CN103922378B - 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
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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 utilizing gypsum to prepare high-purity metastable state vaterite calcium carbonate.
[background technology]
China needs to discharge a large amount of waste gypsum every year, as ardealite, desulfurated plaster, fluorgypsum etc., and the trend becoming to increase year by year, become one of China's key industry solid waste.At present to pile up, not only contaminated environment but also land occupation resource, the recycling how realizing waste gypsum is the problem needing solution badly.Waste gypsum main component is calcium sulphate dihydrate, and calcium sulfate and ammonium carbonate react prepares calcium carbonate and ammonium sulfate can be turned waste into wealth, and effectively utilizes Sulphur ressource.
Calcium carbonate is a kind of traditional chemical industry of inorganic salt product, can artificial regulatory color and luster, particle diameter, surface characteristic, decentralization, rheological characteristic, thixotropy and crystal formation etc., chemical purity is high, inertia is strong, Heat stability is good, there is oil absorbency low, hardness is low, wearing valve is little, nontoxic, odorless, tasteless, the advantages such as good dispersion, 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, amenities, sealant, adhesive, pesticide 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 anorthic system, nature is common is water chestnut face cube, thermodynamic stability is the strongest, aragonite belongs to rhombic system, usually in needle-like or column, thermodynamic stability is poor, and vaterite is the crystal formation of the least stable calcium carbonate of thermodynamics, is very easy in the solution change stable calcite crystal formation into.Vaterite belongs to hexagonal crystal system, presents spherical more.Compared to other two kinds of crystal formations, vaterite, because of the feature such as its high surface, highly dissoluble, polymolecularity, proportion is little, is expected to have in industrial or agricultural field apply widely.
It take gypsum as the method that superfine light calcium carbonate prepared by raw material that China publication CN101045544 gives a kind of, be that raw material adds water to react with ammonium carbonate or carbonic hydroammonium after slurrying and adds the mode that ammoniacal liquor regulates simultaneously and prepare calcium carbonate with gypsum, the method does not carry out purifying explanation to the crystal formation of calcium carbonate; Current industrial synthesis vaterite calcium carbonate is mainly through adding organic crystallization modifier to control the synthesis of vaterite calcium carbonate.CN1631792 discloses a kind of single dispersing micron chopped fiber-like aragonite calcium carbonate preparation method, in the aqueous solution being added with organic solvent, and precipitation calcium carbonate under low-carbon (LC) acid group concentration and calcium ion concentration 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, with parents' water type hyperbranched polymer molecule for template, is obtained by the precipitation reaction of water-soluble Ca salt and carbonate; Japan Patent H5-434011 using amino acid and amino-acid salt as additive, by controlling additive capacity and carbonization time restriction to obtain pure vaterite; Chinese patent CN102583485 gives 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 wherein after using low concentration soluble calcium salt and carbonate or bicarbonate to react and obtains the vaterite calcium carbonate that uniform particle diameter stable crystal form has industrial application value; CN102249281 gives a kind of preparation method of lenticular high-purity ball aragonite calcium carbonate.The method reacts obtained by sodium carbonate and calcium chloride in the water environment adding Ionic Liquid as Surface Active Agent.
The preparation of the vaterite-type calcium carbonate crystal reported or need to add organic solvent, or need the organic crystal agent of complicated process of preparation, in the process of preparation, also can introduce organic solvent.The introducing of organic solvent, adds the synthesis cost asking aragonite calcium carbonate; The complicated synthesis technique of organic crystal agent, increases the difficulty of experiment, and the introducing of toxic organic compound matter simultaneously also brings pollution to environment.Therefore the vaterite-type calcium carbonate adopting simple experimental technique efficiently and the synthesis of gentle condition to have industrial value has 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 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, calcium carbonate crystal formation is the metastable state vaterite of single crystal form, and 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) ammonium sulfate is got involved constant temperature in reactor and, to reaction temperature, add gypsum wherein, open stirring pulping 25 ~ 35min;
Described ammonium sulfate concentration range is 1.0 ~ 3.5mol/1, and reaction temperature is 25 ~ 65 DEG C.
(2) in reactor, sal volatile is added;
Ammonium sulfate concentrations in described sal volatile molar concentration and step (1) is equal, and in the mole of ammonium carbonate and step (1), the material ratio of gypsum is 1.05 ~ 1.2: 1;
(3) take account for gypsum quality mark be 0.1 ~ 5% anion surfactant add in the reactor in step (1);
Described anion surfactant is: odium stearate, enuatrol, neopelex, any one in ethyl orthosilicate, and surfactant qualities is no more than 5% of gypsum gross weight.
(4) rotating speed of agitator is regulated, isothermal reaction;
Described speed of agitator is: 0.4 ~ 1.5ms
-1, the reaction time is 1.5 ~ 2.5h;
(5) product in step (4) is filtered in a usual manner, washing, dry, obtain product.
Described baking temperature is 30 ~ 80 DEG C.
Compared with prior art, good effect of the present invention is:
(1) with non-solubility calcium salt for raw material, break through soluble calcium salt and prepare the limit of vaterite calcium carbonate, efficiently solve the problem of the low-quality utilization of domestic gypsum;
(2) the present invention can prepare the vaterite-type calcium carbonate that high-quality is easy to control at normal temperatures and pressures, and technique is simple, with low cost, is easy to suitability for industrialized production;
(3) vaterite-type calcium carbonate originally researched and produced take gypsum as raw material, can provide technical support, realize turning waste into wealth for the recycling problem solving Industrial Solid Waste waste gypsum; Vaterite calcium carbonate crystal form purity prepared by this method is high, and preparation technology is simple, and the reaction of high concentration carbon ammonium concentration improves the productive rate asking aragonite calcium carbonate, greatly can reduce the production cost of vaterite calcium carbonate.
[accompanying drawing explanation]
Fig. 1 is process chart 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
[detailed description of the invention]
The present invention is below provided to utilize gypsum to prepare the detailed description of the invention of the method for high-purity metastable state vaterite calcium carbonate.
Embodiment 1:
Refer to accompanying drawing 1-3, add the ammonium sulfate of 3mol/1, constant temperature to 25 DEG C in reactor, in reactor, add gypsum, unlatching mixing speed is 1.0m.s
-1, slurrying half an hour; In slurry, add the sal volatile of 3mol/1, the material ratio of added ammonium carbonate and gypsum is 1.1; The odium stearate of gypsum quality 2.5% is added, isothermal reaction 2h in slurry.After reaction terminates, suction filtration, filter cake spends deionized water 5 times, at 80 DEG C of baking oven inner drying 12h.
Embodiment 2:
In reactor, add the ammonium sulfate of 2mol/1, constant temperature to 45 DEG C, in reactor, add gypsum, unlatching mixing speed is 0.7m.s
-1, slurrying half an hour; In slurry, add the sal volatile of 2mol/1, the material ratio of added ammonium carbonate and gypsum is 1.05; Isothermal reaction 2h.After reaction terminates, suction filtration, filter cake spends deionized water 5 times, at 80 DEG C of baking oven inner drying 12h.
Embodiment 3:
In reactor, add the ammonium sulfate of 2mol/1, constant temperature to 55 DEG C, in reactor, add gypsum, unlatching mixing speed is 1.0m.s
-1, slurrying half an hour; In slurry, add the sal volatile of 2mol/1, the material ratio of added ammonium carbonate and gypsum is 1.1; The positive silicic acid ester of gypsum quality 3% is added, isothermal reaction 2h in slurry.After reaction terminates, suction filtration, filter cake spends deionized water 5 times, at 80 DEG C of baking oven inner drying 12h.
Embodiment 4:
In reactor, add the ammonium sulfate of 3.5mol/1, constant temperature to 25 DEG C, in reactor, add gypsum, unlatching mixing speed is 1.8m.s
-1, slurrying half an hour; In slurry, add the sal volatile of 3.5mol/1, the material ratio of added ammonium carbonate and gypsum is 1.2; The enuatrol of gypsum quality 2% is added, isothermal reaction 2h in slurry.After reaction terminates, suction filtration, filter cake spends deionized water 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 (4)
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) ammonium sulfate is got involved constant temperature in reactor and, to reaction temperature, add gypsum wherein, open stirring pulping 25 ~ 35min;
Described ammonium sulfate concentration is 1.0 ~ 3.5mol/l, and reaction temperature is 25 ~ 65 DEG C;
(2) in reactor, sal volatile is added;
Ammonium sulfate concentrations in described sal volatile molar concentration and step (1) is equal, and in the mole of ammonium carbonate and step (1), the material ratio of gypsum is 1.05 ~ 1.2:1;
(3) take account for gypsum quality mark be 0.1 ~ 5% anion surfactant add in the reactor in step (1);
Described anion surfactant is: odium stearate, enuatrol, neopelex, any one in ethyl orthosilicate;
(4) rotating speed of agitator is regulated, isothermal reaction;
Described speed of agitator is: 0.4 ~ 1.5ms
-1, the reaction time is 1.5 ~ 2.5h;
(5) product in step (4) is filtered in a usual manner, washing, dry, obtain product.
2. a kind of method utilizing gypsum to prepare high-purity metastable state vaterite calcium carbonate as claimed in claim 1, it is characterized in that, in described step (5), described baking temperature is 30 ~ 80 DEG C.
3. the calcium carbonate prepared of a kind of method utilizing gypsum to prepare high-purity metastable state vaterite calcium carbonate as claimed in claim 1, it is characterized in that, calcium carbonate crystal formation is the metastable state vaterite of single crystal form.
4. the calcium carbonate prepared of a kind of method utilizing gypsum to prepare high-purity metastable state vaterite calcium carbonate as claimed in claim 1, it is characterized in that, the purity of calcium carbonate product is 99.9%.
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US20170369329A1 (en) * | 2015-01-14 | 2017-12-28 | Imerys Usa, Inc. | A process for converting natural calcium carbonate into precipitated calcium carbonate |
| US9682868B2 (en) * | 2015-01-30 | 2017-06-20 | Sparstane Technologies LLC | Partially continuous countercurrent process for converting gypsum to 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 |
| 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 |
| CN110589863B (en) * | 2019-09-18 | 2022-04-05 | 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 |
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| 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 |
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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)
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| Factor affecting the precipitation of ppure calcium carbonate during the direct aqueous carbonation of flue gas desulfurization gypsum;Kyungsun Song et al.;《Energy》;20131205;第527~532页 * |
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