CN103922378A - Method for preparing high-purity metastable vaterite calcium carbonate from gypsum - Google Patents
Method for preparing high-purity metastable vaterite calcium carbonate from gypsum Download PDFInfo
- Publication number
- CN103922378A CN103922378A CN201410161345.5A CN201410161345A CN103922378A CN 103922378 A CN103922378 A CN 103922378A CN 201410161345 A CN201410161345 A CN 201410161345A CN 103922378 A CN103922378 A CN 103922378A
- Authority
- CN
- China
- Prior art keywords
- calcium carbonate
- gypsum
- metastable state
- vaterite calcium
- reactor
- 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.)
- Granted
Links
Landscapes
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention relates to a method for preparing high-purity metastable vaterite calcium carbonate from gypsum. The method comprises the following concrete steps: (1) adding an ammonium sulfate solution into a reactor from the constant temperature to the reaction temperature, adding the gypsum into the reactor, and stirring for pulping for 25-35 minutes; (2) adding an ammonium carbonate solution into the reactor; (3) adding an anionic surfactant accounting for 0.1%-5% by mass of the gypsum into the reactor in the step (1); (4) adjusting the rotary speed of a stirring paddle and reacting at the constant temperature to obtain a reaction product; and (5) filtering the reaction product in the step (4) in a conventional way, washing, and drying to obtain the high-purity metastable vaterite calcium carbonate. The vaterite calcium carbonate produced by adopting the method adopts the gypsum as a raw material, a technical support can be provided for solving the problem of recycling of industrial solid wastes-gypsum, and wastes are turned into wealth; the vaterite calcium carbonate is high in crystal purity and easy to prepare, the yield of the vaterite calcium carbonate is increased due to high-concentration ammonium carbonate reaction, and the production cost of the vaterite calcium carbonate can be greatly reduced.
Description
[technical field]
The present invention relates to a kind of high-purity single crystal form vaterite-type calcium carbonate technical field, be specifically related to a kind of method of utilizing gypsum to prepare high purity metastable state vaterite calcium carbonate.
[background technology]
China need to discharge a large amount of waste gypsums every year, as phosphogypsum, desulfurated plaster, fluorgypsum etc., and the trend of one-tenth increase year after year, become one of China's major industry solid waste.At present to pile up as main, not only contaminate environment but also land occupation resource, recycling how to realize waste gypsum is the problem of needing solution badly.Waste gypsum main component is terra alba, and calcium sulfate reacts with volatile salt prepares calcium carbonate and ammonium sulfate can be turned waste into wealth, and effectively utilizes sulphur resource.
Calcium carbonate is a kind of traditional chemical industry of inorganic salt product, can artificial regulatory color and luster, particle diameter, surface property, dispersity, rheological, thixotropy and crystal formation etc., chemical purity is high, inertia is strong, Heat stability is good, there is oil absorbency low, hardness is low, wear(ing)value is little, nontoxic, odorless, tasteless, the advantages such as good dispersity, be widely used in industrial or agricultural field, as rubber, plastics, papermaking, coating, paint, ink, cable, pharmacy, chemical fertilizer, feed, food, sugaring, weaving, glass, pottery, sanitary product, sealing agent, tackiness agent, sterilant and farm chemical carrier and flue sulphur removal, the environmental protection aspects such as water treatment.
The common crystal formation of calcium carbonate has 3 kinds: calcite, aragonite, vaterite.Calcite belongs to triclinic(crystalline)system, nature is common is water chestnut face cubes, thermodynamic stability is the strongest, aragonite belongs to rhombic system, conventionally be needle-like or column, thermodynamic stability is poor, and vaterite is the thermodynamics crystal formation of unsettled calcium carbonate, is very easy to change into stable calcite crystal formation in solution.Vaterite belongs to hexagonal system, presents spherical more.Than other two kinds of crystal formations, vaterite, because of features such as its high surface area, high resolution, polymolecularity, proportion are little, is expected to have in industrial or agricultural field application widely.
China publication CN101045544 has provided a kind of method of preparing superfine light calcium carbonate taking gypsum as raw material, add water taking gypsum as raw material and react the mode that simultaneously adds ammoniacal liquor to regulate with volatile salt or bicarbonate of ammonia after slurrying and prepare calcium carbonate, the method is not carried out purifying explanation to the crystal formation of calcium carbonate; Industrial synthetic vaterite calcium carbonate is mainly controlled the synthetic of vaterite calcium carbonate by adding organic crystallization modifier at present.CN1631792 discloses a kind of single dispersing micron chopped fiber-like aragonite calcium carbonate preparation method, in the aqueous solution that is added with organic solvent, and precipitation calcium carbonate under low-carbon (LC) acid group concentration and calcium ion concn condition, vaterite-type calcium carbonate content is greater than 90%; CN102515236 discloses a kind of preparation method of vaterite-phase calcium carbonate microspheres with uniform size, taking two hydrophilic hyperbranched polymer molecules as template, makes by the precipitin reaction of water-soluble Ca salt and carbonate; Japanese Patent H5-434011, using amino acid and amino acid salts as additive, limits to obtain pure vaterite by controlling additive capacity and carbonization time; Chinese patent CN102583485 has provided a kind of preparation method of monodisperse sphere vaterite type calcium carbonate micron ball, and the method adds functional hyperbranched poly epihydric alcohol ethereal solution to obtain uniform particle diameter stable crystal form after using lower concentration soluble calcium salt to react with carbonate or supercarbonate to have the vaterite calcium carbonate of industrial application value wherein; CN102249281 has provided a kind of preparation method of lensing high-purity ball aragonite calcium carbonate.The method is reacted and is made with calcium chloride by sodium carbonate in the water surrounding that has added Ionic Liquid as Surface Active Agent.
The preparation of the vaterite-type calcium carbonate crystal of having reported maybe needs to add organic solvent, or needs the organic crystal agent of complicated process of preparation, in the process of preparation, also can introduce organic solvent.The introducing of organic solvent, has increased the synthetic cost of asking aragonite calcium carbonate; The complicated synthesis technique of organic crystal agent, has increased the difficulty of experiment, and the introducing of toxic organic compound matter simultaneously has also brought pollution to environment.Therefore adopt simple experimental technique efficiently and the gentle synthetic vaterite-type calcium carbonate with industrial value of condition to there is important practical significance.
[summary of the invention]
The object of the invention is to overcome the deficiencies in the prior art, a kind of method of utilizing gypsum to prepare high purity metastable state vaterite calcium carbonate is provided.
The object of the invention is to be achieved through the following technical solutions:
Utilize gypsum to prepare a method for high purity metastable state vaterite calcium carbonate, the metastable state vaterite that calcium carbonate crystal formation is single crystal form, the purity of calcium carbonate product is higher, the highlyest can reach 99.9%, and the method is carried out as follows: its concrete steps are:
(1) ammoniumsulphate soln is got involved to constant temperature in reactor and, to temperature of reaction, added wherein gypsum, open stirring pulping 25～35min;
Described ammoniumsulphate soln concentration range is 1.0～3.5mol/1, and temperature of reaction is 25～65 DEG C.
(2) in reactor, add sal volatile;
Ammonium sulfate concentrations in described sal volatile volumetric molar concentration and step (1) equates, and in the molar weight of volatile salt and step (1), the material ratio of gypsum is 1.05～1.2: 1;
(3) take that to account for gypsum quality mark be that 0.1～5% anion surfactant adds in the reactor in step (1);
Described anion surfactant is: sodium stearate, and sodium oleate, Sodium dodecylbenzene sulfonate, any one in tetraethoxy, tensio-active agent quality is no more than 5% of gypsum gross weight.
(4) regulate rotating speed of agitator, isothermal reaction;
Described mixing speed is: 0.4～1.5ms
-1, the reaction times is 1.5～2.5h;
(5) product in step (4) is filtered in a usual manner, washing, dry, obtain product.
Described drying temperature is 30～80 DEG C.
Compared with prior art, positively effect of the present invention is:
(1) taking non-solubility calcium salt as raw material, break through the limit that soluble calcium salt is prepared vaterite calcium carbonate, efficiently solve the problem of the low-quality utilization of domestic gypsum;
(2) the present invention can prepare at normal temperatures and pressures high quality be easy to control vaterite-type calcium carbonate, technique is simple, with low cost, is easy to suitability for industrialized production;
(3) vaterite-type calcium carbonate of originally researching and producing, taking gypsum as raw material, can provide technical support for the recycling problem that solves Industrial Solid Waste waste gypsum, and realization is turned waste into wealth; Vaterite calcium carbonate crystal formation purity prepared by present method is high, and preparation technology is simple, and the reaction of high concentration carbon ammonium concentration has improved the productive rate of asking aragonite calcium carbonate, can greatly reduce the production cost of vaterite calcium carbonate.
[brief description of the drawings]
Fig. 1 is process flow sheet of the present invention;
Fig. 2 is the XRD figure of metastable state vaterite in the present invention;
Fig. 3 is the SEM figure of middle metastable state vaterite of the present invention
[embodiment]
Below provide the present invention to utilize gypsum to prepare the embodiment of the method for high purity metastable state vaterite calcium carbonate.
Embodiment 1:
Refer to accompanying drawing 1-3, to the ammoniumsulphate soln that adds 3mol/1 in reactor, constant temperature to 25 DEG C adds gypsum in reactor, and unlatching stirring velocity is 1.0m.s
-1, slurrying half an hour; To the sal volatile that adds 3mol/1 in slurry, add volatile salt and gypsum material ratio be 1.1; To the sodium stearate that adds gypsum quality 2.5% in slurry, isothermal reaction 2h.After reaction finishes, suction filtration, filter cake deionized water wash 5 times, at 80 DEG C of baking oven inner drying 12h.
Embodiment 2:
To the ammoniumsulphate soln that adds 2mol/1 in reactor, constant temperature to 45 DEG C adds gypsum in reactor, and unlatching stirring velocity is 0.7m.s
-1, slurrying half an hour; To the sal volatile that adds 2mol/1 in slurry, add volatile salt and gypsum material ratio be 1.05; Isothermal reaction 2h.After reaction finishes, suction filtration, filter cake deionized water wash 5 times, at 80 DEG C of baking oven inner drying 12h.
Embodiment 3:
To the ammoniumsulphate soln that adds 2mol/1 in reactor, constant temperature to 55 DEG C adds gypsum in reactor, and unlatching stirring velocity is 1.0m.s
-1, slurrying half an hour; To the sal volatile that adds 2mol/1 in slurry, add volatile salt and gypsum material ratio be 1.1; To the positive silicic acid ester that adds gypsum quality 3% in slurry, isothermal reaction 2h.After reaction finishes, suction filtration, filter cake deionized water wash 5 times, at 80 DEG C of baking oven inner drying 12h.
Embodiment 4:
To the ammoniumsulphate soln that adds 3.5mol/1 in reactor, constant temperature to 25 DEG C adds gypsum in reactor, and unlatching stirring velocity is 1.8m.s
-1, slurrying half an hour; To the sal volatile that adds 3.5mol/1 in slurry, add volatile salt and gypsum material ratio be 1.2; To the sodium oleate that adds gypsum quality 2% in slurry, isothermal reaction 2h.After reaction finishes, suction filtration, filter cake deionized water wash 5 times, at 80 DEG C of baking oven inner drying 12h.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, without departing from the inventive concept of the premise; can also make some improvements and modifications, these improvements and modifications also should be considered within the scope of protection of the present invention.
Claims (8)
1. utilize gypsum to prepare a method for high purity metastable state vaterite calcium carbonate, it is characterized in that, its concrete steps are:
(1) ammoniumsulphate soln is got involved to constant temperature in reactor and, to temperature of reaction, added wherein gypsum, open stirring pulping 25～35min;
(2) in reactor, add sal volatile;
(3) take that to account for gypsum quality mark be that 0.1～5% anion surfactant adds in the reactor in step (1);
(4) regulate rotating speed of agitator, isothermal reaction;
(5) product in step (4) is filtered in a usual manner, washing, dry, obtain product.
2. a kind of method of utilizing gypsum to prepare high purity metastable state vaterite calcium carbonate as claimed in claim 1, it is characterized in that, in described step (1), described ammoniumsulphate soln concentration is 1.0～3.5mol/1, and temperature of reaction is 25～65 DEG C.
3. a kind of method of utilizing gypsum to prepare high purity metastable state vaterite calcium carbonate as claimed in claim 1, it is characterized in that, in described step (2), ammonium sulfate concentrations in described sal volatile volumetric molar concentration and step (1) equates, and in the molar weight of volatile salt and step (1), the material ratio of gypsum is 1.05～1.2: 1.
4. a kind of method of utilizing gypsum to prepare high purity metastable state vaterite calcium carbonate as claimed in claim 1, it is characterized in that, in described step (3), described anion surfactant is: sodium stearate, sodium oleate, Sodium dodecylbenzene sulfonate, any one in tetraethoxy.
5. a kind of method of utilizing gypsum to prepare high purity metastable state vaterite calcium carbonate as claimed in claim 1, is characterized in that, in described step (4), described mixing speed is: 0.4～1.5ms
-1, the reaction times is 1.5～2.5h.
6. a kind of method of utilizing gypsum to prepare high purity metastable state vaterite calcium carbonate as claimed in claim 1, is characterized in that, in described step (5), described drying temperature is 30～80 DEG C.
7. the calcium carbonate that prepared by a kind of method of utilizing gypsum to prepare high purity metastable state vaterite calcium carbonate as claimed in claim 1, is characterized in that the metastable state vaterite that calcium carbonate crystal formation is single crystal form.
8. the calcium carbonate that prepared by a kind of method of utilizing gypsum to prepare high purity metastable state vaterite calcium carbonate as claimed in claim 1, is characterized in that, the purity of calcium carbonate product is 99.9%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410161345.5A CN103922378B (en) | 2014-04-22 | 2014-04-22 | Method for preparing high-purity metastable vaterite calcium carbonate from gypsum |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410161345.5A CN103922378B (en) | 2014-04-22 | 2014-04-22 | Method for preparing high-purity metastable vaterite calcium carbonate from gypsum |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103922378A true CN103922378A (en) | 2014-07-16 |
| CN103922378B CN103922378B (en) | 2015-03-25 |
Family
ID=51140813
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410161345.5A Active CN103922378B (en) | 2014-04-22 | 2014-04-22 | Method for preparing high-purity metastable vaterite calcium carbonate from gypsum |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103922378B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104876252A (en) * | 2015-04-14 | 2015-09-02 | 华东理工大学 | Method for preparing calcium carbonate by using ammonia carbonization-calcium conversion two-step method through low-temperature conversion |
| CN105038369A (en) * | 2015-07-02 | 2015-11-11 | 青阳县金峰石业有限公司 | Modified calcium carbonate filler for paint and preparation method thereof |
| CN107250397A (en) * | 2015-01-30 | 2017-10-13 | 斯帕斯坦技术有限责任公司 | For gypsum to be converted into the continuous countercurrent method in the part of ammonium sulfate and calcium carbonate |
| CN107532388A (en) * | 2015-01-14 | 2018-01-02 | 英默里斯美国公司 | Controlled method for winnofil |
| CN110156061A (en) * | 2019-05-29 | 2019-08-23 | 湖北大学 | A method of micro-nano structure calcium carbonate and ammonium sulfate are prepared using waste phosphogypsum |
| CN110589863A (en) * | 2019-09-18 | 2019-12-20 | 西部矿业集团有限公司 | Method for rapidly preparing high-purity micro-nano-scale porous metastable vaterite calcium carbonate from ammonia distillation waste liquid |
| CN111777089A (en) * | 2019-04-04 | 2020-10-16 | 西南科技大学 | Preparation method of high-purity vaterite type calcium carbonate microspheres |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1053412A (en) * | 1996-08-02 | 1998-02-24 | Yahashi Kogyo Kk | Production of spherical calcium carbonate |
| WO2007079018A1 (en) * | 2005-12-28 | 2007-07-12 | Mark Robert Steinhauser | Collapsible package, and methods |
| CN101993105A (en) * | 2010-12-10 | 2011-03-30 | 合肥工业大学 | Method for preparing light calcium carbonate and co-producing ammonium sulfate from phosphogypsum |
-
2014
- 2014-04-22 CN CN201410161345.5A patent/CN103922378B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1053412A (en) * | 1996-08-02 | 1998-02-24 | Yahashi Kogyo Kk | Production of spherical calcium carbonate |
| WO2007079018A1 (en) * | 2005-12-28 | 2007-07-12 | Mark Robert Steinhauser | Collapsible package, and methods |
| CN101993105A (en) * | 2010-12-10 | 2011-03-30 | 合肥工业大学 | Method for preparing light calcium carbonate and co-producing ammonium sulfate from phosphogypsum |
Non-Patent Citations (2)
| Title |
|---|
| KYUNGSUN SONG ET AL.: "Factor affecting the precipitation of ppure calcium carbonate during the direct aqueous carbonation of flue gas desulfurization gypsum", 《ENERGY》 * |
| T.H CHONG: "Thermodynamics and kinetics for mixed calcium carbonate and calcium sulfate precipitation", 《CHEMICAL ENGINEERING SCIENCE》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107532388A (en) * | 2015-01-14 | 2018-01-02 | 英默里斯美国公司 | Controlled method for winnofil |
| CN107250397A (en) * | 2015-01-30 | 2017-10-13 | 斯帕斯坦技术有限责任公司 | For gypsum to be converted into the continuous countercurrent method in the part of ammonium sulfate and calcium carbonate |
| CN104876252A (en) * | 2015-04-14 | 2015-09-02 | 华东理工大学 | Method for preparing calcium carbonate by using ammonia carbonization-calcium conversion two-step method through low-temperature conversion |
| CN105038369A (en) * | 2015-07-02 | 2015-11-11 | 青阳县金峰石业有限公司 | Modified calcium carbonate filler for paint and preparation method thereof |
| CN111777089A (en) * | 2019-04-04 | 2020-10-16 | 西南科技大学 | Preparation method of high-purity vaterite type calcium carbonate microspheres |
| CN110156061A (en) * | 2019-05-29 | 2019-08-23 | 湖北大学 | A method of micro-nano structure calcium carbonate and ammonium sulfate are prepared using waste phosphogypsum |
| CN110156061B (en) * | 2019-05-29 | 2021-08-13 | 湖北大学 | Method for preparing micro-nano structure calcium carbonate and ammonium sulfate by using waste phosphogypsum |
| CN110589863A (en) * | 2019-09-18 | 2019-12-20 | 西部矿业集团有限公司 | Method for rapidly preparing high-purity micro-nano-scale porous metastable vaterite calcium carbonate from ammonia distillation waste liquid |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103922378B (en) | 2015-03-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103922378B (en) | Method for preparing high-purity metastable vaterite calcium carbonate from gypsum | |
| CN103466637B (en) | Method for producing precipitate silicon dioxide by using sodium bicarbonate to control supersaturation degree | |
| CN102757075B (en) | Method for preparing calcium carbonate powders of different structures and shapes | |
| CN101234776A (en) | Process for preparing nano calcium carbonate | |
| CN101045544A (en) | Method for preparing superthin light calcium carbonate using plaster as raw material | |
| CN101684570A (en) | Method for preparing calcium carbonate crystal whisker with controllable shape | |
| CN103274439B (en) | A kind of method of oyster shells reprocessing cycle preparing nano calcium carbonate | |
| CN101935866B (en) | Method for preparing flaky calcite calcium carbonate crystal | |
| CN102502726A (en) | Preparation method of hexagonal flaky magnesium hydroxide | |
| CN102249281A (en) | Lensing spherical vaterite calcium carbonate crystal with high purity and preparation method thereof | |
| CN104326480A (en) | Method for preparing micro-hole calcium silicate by adopting water glass and lime emulsion | |
| CN105271344B (en) | A kind of preparation method of strobile pattern calcite type micron order calcium carbonate granule | |
| CN101700899A (en) | Technology for producing and preparing high-purity lamellar magnesium hydroxide | |
| CN102424415B (en) | Preparation method for needle cluster-like micrometer-scale calcium carbonate | |
| CN103601210B (en) | Wilkinite one step alkali is fused into the method for zeolite | |
| CN114921851A (en) | Calcium carbonate whisker prepared by carbide slag carbonization and preparation method thereof | |
| CN102424409A (en) | Method for preparing light magnesium carbonate | |
| CN107324366A (en) | A kind of high vaterite content winnofil and preparation method thereof | |
| CN104876252A (en) | Method for preparing calcium carbonate by using ammonia carbonization-calcium conversion two-step method through low-temperature conversion | |
| CN103642051A (en) | Method for treating alkali absorbed sulfur dioxide waste liquid by using lignin | |
| CN104118896B (en) | A kind of acidolysis Wingdale prepares the method for high purity aragonitic nano-calcium carbonate | |
| CN102910662A (en) | Preparation method of granularity-controllable CaCO3 | |
| CN103523813A (en) | Industrial preparation method of producing nano calcium carbonate by recycling filter-pressing water | |
| CN102134746A (en) | Preparation method of alkali type magnesium chloride whisker | |
| CN112441605B (en) | Preparation method of vermicular precipitated calcium carbonate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |