dry 5h under 100 DEG C of conditions, and obtain mean length 180 μm, the hemihydrate calcium sulfate crystal whisker that mean diameter is 1.6 μm, product yield is 95%, and length-to-diameter ratio is about 110.
Comparative example 1
Plaster stone and water are made into massfraction be 8% slip, this slip is added hydrothermal reaction kettle, at temperature 130 DEG C of hydrothermal treatment consists 7h.By the suspension filtered after hydro-thermal reaction, products obtained therefrom is dry 7h under 100 DEG C of conditions, obtains mean length 87 μm, and mean diameter is the hemihydrate calcium sulfate crystal whisker of 3.1 μm, and product yield is 80%, and length-to-diameter ratio is 28.
Comparative example 2
With natural plaster stone for raw material, magnesium chloride is crystal promoter, plaster stone and water are made into massfraction be 13% slip, this slip is added hydrothermal reaction kettle, at temperature 140 DEG C of hydrothermal treatment consists 6h.By the suspension filtered after hydro-thermal reaction, products obtained therefrom is dry 7h under 100 DEG C of conditions, obtains mean length 96 μm, and mean diameter is the hemihydrate calcium sulfate crystal whisker of 2.7 μm, and product yield is 82%, and length-to-diameter ratio is 35.
As can be seen here, adopt method of the present invention, higher pulp density can be obtained, and the length-to-diameter ratio of product is all more than 100, far above the product of comparative example, equally, method of the present invention can obtain the productive rate of more than 90%, and this is also that the method for prior art is difficult to realize.
Claims (4)
1. prepare the method for calcium sulfate crystal whiskers for one kind, it is characterized in that the method with oyster shells, Industry Waste hydrochloric acid and sodium sulfate for raw material, first rear for oyster shells pulverizing and industrial waste salt acid-respons are prepared calcium chloride solution, then sodium sulfate is added, obtain calcium sulfate slip, obtained calcium sulfate crystal whiskers after hydro-thermal reaction; The method comprises the steps:
(1), after being soaked in rare Industry Waste hydrochloric acid by oyster shells, cleaning, drying, is broken into powder with pulverizer by the oyster shell powder after oven dry for subsequent use, obtained oyster shells powder and industrial waste salt acid-respons is obtained the calcium chloride solution of concentration 0.1 ~ 3.0mol/L;
(2) under the condition of temperature 20 ~ 80 DEG C, while stirring the metabisulfite solution of concentration 0.1 ~ 3.0mol/L is joined in the calcium chloride solution obtained by step (1), reaction 10 ~ 90min is continued after reinforced, obtain the calcium sulfate slip that concentration is 18% ~ 30%, this slip is added hydrothermal reaction kettle, at temperature 100 ~ 200 DEG C of Water Under thermal treatment 1 ~ 10h;
(3) by the suspension filtered after step (2) hydro-thermal reaction, products obtained therefrom is dry 2 ~ 10h under 100 DEG C of conditions, obtained hemihydrate calcium sulfate crystal whisker.
2. the method preparing calcium sulfate crystal whiskers according to claim 1, is characterized in that in step (1), calcium chloride solution concentration is 1.0 ~ 2.5mol/L.
3. the method preparing calcium sulfate crystal whiskers according to claim 1, is characterized in that in step (2), calcium sulfate pulp density is 25% ~ 30%.
4. the method preparing calcium sulfate crystal whiskers according to claim 3, it is characterized in that preparing length 30 ~ 200 μm, the hemihydrate calcium sulfate crystal whisker that diameter is 0.5 ~ 8 μm, product yield is 90% ~ 97%, and length-to-diameter ratio is 100 ~ 300.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105483816A (en) * | 2015-12-15 | 2016-04-13 | 湖南科技大学 | Method for preparing calcium sulfate whiskers from acetylene sludge and waste sulfuric acid |
| CN106319631A (en) * | 2016-08-30 | 2017-01-11 | 湖北永绍科技股份有限公司 | Comprehensive treating and utilizing method of sulfuric acid waste liquor and hydrochloric acid waste liquor |
| CN106350870A (en) * | 2016-08-30 | 2017-01-25 | 湖北永绍科技股份有限公司 | Disposal and utilization method for sulfuric acid waste liquid |
| CN109837592A (en) * | 2019-03-07 | 2019-06-04 | 山东虎力机械有限公司 | A kind of joint disposal of industrial wastes utilizes method |
| CN109735899B (en) * | 2019-03-07 | 2019-08-02 | 雅邦新材料研发南京有限公司 | A kind of resource utilization method of trade waste |
| CN111270312A (en) * | 2020-02-12 | 2020-06-12 | 烟台大学 | Method for preparing gypsum whisker from titanium gypsum |
| CN112342606A (en) * | 2020-10-29 | 2021-02-09 | 河南城建学院 | Method for preparing calcium sulfate whisker by using salt slurry |
| CN112408453A (en) * | 2020-12-01 | 2021-02-26 | 任杰 | Process for producing calcium sulfate by using waste sulfuric acid |
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| CN105483816A (en) * | 2015-12-15 | 2016-04-13 | 湖南科技大学 | Method for preparing calcium sulfate whiskers from acetylene sludge and waste sulfuric acid |
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| CN109837592A (en) * | 2019-03-07 | 2019-06-04 | 山东虎力机械有限公司 | A kind of joint disposal of industrial wastes utilizes method |
| CN109735899B (en) * | 2019-03-07 | 2019-08-02 | 雅邦新材料研发南京有限公司 | A kind of resource utilization method of trade waste |
| CN109837592B (en) * | 2019-03-07 | 2019-09-27 | 广西阿米巴科技有限公司 | A kind of joint disposal of industrial wastes utilizes method |
| CN111270312A (en) * | 2020-02-12 | 2020-06-12 | 烟台大学 | Method for preparing gypsum whisker from titanium gypsum |
| CN112342606A (en) * | 2020-10-29 | 2021-02-09 | 河南城建学院 | Method for preparing calcium sulfate whisker by using salt slurry |
| CN112342606B (en) * | 2020-10-29 | 2021-08-24 | 河南城建学院 | Method for preparing calcium sulfate whisker by using salt slurry |
| CN112408453A (en) * | 2020-12-01 | 2021-02-26 | 任杰 | Process for producing calcium sulfate by using waste sulfuric acid |
| CN113106536A (en) * | 2021-03-11 | 2021-07-13 | 山东创领新材料科技有限公司 | Method for preparing calcium sulfate whiskers from calcium chloride solution and sodium sulfate as phosphoric acid byproducts |
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