CN105040105B - A method of calcium sulfate crystal whiskers are prepared by oyster shell - Google Patents
A method of calcium sulfate crystal whiskers are prepared by oyster shell Download PDFInfo
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- CN105040105B CN105040105B CN201510306235.8A CN201510306235A CN105040105B CN 105040105 B CN105040105 B CN 105040105B CN 201510306235 A CN201510306235 A CN 201510306235A CN 105040105 B CN105040105 B CN 105040105B
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- calcium sulfate
- oyster shell
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- crystal whiskers
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Abstract
The present invention relates to a kind of preparation methods of calcium sulfate crystal whiskers, this method is using oyster shell, Industry Waste hydrochloric acid and sodium sulphate as raw material, it is reacted after oyster shell is crushed first with Industry Waste hydrochloric acid and prepares calcium chloride solution, then sodium sulphate is added, calcium sulfate slurry is obtained, calcium sulfate crystal whiskers are made after hydro-thermal reaction.This method can prepare high added value, high yield calcium sulfate crystal whiskers, expand the application range of oyster shell, while improve the production capacity of calcium sulfate crystal whiskers.
Description
[technical field]
The present invention relates to a kind of preparation methods of calcium sulfate crystal whiskers, and in particular to one kind prepares calcium sulfate crystal whiskers by oyster shell
Method, belong to calcium sulfate crystal whiskers preparation field.
[background technique]
China coastline is very long, and the Mollusca Resources such as oyster are extremely abundant, but the exploitation to Mollusca Resources such as oysters at present
Its edible portion is mainly processed, a large amount of marine product shell is then used as rubbish to be discarded, residual in these discarded marine product shells
During long-term stack, corruption is smelly to be caused seriously to pollute the organic matter stayed to environment.How sufficiently, it utilizes to high level male
Oyster resource is both the huge opportunity that oyster industry faces and the severe challenge that oyster industry faces.
Oyster shell is made of cuticula, prismatic layer, nacre, and major part is prismatic layer, is distributed a large amount of micropores, have compared with
Strong adsorption capacity.Oyster shell is mainly made of the organic matters such as minerals and protein, polysaccharide on composition, and minerals are then with calcium member
Based on element, calcium carbonate content is up to 90%.Two aspects are broadly divided into the higher value application of oyster shell at present, first is that utilizing
The adsorption capacity of oyster shell is used for the extraction of textile printing heavy metals in industrial wastewater ion, phosphorus etc., referring specifically to China
Patent application CN103551119A, CN103585990A, CN103962104A, CN104174362A etc..Second is that calcium in oyster shell
The high-value-use of element, such as there is document report to prepare calcium citrate, calcium gluconate or calcium carbonate by oyster shell and scallop shell
Method, but these method and steps are simple, and the product quality produced is general, and do not have desired crystal form generally,
It is simply possible to use in basic industrial application, does not there is the report for preparing calcium sulfate crystal whiskers using oyster shell also at present.
Calcium sulfate crystal whiskers are a kind of microdenier staples, and loose density is minimum, and specific surface area is huge, have good toughness, electricity absolutely
The advantages that edge is good, intensity is high, high temperature resistant, resist chemical, acid and alkali-resistance can be used as reinforcing material for polyurethane, plastics, rubber
The fields such as glue, cement, ceramics, papermaking, adhesive, friction material can also be used as the material of absorption with filtering, de- for waste water
Color, except oil emulsion, remove objectionable impurities (such as lead ion).Calcium sulfate crystal whiskers are using the natural gypsum or Industry Waste debris mostly at present
Cream is raw material, is prepared using hydro-thermal method or normal pressure acidization.
Normal pressure acidization is that at a certain temperature, high concentration calcium sulphate dihydrate suspension is changed into needle-shaped in an acidic solution
Or fibrous hemihydrate calcium sulfate crystal whisker.The method does not need operation with high pressure, and material quality score is relatively high, and theoretically product cost can
It is greatly reduced, it is easy to industrialized production.But since its preparation carries out in strong acid media, severe corrosion to equipment is operated and is controlled
System is more difficult, and equipment requirement is higher, while generating a large amount of acid-bearing wastewaters, causes serious problem of environmental pollution.
Hydro-thermal method is usually by the calcium sulphate dihydrate suspension of certain mass score in closed reaction kettle, by adding
Heat creates the reaction environment an of high temperature, high pressure, makes it through dissolution and recrystallization is converted into needle-shaped or fibrous half water sulphur
Sour calcium pyroborate.Although the material concentration that the document that the method compared with acidization less pollution, is reported at present uses is lower, for example,
Yang Ronghua etc. (inorganic chemicals industry, 2010,42 (1): 44-47) is prepared in the research of calcium sulfate crystal whiskers with the natural gypsum, is used
Pulp quality score be 5%；102965721 A of Chinese patent CN describes one kind with powdered whiting and anhydrite as original
Expect the method for hydrothermal synthesis hemihydrate calcium sulfate crystal whisker, the slurry concentration that this method uses is up to 10%；Chinese patent
CN100334264C describes a kind of method for preparing calcium sulfate crystal whiskers as raw material using gypsum, the pulp density that this method uses
It is 14%.Nevertheless, hydro-thermal method prepares limitation of the calcium sulfate crystal whiskers due to pulp density at present, production efficiency is relatively low,
Production capacity is smaller, leads to energy consumption and higher cost.
It can be seen that in the method for prior art production calcium sulfate crystal whiskers, there are the above drawbacks, are badly in need of a kind of production efficiency
Height, it is low in cost, and the preparation method of the calcium sulfate crystal whiskers of good quality of product.
[summary of the invention]
[technical problems to be solved]
The object of the present invention is to provide a kind of preparation methods of calcium sulfate crystal whiskers.
It is a further object to provide the methods to prepare the purposes in calcium sulfate crystal whiskers.
[technical solution]
According to the utilization status of current oyster shell and calcium sulfate crystal whiskers technology of preparing defect, the purpose of the present invention is find one
Kind prepares high added value, the method for high yield calcium sulfate crystal whiskers using oyster shell as primary raw material, and expand oyster shell applies model
It encloses, while improving the production capacity of calcium sulfate crystal whiskers.
The present invention is achieved through the following technical solutions.
A method of preparing calcium sulfate crystal whiskers, it is characterised in that this method is with oyster shell, Industry Waste hydrochloric acid and sodium sulphate
For raw material, is reacted after first crushing oyster shell with Industry Waste hydrochloric acid and prepare calcium chloride solution, sodium sulphate is then added, obtain sulphur
Calcium sulfate crystal whiskers are made in sour calcium slurry after hydro-thermal reaction.
According to another preferred method of implementation of the present invention, it is characterised in that this method comprises the following steps:
(1) by oyster shell after being impregnated in dilute Industry Waste hydrochloric acid, cleaning, drying, with pulverizer by the oyster shell after drying
It is ground into that powder is spare, oyster shell powder obtained is reacted to the chlorination that 0.1~3.0mol/L of concentration is made with Industry Waste hydrochloric acid
Calcium solution；
(2) under conditions of 20~80 DEG C of temperature, the metabisulfite solution of 0.1~3.0mol/L of concentration is added while stirring
Into the calcium chloride solution as made from step (1), the reaction was continued after charging 10~90min, obtain concentration be 18%~
Hydrothermal reaction kettle, 1~10h of hydro-thermal process under the conditions of 100~200 DEG C of temperature is added in the slurry by 30% calcium sulfate slurry；
(3) suspension after step (2) hydro-thermal reaction is filtered, products obtained therefrom dry 2~10h, system under the conditions of 100 DEG C
Obtain hemihydrate calcium sulfate crystal whisker.
According to another preferred method of implementation of the present invention, it is characterised in that calcium chloride solution concentration is 1.0 in step (1)
~2.5mol/L.
According to another preferred method of implementation of the present invention, it is characterised in that calcium sulfate pulp density is in step (2)
25%~30%.
According to another preferred method of implementation of the present invention, it is characterised in that be prepared 30~200 μm of length, diameter
0.5~8 μm of hemihydrate calcium sulfate crystal whisker, product yield are 90%~97%, and draw ratio is 100~300.
The method of the present invention includes the following steps: using oyster shell, Industry Waste hydrochloric acid and sodium sulphate as raw material, first by oyster shell
It is reacted after crushing with Industry Waste hydrochloric acid and prepares calcium chloride solution, sodium sulphate is then added, calcium sulfate slurry is obtained, through hydro-thermal reaction
Calcium sulfate crystal whiskers are made afterwards.Its flow diagram is shown in attached drawing 2.
The oyster shell component that the present invention uses also contains more than 20 based on inorganic matter other than calcium carbonate in inorganic matter
Micro and trace element, table 1 list the content of Partial Elements.In the hydro-thermal mistake for preparing calcium sulfate crystal whiskers for raw material by oyster shell
Cheng Zhong, the metal ions such as magnesium, potassium, manganese, iron in oyster shell play certain regulation to the growth of whisker as chemical additives
Effect.In addition, generating a large amount of sodium chloride in party's law system, sodium chloride and other metal ions are together as chemical additives
Coordinated regulation is carried out to the growth of whisker.Because of the effect of coordinated regulation, the pulp density that the present invention allows is significantly larger than tradition
Method, compared with the synthetic method of traditional addition chemical additives, this method does not need in addition to add chemical additives, and
Regulating effect is better than conventional method, and the regular appearance of gained whisker, major diameter is bigger, and it is brilliant that resulting calcium sulfate is described in table 2
The performance indicator of palpus.
The chemical component of 1 oyster shell of table
2 whisker performance indicator of table
[beneficial effect]
Technical solution of the present invention can obtain following technical effect:
(1) method raw material of the invention is cheap, can obtain high value-added product.The high income of product simultaneously, product
Yield is 90%~97%, is that one kind can expand the application range of oyster shell, while improve the production capacity of calcium sulfate crystal whiskers
Method.
(2) the calcium sulfate pulp density that the present invention allows is significantly larger than conventional method, with traditional addition chemical additives
Synthetic method compare, this method does not need in addition to add chemical additives, and regulating effect is better than conventional method, and gained is brilliant
The regular appearance of palpus, major diameter are bigger.
[Detailed description of the invention]
Calcium sulfate crystal whiskers SEM figure is prepared in Fig. 1 the application；
Fig. 2 the application prepares the flow chart of calcium sulfate crystal whiskers.
[specific embodiment]
Embodiment 1
By oyster shell after being impregnated in dilute hydrochloric acid, cleaning, drying, with high speed Universal pulverizer by the oyster shell powder after drying
It is spare to be broken into powder.Oyster shell powder obtained is reacted to the calcium chloride solution that concentration 2.2mol/L is made with Industry Waste hydrochloric acid.
Under conditions of temperature 60 C, the metabisulfite solution of 0.1~3.0mol/L of concentration is added to calcium chloride obtained while stirring
The reaction was continued in solution, after charging 60min obtains the calcium sulfate slurry that concentration is 20%.It is anti-that hydro-thermal is added in the slurry
Kettle is answered, hydro-thermal process 5h under the conditions of 150 DEG C of temperature.By the suspension filtering after hydro-thermal reaction, products obtained therefrom is in 100 DEG C of conditions
Lower dry 8h, obtains 120 μm of average length, the hemihydrate calcium sulfate crystal whisker that 0.5 μm of average diameter, product yield 90%, major diameter
Than being about 240.
Embodiment 2
By oyster shell after being impregnated in dilute hydrochloric acid, cleaning, drying, with high speed Universal pulverizer by the oyster shell powder after drying
It is spare to be broken into powder.Oyster shell powder obtained is reacted to the calcium chloride solution that concentration 2.4mol/L is made with Industry Waste hydrochloric acid.
Under conditions of 55 DEG C of temperature, the metabisulfite solution of 0.1~3.0mol/L of concentration is added to calcium chloride obtained while stirring
The reaction was continued in solution, after charging 55min obtains the calcium sulfate slurry that concentration is 22%.It is anti-that hydro-thermal is added in the slurry
Kettle is answered, hydro-thermal process 6h under the conditions of 185 DEG C of temperature.By the suspension filtering after hydro-thermal reaction, products obtained therefrom is in 100 DEG C of conditions
Lower dry 7h, obtains 150 μm of average length, the hemihydrate calcium sulfate crystal whisker that 0.7 μm of average diameter, product yield 92%, major diameter
Than being about 210.
Embodiment 3
By oyster shell after being impregnated in dilute hydrochloric acid, cleaning, drying, with high speed Universal pulverizer by the oyster shell powder after drying
It is spare to be broken into powder.Oyster shell powder obtained is reacted to the calcium chloride solution that concentration 2.9mol/L is made with Industry Waste hydrochloric acid.
Under conditions of 75 DEG C of temperature, the metabisulfite solution of 0.1~3.0mol/L of concentration is added to calcium chloride obtained while stirring
The reaction was continued in solution, after charging 80min obtains the calcium sulfate slurry that concentration is 26%.It is anti-that hydro-thermal is added in the slurry
Kettle is answered, hydro-thermal process 4h under the conditions of 145 DEG C of temperature.By the suspension filtering after hydro-thermal reaction, products obtained therefrom is in 100 DEG C of conditions
Lower dry 5h, obtains 180 μm of average length, the hemihydrate calcium sulfate crystal whisker that 1.6 μm of average diameter, product yield 95%, major diameter
Than being about 110.
Comparative example 1
Gypsum and water are made into the slurry that mass fraction is 8%, which are added hydrothermal reaction kettle, in temperature
130 DEG C of hydro-thermal process 7h.By the suspension filtering after hydro-thermal reaction, products obtained therefrom dry 7h under the conditions of 100 DEG C is averaged
87 μm of length, the hemihydrate calcium sulfate crystal whisker that average diameter is 3.1 μm, product yield 80%, draw ratio 28.
Comparative example 2
Using natural gypsum as raw material, magnesium chloride is crystal promoter, and it is 13% that gypsum and water, which are made into mass fraction,
Slurry, by the slurry be added hydrothermal reaction kettle, in 140 DEG C of hydro-thermal process 6h of temperature.By the suspension mistake after hydro-thermal reaction
Filter, products obtained therefrom dry 7h under the conditions of 100 DEG C, obtains 96 μm of average length, and the half-H 2 O calcium sulphate that average diameter is 2.7 μm is brilliant
Must, product yield 82%, draw ratio 35.
It can be seen that using method of the invention, it is possible to obtain higher pulp density, and the draw ratio of product exists
100 or more, much higher than the product of comparative example, equally, method of the invention can obtain 90% or more yield, this is also
What the method for the prior art was difficult to realize.
Claims (3)
1. a kind of method for preparing calcium sulfate crystal whiskers, it is characterised in that this method is with oyster shell, Industry Waste hydrochloric acid and sodium sulphate
Raw material reacts with Industry Waste hydrochloric acid after first crushing oyster shell and prepares calcium chloride solution, sodium sulphate is then added, obtains sulfuric acid
Calcium sulfate crystal whiskers are made in calcium slurry after hydro-thermal reaction；This method comprises the following steps:
(1) by oyster shell after dilute industrial waste salt acid soak, the oyster shell powder after drying is broken by cleaning, drying with pulverizer
Powder is spare, and oyster shell powder obtained is reacted to the calcium chloride solution that 0.1~3.0mol/L of concentration is made with Industry Waste hydrochloric acid；
(2) under conditions of 20~80 DEG C of temperature, while stirring by the metabisulfite solution of 0.1~3.0mol/L of concentration be added to by
In calcium chloride solution made from step (1), the reaction was continued after charging 10~90min, obtaining concentration is 18%~30%
Hydrothermal reaction kettle, 1~10h of hydro-thermal process under the conditions of 100~200 DEG C of temperature is added in the slurry by calcium sulfate slurry；
(3) suspension after step (2) hydro-thermal reaction is filtered, products obtained therefrom dry 2~10h under the conditions of 100 DEG C is made half
H 2 O calcium sulphate whisker；
This method is prepared 30~200 μm of length, the hemihydrate calcium sulfate crystal whisker that 0.5~8 μm of diameter, and product yield is 90%~
97%, draw ratio is 100~300.
2. the method described in claim 1 for preparing calcium sulfate crystal whiskers, it is characterised in that calcium chloride solution concentration is in step (1)
1.0~2.5mol/L.
3. the method described in claim 1 for preparing calcium sulfate crystal whiskers, it is characterised in that calcium sulfate pulp density is in step (2)
25%~30%.
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Families Citing this family (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 |
| CN106319631B (en) * | 2016-08-30 | 2019-02-22 | 湖北永绍科技股份有限公司 | The joint disposal of a kind of sulfuric acid waste and hydrochloride waste utilizes method |
| CN106350870B (en) * | 2016-08-30 | 2019-02-22 | 湖北永绍科技股份有限公司 | A kind for the treatment of and use method of sulfuric acid 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 |
| 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 |
| CN111270312B (en) * | 2020-02-12 | 2021-09-07 | 烟台大学 | Method for preparing gypsum whisker from titanium gypsum |
| 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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| CN102212884A (en) * | 2011-05-04 | 2011-10-12 | 上海大学 | Method for preparing calcium sulfate crystal whisker from many kinds of industrial waste residue gypsum serving as raw materials |
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| CN102776569A (en) * | 2012-07-09 | 2012-11-14 | 泰山医学院 | Method for preparing calcium sulfate crystal whiskers by using natural gypsum |
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| CN102212884A (en) * | 2011-05-04 | 2011-10-12 | 上海大学 | Method for preparing calcium sulfate crystal whisker from many kinds of industrial waste residue gypsum serving as raw materials |
| CN102677177A (en) * | 2012-04-13 | 2012-09-19 | 昆明理工大学 | Preparation method of calcium sulfate hemihydrate crystal whiskers high in length diameter ratio |
| CN102776569A (en) * | 2012-07-09 | 2012-11-14 | 泰山医学院 | Method for preparing calcium sulfate crystal whiskers by using natural gypsum |
| CN103446622A (en) * | 2013-08-13 | 2013-12-18 | 江苏大学 | Method for releasing calcium and vancomycin by utilizing alpha-calcium sulfate hemihydrate whiskers |
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