CN104005086B - The method of Dihydrate gypsum whiskers prepared by a kind of ardealite - Google Patents
The method of Dihydrate gypsum whiskers prepared by a kind of ardealite Download PDFInfo
- Publication number
- CN104005086B CN104005086B CN201410135538.3A CN201410135538A CN104005086B CN 104005086 B CN104005086 B CN 104005086B CN 201410135538 A CN201410135538 A CN 201410135538A CN 104005086 B CN104005086 B CN 104005086B
- Authority
- CN
- China
- Prior art keywords
- ardealite
- dihydrate gypsum
- gypsum whiskers
- dihydrate
- hydrochloric acid
- 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.)
- Expired - Fee Related
Links
Landscapes
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The present invention relates to industrial chemicals preparing technical field, the method for Dihydrate gypsum whiskers prepared by a kind of ardealite, by the preparation of removal of impurities calcium sulphate dihydrate；The preparation of whisker；Washing；Drying steps prepares Dihydrate gypsum whiskers；After to hydrochloric acid the pre-heat treatment, and under constant temperature, a certain amount of proportioning is carried out with ardealite, enable reaction to go on, and guarantee that raw material is not wasted, it is possible to appropriate gets rid of to greatest extent by the impurity contained in ardealite, reduce the impurity generation contributive rate to Dihydrate gypsum whiskers, improve the content of calcium sulfate composition, improve the productivity ratio of Dihydrate gypsum whiskers, reduce ardealite comprehensive utilization and produce the production cost of Dihydrate gypsum whiskers.
Description
Technical field
The present invention relates to industrial chemicals preparing technical field, two water prepared by especially a kind of ardealite
The method of calcium sulfate crystal whiskers.
Background technology
Ardealite is the accompaniment during Wet-process Phosphoric Acid Production, is mainly composed of sulfate dihydrate
Calcium.At present, stacking is the main methods of ardealite naturally, the ardealite volume of cargo in storage of China
At 300,000,000 more than t, and increasing with the scale of annual 4000～50,000,000 t, this not only needs to expend in a large number
Fund, take tract, and stack for a long time, institute's fluoride in ardealite, free
Phosphoric acid, P2O5, the impurity such as phosphate ecological environment can be caused serious harm；Meanwhile, phosphorus stone
Cream is applied to construction material, soil conditioner and the field such as build the road there is also that power consumption is high, secondary
The problem such as pollute, added value of product is low.Therefore develop high value added product, turn waste into wealth, real
Existing ardealite recycling is of great practical significance.
But, possibly together with other impurity multiple in ardealite, such as: phosphorus quartzy, undecomposed
Lime stone, insoluble P2O5, water-soluble P2O5, eutectic P2O5, fluoride and fluorine, aluminium, magnesium,
The phosphate of iron and sulfate etc., therefore, it is ardealite comprehensive utilization that ardealite carries out pretreatment
Precondition.
The production of calcium sulfate crystal whiskers is the ardealite processing method of a kind of low cost high added value.
Calcium sulfate crystal whiskers typically refers to gypsum as raw material, by manual control, with monocrystalline
Form growth, there is uniform cross section, complete profile, the fibre of perfect internal structure
Dimension shape (palpus shape) monocrystal.There is Dihydrate gypsum whiskers (CaSO4·2H2O), half water sulphur
Acid calcium pyroborate (CaSO4·0.5H2And anhydrous calcium sulfate whisker (CaSO O)4) point, it
Outward appearance be white fluffy solid.It is a kind of function admirable, cheap novel
Functional material, is widely used in plastics, rubber, adhesive, nylon, papermaking, water process etc.
In industry.
Preparing calcium sulfate crystal whiskers with ardealite for raw material, it is the most granular
CaSO4·2H2O is to fibrous half water or anhydrous CaSO4Conversion process, essence be one " molten
Solve exsiccation " process.But ardealite exists P2O5, F, Fe, Mg etc. many
Plant impurity and can destroy the dissolution equilibrium of calcium sulphate dihydrate, affect the generation of nucleus and the life of whisker
Long.
To this end, have researcher with ardealite for raw material by lime neutralizations, ball milling, sieve, float
Select, wash, calcine, the preprocess method such as sulfuric acid to leach produces calcium sulfate crystal whiskers, such as Cui Yishun
" research of preparing calcium sulphate whiskers from ardealite " uses grinds, rinse, acidifying etc. walks
Suddenly, preparing calcium sulfate whiskers productivity is 31.36%, purity 93.61%, draw ratio 95,
Whiteness 65.8%；Yang Lin uses stone in " research of ardealite Hydrothermal Synthesis calcium sulfate crystal whiskers "
The methods such as ash neutralization, ball milling, screening, prepare average diameter 1～3 μm, draw ratio about
The calcium sulfate crystal whiskers of 48.
Luo Kangbi Patent No. CN 102634843 A " micron order sulphur produced by a kind of ardealite
Acid calcium particle and the method for whisker " disclose hot sulfuric acid mixed solution process ardealite, then take advantage of
Thermal release, can prepare after leachate cooling calcium sulfate crystal whiskers phosphor fluorine containing less than 0.1%, whiteness 83%
Left and right, particle diameter are less than 50 μm, draw ratio 50～100；Wuhan University Of Technology is in Patent No.
CN 201210485808.4 " a kind of prepares hemihydrate calcium sulfate crystal whisker with ardealite for primary raw material
Method " disclose and a kind of ardealite, hydrochloric acid, sulfuric acid and water carried out dispensing by proportioning, then
Under the speed conditions of normal pressure, 80～110 DEG C and 250～350r/min, stir 1～2h, then exist
Filter under the conditions of 80～110 DEG C, obtain primary filter cake, by primary filter cake with the hot water of 80～100 DEG C
Washing 1～2 time, standby, filtrate and cleaning solution return the method for phosphoric acid production workshop section reuse；Elder brother
Bright Polytechnics Patent No. CN 201210127729.6 " micron order produced by a kind of ardealite
Calcium sulfate particle and the method for whisker " in disclose and a kind of add by every 100mL sulfuric acid solution
The ratio of 0.01～0.1g auxiliary agent adds auxiliary agent in sulfuric acid solution, 60～90 DEG C, constantly stir
Adding ardealite under conditions of mixing, every 100mL sulfuric acid solution adds 10～30g ardealites, stirs
After mixing reaction 0.5～4.0h, filtering, filtrate refrigerated separation obtains the method for crystal；Wengfu (collection
Group) " a kind of by ardealite system in Patent No. CN 200910102849.9 of Co., Ltd
The method of standby ultra-fine calcium sulfate crystal whisker " in disclose one and include: at ardealite fine
Managing to particle diameter is 0.1～100 μm, adds water and is made into the slip that mass percent is 5～15%,
Regulation pH value is 3～5, and at 125～145 DEG C, pressure is reaction 3～5h under the conditions of 2～3MPa,
Suction filtration while hot, is drying to obtain calcium sulfate crystal whiskers at 120～250 DEG C.
Said method is respectively arranged with weak point, is mainly manifested in calcium sulfate whiskers productivity purity
Low, whiteness is low, draw ratio is little, preparation process is complicated；It is embodied in: ardealite is not
The preprocessed preparation being directly used in calcium sulfate crystal whiskers or brilliant for calcium sulfate after pretreatment
Must preparation, but the most preprocessed or through pretreated ardealite, its impurity is equal
It is difficult to sufficiently be removed so that contained plurality of impurities therein will affect the product of whisker
Matter, such as magnesium delay the conversion of gypsum crystal formation, and iron can make crystal broaden, and aluminium affects sulfate dihydrate
The length of calcium crystal and width, the too high reunion etc. making crystal generation stronger of sulfate radical, meanwhile,
Calcium sulfate whiskers purity and whiteness also can be on the low side because of impurity.
In each pretreatment mode preparing calcium sulfate crystal whiskers with ardealite for raw material, pass through ball milling
The whisker of preparation is rough and draw ratio is low；Screening condition difficulty controls, power consumption height, investment
Greatly, it is difficult to realize industrialized production；Washing water consumption is big, and sewage disposal difficulty is big；Wet method phosphorus
The ardealite that acid produces is acid strong, and with high with cost in lime, treatment effect is general, and causes
The waste of phosphor resource；Calcination process can produce the gas of etching apparatus；Sulfuric acid to leach removal of impurities is produced
Product productivity is low, and preparation unit mass calcium sulfate crystal whiskers energy consumption is big.
To this end, we are badly in need of being the pretreating scheme that calcium sulfate crystal whiskers prepared by raw material to ardealite
Make to improve research, it is provided that a kind of new approaches.
Summary of the invention
In order to solve above-mentioned technical problem present in prior art, the present invention provides a kind of phosphorus stone
The method of Dihydrate gypsum whiskers prepared by cream, its have make full use of ardealite, reduce ecological dirty
Contaminate, economize on resources, technique is simple, easily operation, reaction condition are gentle, is not required to HTHP bar
Part, the industry that is readily put into produce, product quality of calcium sulfate whiskers is good, stable crystal form, whiteness
The features such as height, draw ratio are big.
In order to realize above-mentioned technical purpose, it is achieved particular by techniques below scheme:
The method of Dihydrate gypsum whiskers prepared by a kind of ardealite, comprises the following steps:
(1) preparation of removal of impurities calcium sulphate dihydrate: first the hydrochloric acid that concentration is 5～15wt% is preheated
After 80～90 DEG C, stir preheated hydrochloric acid, and when stirring, add ardealite and join
Become slip, after isothermal reaction 8～15min, the most once filter, it is thus achieved that first-time filtrate and once
Filter cake；Reusing filter cake is in slurry, after filtrate crystallisation by cooling, then carries out secondary filter, it is thus achieved that two
Secondary filtrate and secondary filter cake；Secondary filtrate recycle is in slurry, and secondary filter cake is two water after removal of impurities
Calcium sulfate；
(2) preparation of whisker: according to solid-to-liquid ratio 1:20～30 in the calcium sulphate dihydrate after removal of impurities
Add the hydrochloric acid that concentration is 5～15wt%, stir, to heat the calcium sulphate dihydrate after making removal of impurities complete
After dissolving, be added thereto in step 1) in 0.001～0.01% help of hydrochloric acid quality that use
Brilliant agent, adds thermal agitation and is completely dissolved to crystallization in motion agent, then crystallisation by cooling, filters for three times, it is thus achieved that three
Secondary filtrate and three filter cakes, three filtrate recycles are two water sulphur in the preparation of whisker, three filter cakes
Acid calcium pyroborate；
(3) washing: use clear water to be cleaned by three filter cakes, during until three filter cakes are neutrality,
Stop cleaning, and by the preparation of cleaning solution reuse Yu whisker；
(4) it is dried: the Dihydrate gypsum whiskers after scrubbed is placed in temperature is at 50～60 DEG C
It is dried 1～3h and prepares Dihydrate gypsum whiskers.
Preferably, described step 1) in, the concentration of hydrochloric acid is 10wt%.
Preferably, described step 1) in, hydrochloric acid preheating temperature is 85 DEG C.
It is also preferred that the left described step 1) in, mixing speed is 200～300r/min.
It is also preferred that the left described step 1) in, ardealite is 1:20～30 with the proportioning of hydrochloric acid.
Preferably, described step 1) in, the isothermal reaction time is 10min.
Further, described step 1) in, each constituent content of calcium sulphate dihydrate after removal of impurities
CaSO4·2H2O >=98wt%, P2O5With the total amount≤0.001wt% of F, SiO2≤ 0.1wt%,
MgO、Fe2O3And Al2O3Total amount≤0.01wt%.
It is also preferred that the left described step 2) in, mixing speed is 150～250r/min.
Preferably, described step 2) in, crystallization in motion agent is lauryl sodium sulfate, addition
For in step 1) in use hydrochloric acid quality 0.005%.
Preferably, described step 3) in, baking temperature is 55 DEG C of dry 2h.
After to hydrochloric acid the pre-heat treatment, and under constant temperature, carry out a certain amount of with ardealite
Proportioning, enable reaction to go on, and guarantee that raw material is not wasted, it is possible to appropriate general
The impurity contained in ardealite is got rid of to greatest extent, reduces impurity to Dihydrate gypsum whiskers
Generation contributive rate, improve the content of calcium sulfate composition, improve Dihydrate gypsum whiskers
Productivity ratio, reduces ardealite comprehensive utilization and produces the production cost of Dihydrate gypsum whiskers.
Compared with prior art, the technique effect of the present invention is embodied in:
1. making full use of trade waste ardealite, the exploitation one for ardealite is new
Application approach, reduce environmental pollution, saved chemical resource.
2. processing step is simply, easily operate, and reaction condition is gentle, is not required to high-temperature and high-pressure conditions,
The industry that is readily put into produces.
3. reactant liquor can be recycled, less energy consumption, and production cost is low；Without waste residue, waste liquid row
Putting, environmental pollution is little, has good economic benefit and environmental benefit.
4., for sulfuric acid is as pretreatment reaction liquid, calcium sulphate dihydrate is in hydrochloric acid
Solubility is bigger, and unit volume reactant liquor calcium sulfate crystal whiskers productivity is high, and energy consumption reduces.
5. relative to traditional preprocess method, the present invention uses hydrochloric acid pre-Grape berry phosphorus stone
The method of cream, it is possible to the impurity removed in ardealite of relatively limits, it is to avoid magnesium, iron, aluminium,
The impact that Dihydrate gypsum whiskers is formed by the impurity such as sulfate radical so that product calcium sulfate crystal whiskers product
Matter is good, stable crystal form, and whiteness is high, and draw ratio is big, and production efficiency is preferable.
Detailed description of the invention
Below in conjunction with specific embodiment, technical scheme is further limited
Fixed, but claimed scope is not only limited to description.
Embodiment 1
The method of Dihydrate gypsum whiskers prepared by a kind of ardealite, comprises the following steps:
(1) prepared by removal of impurities calcium sulphate dihydrate: the hydrochloric acid solution of 500g5wt% is preheated to 90 DEG C
After, adding ardealite in the ratio of solid-to-liquid ratio 1:30, rotating speed is that stirring is anti-under the conditions of 200r/min
Answer 15min, the most once filter, reusing filter cake, crystallisation by cooling under filtrate room temperature, crystallize
Bi Hou, secondary filter, filter cake is the calcium sulphate dihydrate after removal of impurities, and filtrate is recycled and reused for dissolving
Ardealite.
(2) prepared by whisker: remove miscellaneous after calcium sulphate dihydrate 50g, by the ratio of solid-to-liquid ratio 1:30
Example adds the watery hydrochloric acid of 5wt%, and rotating speed is 150r/min stirring, and heating water bath to 90 DEG C has been allowed to
CL, adds 0.025g lauryl sodium sulfate, after continuing stirring extremely dissolving, is placed in water-bath
Middle natural cooling crystallization, filters for three times, and filtrate is recycled and reused for the preparation of whisker, and filter cake is two water
Calcium sulfate crystal whiskers.
(3) washing: be washed with a small amount Dihydrate gypsum whiskers the most neutral,
(4) it is dried: by washing to neutral Dihydrate gypsum whiskers, at 50 DEG C, is dried 2h,
Obtain Dihydrate gypsum whiskers product.
Products obtained therefrom is white needles whisker, and crystal formation is uniform, diameter 1～10 μm, draw ratio
80～120, whiteness 95.8%.
Embodiment 2
The method of Dihydrate gypsum whiskers prepared by a kind of ardealite, comprises the following steps:
(1) prepared by removal of impurities calcium sulphate dihydrate: the hydrochloric acid solution of 1000g8wt% is preheated to 85
After DEG C, adding ardealite in the ratio of solid-to-liquid ratio 1:25, rotating speed is stirring under the conditions of 250r/min
Reaction 10min, the most once filters, reusing filter cake, crystallisation by cooling under filtrate room temperature, crystallization
After, secondary filter, filter cake is the calcium sulphate dihydrate after removal of impurities, and filtrate is recycled and reused for molten
Solve ardealite.
(2) prepared by whisker: remove miscellaneous after calcium sulphate dihydrate 100g, by solid-to-liquid ratio 1:25
Ratio adds the watery hydrochloric acid of 8wt%, and rotating speed is 200r/min stirring, and heating water bath to 85 DEG C is allowed to
It is completely dissolved, adds 0.05g lauryl sodium sulfate, after continuing stirring extremely dissolving, be placed in room
The lower crystallisation by cooling of temperature, filters for three times, and filtrate is recycled and reused for the preparation of whisker, and filter cake is two water sulphur
Acid calcium pyroborate.
(3) washing: with a small amount of clear water washing Dihydrate gypsum whiskers to neutral.
(4) it is dried: by washing to neutral Dihydrate gypsum whiskers, at 50 DEG C, is dried 2h,
Obtain Dihydrate gypsum whiskers product.
Products obtained therefrom is for white needles whisker, and crystal formation is uniform, diameter 1～10 μm, draw ratio
80～120, whiteness 96.4%.
Embodiment 3
The method of Dihydrate gypsum whiskers prepared by a kind of ardealite, comprises the following steps:
(1) preparation of removal of impurities calcium sulphate dihydrate: the hydrochloric acid solution of 1000g10wt% is preheated to
After 80 DEG C, adding ardealite in the ratio of solid-to-liquid ratio 1:20, rotating speed is to stir under the conditions of 300r/min
Mix reaction 8min, the most once filter, reusing filter cake, crystallisation by cooling under filtrate room temperature, crystallization
After, secondary filter, filter cake is the calcium sulphate dihydrate after removal of impurities, and filtrate is recycled and reused for molten
Solve ardealite.
(2) prepared by whisker: remove miscellaneous after calcium sulphate dihydrate 100g, by solid-to-liquid ratio 1:20
Ratio adds the watery hydrochloric acid of 10wt%, and rotating speed is 250r/min stirring, and heating water bath to 80 DEG C makes
Be completely dissolved, add 0.05g lauryl sodium sulfate, continue stirring to dissolve after, be placed in
Crystallisation by cooling under room temperature, filters for three times, and filtrate is recycled and reused for the preparation of whisker, and filter cake is two water
Calcium sulfate crystal whiskers.
(3) washing: with a small amount of clear water washing Dihydrate gypsum whiskers to neutral.
(4) it is dried: by washing to neutral Dihydrate gypsum whiskers, at 50 DEG C, is dried 2h,
Obtain Dihydrate gypsum whiskers product.
Products obtained therefrom is for white needles whisker, and crystal formation is uniform, diameter 1～10 μm, draw ratio
80～120, whiteness 96%.
Embodiment 4
The method of Dihydrate gypsum whiskers prepared by a kind of ardealite, comprises the following steps:
(1) preparation of removal of impurities calcium sulphate dihydrate: the hydrochloric acid solution of 5000g12wt% is preheated to
After 80 DEG C, adding ardealite in the ratio of solid-to-liquid ratio 1:20, rotating speed is to stir under the conditions of 300r/min
Mix reaction 8min, the most once filter, reusing filter cake, crystallisation by cooling under filtrate room temperature, crystallization
After, secondary filter, filter cake is the calcium sulphate dihydrate after removal of impurities, and filtrate is recycled and reused for molten
Solve ardealite.
(2) prepared by whisker: remove miscellaneous after calcium sulphate dihydrate 500g, by solid-to-liquid ratio 1:20
Ratio adds the watery hydrochloric acid of 12wt%, and rotating speed is 250r/min stirring, and heating water bath to 80 DEG C makes
Be completely dissolved, add 0.25g lauryl sodium sulfate, continue stirring to dissolve after, be placed in
Natural cooling crystallization in water-bath, filters for three times, and filtrate is recycled and reused for the preparation of whisker, and filter cake is
Dihydrate gypsum whiskers.
(3) washing: with a small amount of clear water washing Dihydrate gypsum whiskers to neutral.
(4) it is dried: by washing to neutral Dihydrate gypsum whiskers, at 50 DEG C, is dried 2h,
Obtain Dihydrate gypsum whiskers product.
Products obtained therefrom is white needles whisker, and crystal formation is uniform, diameter 1～10 μm, draw ratio
80～120, whiteness 95.2%.
Embodiment 5
The method of Dihydrate gypsum whiskers prepared by a kind of ardealite, comprises the following steps:
(1) preparation of removal of impurities calcium sulphate dihydrate: the hydrochloric acid solution of 10kg15wt% is preheated to
After 85 DEG C, adding ardealite in the ratio of solid-to-liquid ratio 1:20, rotating speed is to stir under the conditions of 300r/min
Mix reaction 8min, the most once filter, reusing filter cake, crystallisation by cooling under filtrate room temperature, crystallization
After, secondary filter, filter cake is the calcium sulphate dihydrate after removal of impurities, and filtrate is recycled and reused for molten
Solve ardealite.
(2) prepared by whisker: remove miscellaneous after calcium sulphate dihydrate 1000g, by solid-to-liquid ratio 1:20
Ratio adds the watery hydrochloric acid of 15wt%, and rotating speed is 250r/min stirring, and heating water bath to 85 DEG C makes
Be completely dissolved, add 0.5g lauryl sodium sulfate, continue stirring to dissolve after, be placed in water
Natural cooling crystallization in bath, filters for three times, and filtrate is recycled and reused for the preparation of whisker, and filter cake is two
H 2 O calcium sulphate whisker.
(3) washing: with a small amount of clear water washing Dihydrate gypsum whiskers to neutral.
(4) it is dried: by washing to neutral Dihydrate gypsum whiskers, at 50 DEG C, is dried 2h,
Obtain Dihydrate gypsum whiskers product.
Products obtained therefrom is needle-like whisker, and crystal formation is uniform, diameter 1～10 μm, draw ratio 80～120,
Whiteness 96.5%.
Embodiment 6-11
On the basis of embodiment 1-5, the numerical value change of the detailed description of the invention of embodiment 6-11 is such as
Shown in lower:
Embodiment 12
The method of Dihydrate gypsum whiskers prepared by a kind of ardealite, comprises the following steps: implementing
On the basis of example 1-11,
(1) preparation of removal of impurities calcium sulphate dihydrate；(2) preparation of whisker: after choosing removal of impurities
Each constituent content CaSO of calcium sulphate dihydrate4·2H2O >=98wt%, P2O5With the total amount of F≤
0.001wt%, SiO2≤ 0.1wt%, MgO, Fe2O3And Al2O3Total amount≤0.01wt%；
According to solid-to-liquid ratio hydrochloric acid, stir, heat after the calcium sulphate dihydrate after making removal of impurities is completely dissolved, to
Wherein add crystallization in motion agent, add thermal agitation and be completely dissolved to crystallization in motion agent, then crystallisation by cooling, three mistakes
Filter, it is thus achieved that three filtrates and three filter cakes, three filtrate recycles are in the preparation of whisker, three filters
Cake is Dihydrate gypsum whiskers；(3) washing；(4) it is dried prepared Dihydrate gypsum whiskers.
Test example:
The conventional method that the document that the present invention and present specification background section are quoted is introduced
Piglet s colibacillosis, result shows as follows:
Shown in upper table, from the point of view of the present invention is relative to traditional prior art, the present invention diameter,
Draw ratio and whiteness aspect are respectively provided with significant effect, and the most progressive, it is seen then that the present invention
There is significant economic benefit, reduce cost prepared by Dihydrate gypsum whiskers, improve two
Profit prepared by H 2 O calcium sulphate whisker.
It is important to point out at this: the embodiment of above of the present invention and experiment method, only limit
Further illustrating in the present invention, for the excellent good embodiment of the present invention；Those skilled in the art
The unsubstantiality progress that member makes on this basis, for the content of technical solution of the present invention.
Claims (10)
1. the method that Dihydrate gypsum whiskers prepared by an ardealite, it is characterised in that: include with
Lower step:
(1) preparation of removal of impurities calcium sulphate dihydrate: first the hydrochloric acid that concentration is 5～15wt% is preheated
After 80～90 DEG C, stir preheated hydrochloric acid, and when stirring, add ardealite and join
Become slip, after isothermal reaction 8～15min, the most once filter, it is thus achieved that first-time filtrate and once
Filter cake；Reusing filter cake is in slurry, after filtrate crystallisation by cooling, then carries out secondary filter, it is thus achieved that two
Secondary filtrate and secondary filter cake；Secondary filtrate recycle is in slurry, and secondary filter cake is two water after removal of impurities
Calcium sulfate；
(2) preparation of whisker: in the calcium sulphate dihydrate after removal of impurities according to solid-to-liquid ratio be
1:20～30 adds the hydrochloric acid that concentration is 5～15wt%, stirs, heats two water sulphur after making removal of impurities
After acid calcium is completely dissolved, it is added thereto in step 1) the hydrochloric acid quality of employing
0.001～the crystallization in motion agent of 0.01%, add thermal agitation and be completely dissolved to crystallization in motion agent, then crystallisation by cooling,
Three times filter, it is thus achieved that three filtrates and three filter cakes, three filtrate recycles in the preparation of whisker,
Three filter cakes are Dihydrate gypsum whiskers；
(3) washing: use clear water to be cleaned by three filter cakes, during until three filter cakes are neutrality,
Stop cleaning, and cleaning solution is back to the preparation of whisker；
(4) it is dried: the Dihydrate gypsum whiskers after scrubbed is placed in temperature is at 50～60 DEG C
It is dried 1～3h and prepares Dihydrate gypsum whiskers.
2. the method that Dihydrate gypsum whiskers prepared by ardealite as claimed in claim 1, it is special
Levying and be: in described step 1), the concentration of hydrochloric acid is 10wt%.
3. the method that Dihydrate gypsum whiskers prepared by ardealite as claimed in claim 1, it is special
Levying and be: in described step 1), hydrochloric acid preheating temperature is 85 DEG C.
4. the method that Dihydrate gypsum whiskers prepared by ardealite as claimed in claim 1, it is special
Levying and be: in described step 1), mixing speed is 200～300r/min.
5. the method that Dihydrate gypsum whiskers prepared by ardealite as claimed in claim 1, it is special
Levying and be: in described step 1), ardealite is 1:20～30 with the proportioning of hydrochloric acid.
6. the method that Dihydrate gypsum whiskers prepared by ardealite as claimed in claim 1, it is special
Levying and be: in described step 1), the isothermal reaction time is 10min.
7. the method that Dihydrate gypsum whiskers prepared by ardealite as claimed in claim 1, it is special
Levy and be: in described step 1), the calcium sulphate dihydrate each constituent content CaSO after removal of impurities4·
2H2O >=98wt%, P2O5With the total amount≤0.001wt% of F, SiO2≤ 0.1wt%, MgO,
Fe2O3And Al2O3Total amount≤0.01wt%.
8. the method that Dihydrate gypsum whiskers prepared by ardealite as claimed in claim 1, it is special
Levy and be: described step 2) in, mixing speed is 150～250r/min.
9. the method that Dihydrate gypsum whiskers prepared by ardealite as claimed in claim 1, it is special
Levy and be: described step 2) in, crystallization in motion agent is lauryl sodium sulfate, addition be
The 0.005% of the hydrochloric acid quality used in step 1).
10. the method that Dihydrate gypsum whiskers prepared by ardealite as claimed in claim 1, it is special
Levying and be: in described step 3), baking temperature is 55 DEG C of dry 2h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410135538.3A CN104005086B (en) | 2014-04-04 | 2014-04-04 | The method of Dihydrate gypsum whiskers prepared by a kind of ardealite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410135538.3A CN104005086B (en) | 2014-04-04 | 2014-04-04 | The method of Dihydrate gypsum whiskers prepared by a kind of ardealite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104005086A CN104005086A (en) | 2014-08-27 |
| CN104005086B true CN104005086B (en) | 2016-08-17 |
Family
ID=51365986
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410135538.3A Expired - Fee Related CN104005086B (en) | 2014-04-04 | 2014-04-04 | The method of Dihydrate gypsum whiskers prepared by a kind of ardealite |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104005086B (en) |
Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104532339B (en) * | 2014-12-16 | 2018-02-27 | 青海博川矿业开发有限公司 | A kind of method that calcium sulfate crystal whiskers are prepared using low grade natural gypsum or gypsum mine |
| CN111188087B (en) * | 2015-01-07 | 2021-10-26 | 西南科技大学 | Method for preparing calcium sulfate whisker from phosphogypsum |
| CN104894650B (en) * | 2015-05-31 | 2017-08-25 | 四川理工学院 | A kind of method for preparing Dihydrate gypsum whiskers with saltcake and calcium water |
| 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 |
| CN105671627B (en) * | 2016-03-31 | 2019-01-22 | 武汉理工大学 | A method of high-purity dihydrate gypsum whisker is prepared using industrial by-products calcium chloride |
| CN106006698B (en) * | 2016-05-23 | 2018-02-06 | 中国建筑第八工程局有限公司 | A kind of ardealite removal of impurities processing method |
| CN106480507A (en) * | 2016-11-15 | 2017-03-08 | 曲靖师范学院 | A kind of new technology of ardealite preparation low cost hemihydrate calcium sulfate crystal whisker |
| CN106698497B (en) * | 2017-01-22 | 2018-05-01 | 武汉工程大学 | A kind of method that calcium sulfate is prepared by ardealite |
| CN109137084B (en) * | 2018-09-10 | 2021-06-18 | 昆明理工大学 | Method for producing calcium sulfate dihydrate crystal whisker by salting-out method |
| CN109706526A (en) * | 2019-03-14 | 2019-05-03 | 江苏一夫科技股份有限公司 | It is a kind of to prepare Dihydrate gypsum whiskers, the method for hemihydrate calcium sulfate crystal whisker and product as made from it |
| CN110117813A (en) * | 2019-05-17 | 2019-08-13 | 哈尔滨工业大学（威海） | A method of preparing calcium sulfate crystal whiskers from gypsum offscum |
| CN112760716B (en) * | 2021-01-15 | 2024-05-24 | 海南蓝岛环保产业股份有限公司 | Recycling treatment method of phosphogypsum |
| CN113512761A (en) * | 2021-07-09 | 2021-10-19 | 浙江钙宝新材料有限公司 | Method for purifying industrial solid waste gypsum and preparing calcium sulfate whisker |
| CN114477262B (en) * | 2022-03-08 | 2023-06-09 | 云南凝创环保科技有限公司 | Method for deeply purifying and purifying calcium sulfate dihydrate by coarse-grained phosphogypsum |
| CN114590830B (en) * | 2022-03-08 | 2023-06-09 | 云南凝创环保科技有限公司 | Method for deeply purifying and purifying calcium sulfate dihydrate by fine-particle phosphogypsum |
| CN115323476B (en) * | 2022-07-28 | 2023-09-12 | 广东邦普循环科技有限公司 | Method for preparing calcium sulfate whisker by phosphogypsum purification |
| CN115196664B (en) * | 2022-08-15 | 2023-10-24 | 一夫科技股份有限公司 | Calcium sulfate dihydrate containing only eutectic phosphorus and preparation method thereof |
| CN115974126A (en) * | 2022-12-16 | 2023-04-18 | 贵州大学 | Method for regulating and controlling crystal morphology of phosphogypsum-based calcium sulfate dihydrate |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101994153A (en) * | 2010-12-13 | 2011-03-30 | 江苏省一夫新材料科技有限公司 | Method for preparing modified calcium sulfate whisker by using desulfurization gypsum |
| CN102115141A (en) * | 2010-12-31 | 2011-07-06 | 张胜勇 | Method for producing industrial calcium sulfate and phosphoric acid by using phosphogypsum |
| CN102115142A (en) * | 2010-12-31 | 2011-07-06 | 张胜勇 | Method for producing industrial calcium sulfate by producing ardealite |
| 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 |
| CN102925956A (en) * | 2012-11-26 | 2013-02-13 | 武汉科技大学 | Method for preparing calcium sulfate hemihydrate whiskers by taking ardealite as main raw material |
-
2014
- 2014-04-04 CN CN201410135538.3A patent/CN104005086B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101994153A (en) * | 2010-12-13 | 2011-03-30 | 江苏省一夫新材料科技有限公司 | Method for preparing modified calcium sulfate whisker by using desulfurization gypsum |
| CN102115141A (en) * | 2010-12-31 | 2011-07-06 | 张胜勇 | Method for producing industrial calcium sulfate and phosphoric acid by using phosphogypsum |
| CN102115142A (en) * | 2010-12-31 | 2011-07-06 | 张胜勇 | Method for producing industrial calcium sulfate by producing ardealite |
| 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 |
| CN102925956A (en) * | 2012-11-26 | 2013-02-13 | 武汉科技大学 | Method for preparing calcium sulfate hemihydrate whiskers by taking ardealite as main raw material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104005086A (en) | 2014-08-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104005086B (en) | The method of Dihydrate gypsum whiskers prepared by a kind of ardealite | |
| CN102965721B (en) | Method for preparing calcium sulfate crystal whisker in low cost | |
| CN102925956B (en) | Method for preparing calcium sulfate hemihydrate whiskers by taking ardealite as main raw material | |
| WO2017045520A1 (en) | Method for producing phosphoric acid and by-producing alpha-hemihydrate gypsum by wet-process | |
| CN104928758B (en) | A kind of additive package and method for producing anhydrous dead roasting type calcium sulfate crystal whiskers | |
| CN104211102B (en) | The continuous way method of modifying of dihydrate gypsum | |
| CN104532339B (en) | A kind of method that calcium sulfate crystal whiskers are prepared using low grade natural gypsum or gypsum mine | |
| CN104496237B (en) | A kind of method of power plant desulfurization gypsum remove impurity | |
| CN104003382B (en) | A kind of high purity graphite chemical purification continuous producing method | |
| CN109290060A (en) | A kind of process for subsequent treatment and phosphate ore floatation method of phosphate ore flotation tailings | |
| CN101284669B (en) | Preparation process of prodan by sodium sulfate method | |
| CN101224908A (en) | Method for producing manganese sulfate by high-temperature crystallization process | |
| CN101941704A (en) | New method for preparing silicon dioxide by utilizing rice hull ash | |
| CN110316708A (en) | The method that phosphorus ore produces half water phosphoric acid coproduction alpha type high-strength gypsum | |
| CN102492994A (en) | Method for preparing calcium sulfate whiskers by using white carbon black industrial wastewater | |
| CN101993085B (en) | Method for producing white carbon black for toothpaste from fly ash | |
| CN108383094A (en) | The method for preparing calcium monohydrogen phosphate and ammonium chloride using reverse flotation phosphorus tailing | |
| CN105133003B (en) | A kind of production method of phosphoric acid by wet process by-product αsemiwatergypsum whisker | |
| CN103224221A (en) | Method for separating sulfuric acid and ferrous sulfate by using ferrous sulfate monohydrate residue | |
| CN101492399B (en) | Method for preparing methylpropene sodium sulfonate | |
| CN101575106A (en) | Coproduction technology of calcium sulphate crystal whiskers and magnesium hydrate crystal whiskers by plaster-ammonium rotation method | |
| CN104556223A (en) | Recycling method of unfused zircon sand in technical process for preparing zirconium oxychloride by alkaline fusion method | |
| CN102851739B (en) | Preparation process of calcium sulfate whisker | |
| CN105332058A (en) | Method for preparing gypsum whiskers for papermaking from phosphogypsum under normal pressure in circulating dissolving method | |
| CN102923713A (en) | Method for sanitary production of sodium fluosilicate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20160715 Address after: No. 237 Jinyang City Kailin Lake District Road 550009 Guizhou city of Guiyang Province Applicant after: Phosphorylcholine group limited-liability company is opened in Guizhou Address before: Xifeng County in Guizhou Province, Guiyang city town 551109 Applicant before: Zhonghuakai Phosphorous Chemical Fertilizer Co., Ltd., Guiyang |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160817 Termination date: 20210404 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |