CN104528798A - Method for purifying low-grade natural gypsum or gypsum tailings by recrystallization - Google Patents
Method for purifying low-grade natural gypsum or gypsum tailings by recrystallization Download PDFInfo
- Publication number
- CN104528798A CN104528798A CN201410781738.6A CN201410781738A CN104528798A CN 104528798 A CN104528798 A CN 104528798A CN 201410781738 A CN201410781738 A CN 201410781738A CN 104528798 A CN104528798 A CN 104528798A
- Authority
- CN
- China
- Prior art keywords
- gypsum
- calcium sulfate
- low
- grade
- method preparing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
The invention relates to the field of preparation of high purity gypsum and particularly relates to a method for purifying low-grade natural gypsum or gypsum tailings by recrystallization. The method provided by the invention mainly comprises the following six steps: crushing; screening; dissolving; crystallizing; washing; and drying. The method specifically comprises the following steps: crushing and screening the low-grade natural gypsum or gypsum tailings; then, adding the low-grade natural gypsum or gypsum tailings into an acid at special solubility; heating to a certain temperature till the low-grade natural gypsum or gypsum tailings is/are fully dissolved; carrying out solid-liquid separation to remove undissolved solid phase impurities while the solution is hot; cooling, recrystallizing a liquid phase at a relatively low temperature and carrying out solid-liquid separation; and washing and drying a filter cake to obtain the high purity gypsum. The liquid phase in the dissolving and crystallizing processes can be repeatedly used. According to the method provided by the invention, proper raw material granularity, solid liquid ratio, temperature and acid concentration are selected and the raw materials are dissolved and crystallized for a certain time to prepare gypsum with relatively high purity, so that the grade or performance of the gypsum is remarkably improved.
Description
Technical field
The present invention relates to high purity plaster preparation field, particularly, the present invention relates to a kind of method of recrystallization purification low grade natural gypsum or gypsum mine.
Background technology
The plaster of paris is one of Dominant Mineral Resources of China, and explored reserves have 1,000 hundred million tons, rank first in the world, along with the fast development of Building Trade in China and building materials industry, increasing to the demand of gypsum, simultaneously also more and more higher to the purity requirement of gypsum.Meanwhile, higher-grade gypsum resource reduces gradually, and therefore fully the low-grade gypsum of development and utilization or gypsum mine resource more and more come into one's own.And low grade natural gypsum or gypsum mine because of its contain impurity component complexity, grating is poor, purity is lower, for low grade natural gypsum or gypsum mine recycling cause obstacle.If gypsum mine is not utilized namely become trade waste, land occupation, contaminate environment, pollution is caused to environment and society, simultaneously also cause burden to enterprise, if reasonably gypsum mine can be utilized, not only to environment and society favourable, also can reduce the heavy burdens to enterprise, increase economic efficiency.
Still do not have at present a kind of effective means can remove impurity in low grade natural gypsum or gypsum mine, the potential using value of low grade natural gypsum or gypsum mine is very large, the plaster of Paris is produced in building materials industry, brushing gypsum, gypsum block, Thistle board, plaster hollow board, nature plane earth gypsum slurry, cement setting retarder etc., agricultural aspect is for the production of chemical fertilizer, improvement salt affected soil etc., low grade natural gypsum or gypsum mine can be used for producing high-strength semi-hydrated gypsum through purifying after treatment, the added values such as calcium sulfate crystal whiskers are high, the product that market potential is huge.
Summary of the invention
The existing method of purification of low-grade Gypsum Mine mainly contains fragmentation, stage division and double decomposition.Fragmentation, stage division complex process, refining effect are undesirable, and are difficult to remove foreign ion completely.Double decomposition utilizes the replacement(metathesis)reaction purification gypsum of gypsum and bicarbonate of ammonia, although refining effect is good, its cost is high, has by product.Utilize reclosing crystallization purifying desulphurized gypsum to have employed acid pickling step, need to consume a large amount of acid, cause cost to raise.For the method for purification of gypsum mine, yet there are no report.
The present invention is directed to prior art Problems existing, provide recrystallization and to purify the method for low-grade gypsum or gypsum mine, the method mainly comprises fragmentation, screening, dissolving, crystallization, washing, dry six steps.Low-grade gypsum or gypsum mine are carried out fragmentation, screening, then joined in the acid of specific solubility, being heated to certain temperature makes it all dissolve, carry out solid-liquid separation removing while hot and do not dissolve solid phase impurity, liquid phase is cooled recrystallization, solid-liquid separation under lesser temps, filter cake is washed, dries, obtain high purity plaster.Liquid phase in dissolving, crystallisation process is reusable.According to method provided by the present invention, choose suitable raw material granularity, solid-to-liquid ratio, temperature, acid concentration, dissolving, crystallization certain hour can obtain the higher gypsum of purity, significantly improve grade of gypsum or performance.
The method of recrystallization purification low grade natural gypsum of the present invention or gypsum mine, comprises the following steps:
1) crush and screen: by low-grade Gypsum Mine or gypsum mine crushing and screening, obtain slag;
2) dissolve: by step 1) the excessive acid of gained slag dissolves at 50 ~ 80 DEG C, collecting by filtration filtrate after dissolving, acquisition calcium sulfate leach liquor;
3) crystallization: by step 2) calcium sulfate leach liquor crystallization crystal at 0 ~ 25 DEG C of obtaining, obtain calcium sulphate crystal filter cake after filtering;
4) washing and drying: by obtained high purity plaster dry after the washing of calcium sulphate crystal filter cake, in the high purity plaster obtained after purifying, the massfraction of terra alba is up to 97.0% ~ 99.5%.
According to the method preparing calcium sulfate crystal whiskers of the present invention, described low-grade Gypsum Mine or gypsum mine be gypsum content low or exploitation processing after can not be directly used in synthesis calcium sulfate crystal whiskers Gypsum Mine, wherein SO
3massfraction be 30.2% ~ 40%, the massfraction of terra alba is 65% ~ 85%.
According to the method preparing calcium sulfate crystal whiskers of the present invention, step 1) described low-grade gypsum or gypsum mine adopt pulverizer to pulverize, particle diameter≤120 order of pulverizing.
According to the method preparing calcium sulfate crystal whiskers of the present invention, step 2) acid that uses in dissolution process is hydrochloric acid, nitric acid or both mixtures.Preferably, described hydrochloric acid soln is 0.5 ~ 1.5mol/L; Described salpeter solution concentration is 0.5 ~ 1.5mol/L, and described acid solution can recycle.
According to the method preparing calcium sulfate crystal whiskers of the present invention, step 2) mass ratio of slag and acid solution is 2:100 ~ 8:100 in dissolution process; Preferably, step 2) dissolution time is 2 ~ 10h.
According to the method preparing calcium sulfate crystal whiskers of the present invention, step 3) as long as crystallization time meets crystallization completely, preferably, described crystallization time is 12 ~ 24h.
According to the method preparing calcium sulfate crystal whiskers of the present invention, step 4) temperature of described drying process is 40 ~ 60 DEG C, time of drying is 2 ~ 12h.
The present invention is for the method that low-grade gypsum is purified, and technique is simple, and product purity is high; Relative to recrystallization method purifying desulphurized gypsum, present invention eliminates acid pickling step, simplify technique, reduce cost.So method of purification provided by the invention can solve existing method of purification complex process, cost is high, refining effect is undesirable technical barrier effectively, production cost can be reduced widely, there is good industrialization prospect.
The present invention compared with prior art has the following advantages:
(1) product purity is high, performance good: recrystallization method is that the feature utilizing the solubility with temperature of calcium sulfate in specific acid solution to be changed significantly is purified, and gypsum all can be dissolved and separate out, be removed by magazine.The gypsum product purity obtained is high, and performance is good.Overcome the purification problem of low-grade gypsum or gypsum mine now, improve the application performance of gypsum, expand its range of application, thus reach and solve due to low-grade gypsum or the low and object of the environmental problem that causes and social concern of gypsum mine utilization ratio.
(2) the present invention is without pickling, and acid solution used can be reused, and reduces costs: present method hydrochloric acid used or nitric acid can recycles, reduce costs, increase economic efficiency.
(3) present invention process is simple, and easy to operate, cost is low, is that whole reaction process is nontoxic, harmless, pollution-free.
Embodiment
Set forth the present invention further by the following examples, these embodiments are only presented for purposes of illustration, do not limit the scope of the invention.The test method of unreceipted actual conditions in the following example, usually conveniently condition.
Embodiment 1
Gypsum mine is broken, sieve by 120 mesh sieve, gypsum after 15.00g fragmentation and the hydrochloric acid soln 300ml of the 1.50mol/L prepared in advance are added in 500mL beaker simultaneously, be immersed in by solution in above beaker in 80 DEG C of waters bath with thermostatic control, constant temperature also stirs 5h, after having reacted, suction filtration while hot, and removing the solid residue be not dissolved in hydrochloric acid soln, filtrate is transferred in 500mL beaker, is positioned over crystallisation by cooling 12h in room temperature.Suction filtration after crystallization completes, first pickling is carried out to filter cake, then wash, then namely filter cake dry 6h in 50 DEG C of baking ovens is obtained the high purity plaster product 6.89g that purity is 98.54%.
Embodiment 2
Low-grade Gypsum Mine is broken, sieve by 120 mesh sieve, gypsum after 30.12g fragmentation and the salpeter solution 600mL of the 0.5mol/L prepared in advance are added in 1000mL beaker simultaneously, be immersed in by solution in above beaker in 50 DEG C of waters bath with thermostatic control, constant temperature also stirs 10h, after having reacted, suction filtration while hot, and removing the solid residue be not dissolved in salpeter solution, filtrate is transferred in 1000mL beaker, is positioned over crystallisation by cooling 24h in 20 DEG C of environment.Suction filtration after crystallization completes, first pickling is carried out to filter cake, then wash, then namely filter cake dry 12h in 40 DEG C of baking ovens is obtained the high purity plaster product 14.28g that purity is 99.50%
Embodiment 3
Gypsum mine is broken, sieve by 120 mesh sieve, the hydrochloric acid of the gypsum after 60.00g fragmentation and the 1.0mol/L to prepare in advance and nitric acid mixing solutions 900mL are added in 1000mL beaker simultaneously, be immersed in by solution in above beaker in 60 DEG C of waters bath with thermostatic control, constant temperature also stirs 2h, after having reacted, suction filtration while hot, and removing the solid residue be not dissolved in hydrochloric acid and salpeter solution, filtrate is transferred in 1000mL beaker, is positioned over crystallisation by cooling 18h in 0 DEG C of environment.Suction filtration after crystallization completes, first pickling is carried out to filter cake, then wash, then namely filter cake dry 2h in 60 DEG C of baking ovens is obtained the high purity plaster product 35.19g that purity is 98.70%.
Embodiment 4
Gypsum mine is broken, sieve by 120 mesh sieve, gypsum after 30.12g fragmentation and the hydrochloric acid soln 500mL of the 1.0mol/L prepared in advance are added in 1000mL beaker simultaneously, be immersed in by solution in above beaker in 70 DEG C of waters bath with thermostatic control, constant temperature also stirs 4h, after having reacted, suction filtration while hot, and removing the solid residue be not dissolved in hydrochloric acid soln, filtrate is transferred in 1000mL beaker, is positioned over crystallisation by cooling 15h in 10 DEG C of environment.Suction filtration after crystallization completes, first pickling is carried out to filter cake, then wash, then namely filter cake dry 8h in 60 DEG C of baking ovens is obtained the high purity plaster product 18.28g that purity is 99.32%.
Certainly; the present invention can also have various embodiments; when not deviating from the present invention's spirit and essence thereof; those of ordinary skill in the art can openly make various corresponding change and distortion according to of the present invention, but these change accordingly and are out of shape the protection domain that all should belong to claim of the present invention.
Claims (8)
1. a method for recrystallization purification low grade natural gypsum or gypsum mine, comprises the following steps:
1) crush and screen: by low-grade Gypsum Mine or gypsum mine crushing and screening, obtain slag;
2) dissolve: by step 1) the excessive acid of gained slag dissolves at 50 ~ 80 DEG C, acquisition calcium sulfate leach liquor;
3) crystallization: by step 2) calcium sulfate leach liquor crystallization crystal at 0 ~ 25 DEG C of obtaining, obtain terra alba crystal cake after filtering;
4) washing and drying: by obtained high purity plaster dry after the washing of terra alba crystal cake.
2. the method preparing calcium sulfate crystal whiskers according to claim 1, is characterized in that, step 1) particle diameter≤120 order pulverized of described low-grade gypsum or gypsum mine.
3. the method preparing calcium sulfate crystal whiskers according to claim 1, is characterized in that, step 2) acid that uses in described dissolution process is hydrochloric acid, nitric acid or both mixtures.
4. the method preparing calcium sulfate crystal whiskers according to claim 3, is characterized in that, described concentration of hydrochloric acid solution is 0.5 ~ 1.5mol/L; Described salpeter solution concentration is 0.5 ~ 1.5mol/L.
5. the method preparing calcium sulfate crystal whiskers according to claim 1, is characterized in that, step 2) mass ratio of slag and acid solution is 2:100 ~ 8:100 in dissolution process.
6. the method preparing calcium sulfate crystal whiskers according to claim 1, is characterized in that, step 2) dissolution time is 2 ~ 10h.
7. the method preparing calcium sulfate crystal whiskers according to claim 1, is characterized in that, step 3) described crystallization time is 12 ~ 24h.
8. the method preparing calcium sulfate crystal whiskers according to claim 1, is characterized in that, step 4) temperature of described drying is 40 ~ 60 DEG C, time of drying is 2 ~ 12h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410781738.6A CN104528798A (en) | 2014-12-16 | 2014-12-16 | Method for purifying low-grade natural gypsum or gypsum tailings by recrystallization |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410781738.6A CN104528798A (en) | 2014-12-16 | 2014-12-16 | Method for purifying low-grade natural gypsum or gypsum tailings by recrystallization |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104528798A true CN104528798A (en) | 2015-04-22 |
Family
ID=52844493
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410781738.6A Pending CN104528798A (en) | 2014-12-16 | 2014-12-16 | Method for purifying low-grade natural gypsum or gypsum tailings by recrystallization |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104528798A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110395919A (en) * | 2019-08-09 | 2019-11-01 | 中国科学院沈阳应用生态研究所 | A kind of method that the gypsum resourceization containing arsenic is handled and the application for handling the low arsenic gypsum of gained |
| CN113957273A (en) * | 2021-10-24 | 2022-01-21 | 崇义章源钨业股份有限公司 | Method for efficiently decomposing calcium sulfate by hydrochloric acid |
| CN114988484A (en) * | 2022-05-16 | 2022-09-02 | 安徽大学绿色产业创新研究院 | Gypsum tailing treatment method of solid lithium ore neutralization process |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IL26076A (en) * | 1965-07-07 | 1970-07-19 | Prayon | Method for the manufacture of phosphoric acid and calcium sulphate hemihydrate |
| CN1584130A (en) * | 2004-06-14 | 2005-02-23 | 青岛科技大学 | Method for producing land plaster whiskers from phosphoric acid |
| CN101870494A (en) * | 2010-06-12 | 2010-10-27 | 上海大学 | Method for recrystallizing and purifying desulphurized gypsum |
| CN201713334U (en) * | 2010-05-26 | 2011-01-19 | 上海大学 | Industrial byproduct gypsum recrystallization device |
| CN102352535A (en) * | 2011-09-22 | 2012-02-15 | 东莞上海大学纳米技术研究院 | Method for preparing calcium sulfate crystal whiskers from desulfurized gypsum under normal pressure |
| CN103074667A (en) * | 2013-01-30 | 2013-05-01 | 湘潭大学 | Method for preparing calcium sulfate whisker through recrystallization |
-
2014
- 2014-12-16 CN CN201410781738.6A patent/CN104528798A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IL26076A (en) * | 1965-07-07 | 1970-07-19 | Prayon | Method for the manufacture of phosphoric acid and calcium sulphate hemihydrate |
| CN1584130A (en) * | 2004-06-14 | 2005-02-23 | 青岛科技大学 | Method for producing land plaster whiskers from phosphoric acid |
| CN201713334U (en) * | 2010-05-26 | 2011-01-19 | 上海大学 | Industrial byproduct gypsum recrystallization device |
| CN101870494A (en) * | 2010-06-12 | 2010-10-27 | 上海大学 | Method for recrystallizing and purifying desulphurized gypsum |
| CN102352535A (en) * | 2011-09-22 | 2012-02-15 | 东莞上海大学纳米技术研究院 | Method for preparing calcium sulfate crystal whiskers from desulfurized gypsum under normal pressure |
| CN103074667A (en) * | 2013-01-30 | 2013-05-01 | 湘潭大学 | Method for preparing calcium sulfate whisker through recrystallization |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110395919A (en) * | 2019-08-09 | 2019-11-01 | 中国科学院沈阳应用生态研究所 | A kind of method that the gypsum resourceization containing arsenic is handled and the application for handling the low arsenic gypsum of gained |
| CN113957273A (en) * | 2021-10-24 | 2022-01-21 | 崇义章源钨业股份有限公司 | Method for efficiently decomposing calcium sulfate by hydrochloric acid |
| CN113957273B (en) * | 2021-10-24 | 2022-12-20 | 崇义章源钨业股份有限公司 | Method for efficiently decomposing calcium sulfate by hydrochloric acid |
| CN114988484A (en) * | 2022-05-16 | 2022-09-02 | 安徽大学绿色产业创新研究院 | Gypsum tailing treatment method of solid lithium ore neutralization process |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104532339B (en) | A kind of method that calcium sulfate crystal whiskers are prepared using low grade natural gypsum or gypsum mine | |
| CN111188087B (en) | Method for preparing calcium sulfate whisker from phosphogypsum | |
| CN104495899B (en) | A kind of carbide slag and flyash work in coordination with the method for recycling | |
| CN101870494A (en) | Method for recrystallizing and purifying desulphurized gypsum | |
| CN102001636B (en) | Method for producing broad-concentration phosphoric acid and clean plaster by middle-low grade phosphorus ore wet process | |
| CN102925956B (en) | Method for preparing calcium sulfate hemihydrate whiskers by taking ardealite as main raw material | |
| CN104016379B (en) | A kind of preparation method of potassium sulfate | |
| CN101372402A (en) | Method for preparing magnesian by calcining ammonium salt and magnesium-containing ore | |
| CN105271347A (en) | Method for preparing high-purity barium salt by using witherite-barytocalcite industrial waste residues | |
| WO2018041272A1 (en) | Method for preparing industrial grade lithium carbonate from crude lithium fluoride, and a lithium carbonate product | |
| CN101993256A (en) | Method for preparing agricultural potassium sulfate from potassium-rich rock | |
| CN104477960B (en) | A kind of production method of potassium alum | |
| CN104528798A (en) | Method for purifying low-grade natural gypsum or gypsum tailings by recrystallization | |
| CN105483816A (en) | Method for preparing calcium sulfate whiskers from acetylene sludge and waste sulfuric acid | |
| CN101486481A (en) | Method for coproduction of ammonia sulfate and superfine light calcium carbonate from fluorgypsum | |
| CN103232052B (en) | Method for preparing high-purity calcium carbonate directly from phosphogypsum | |
| CN101633584B (en) | A method for producing nitrogen phosphorus potassium compound fertilizer with water-insoluble potassium-containing rock | |
| CN104086398B (en) | A kind of method of oxalic acid waste liquid Separation and Recovery oxalic acid | |
| CN101613117A (en) | Utilize primary sylvite ore deposit to produce the method for Repone K | |
| CN103131873A (en) | Method for separating lithium from aluminous rocks and preparing lithium carbonate by using mixed acid | |
| CN102583487A (en) | Method for preparing barium chloride by using witherite tailings and barium residues | |
| CN102352528A (en) | Method for extracting phosphorite co-production gypsum whisker by utilizing nitric acid | |
| CN107324337B (en) | Method for recycling waste solar crystalline silicon cutting slurry | |
| CN106477593A (en) | A kind of method that boric acid is prepared as raw material with raphite ore deposit | |
| CN102432052B (en) | Method for extracting aluminum oxide from pulverized fuel ash by using potassium sulfate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20150422 |
|
| RJ01 | Rejection of invention patent application after publication |