CN112723401A - Method for preparing vaterite type calcium carbonate from rock salt brine at room temperature - Google Patents
Method for preparing vaterite type calcium carbonate from rock salt brine at room temperature Download PDFInfo
- Publication number
- CN112723401A CN112723401A CN202011472842.9A CN202011472842A CN112723401A CN 112723401 A CN112723401 A CN 112723401A CN 202011472842 A CN202011472842 A CN 202011472842A CN 112723401 A CN112723401 A CN 112723401A
- Authority
- CN
- China
- Prior art keywords
- calcium carbonate
- room temperature
- type calcium
- rock
- brine
- 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
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 161
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 69
- 239000012267 brine Substances 0.000 title claims abstract description 64
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 title claims abstract description 62
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 title claims abstract description 59
- 239000011780 sodium chloride Substances 0.000 title claims abstract description 49
- 235000002639 sodium chloride Nutrition 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 48
- 239000000047 product Substances 0.000 claims abstract description 53
- 238000003756 stirring Methods 0.000 claims abstract description 45
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 239000000243 solution Substances 0.000 claims abstract description 30
- 239000000843 powder Substances 0.000 claims abstract description 18
- 239000012265 solid product Substances 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000008367 deionised water Substances 0.000 claims abstract description 14
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 12
- 239000011575 calcium Substances 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 7
- 239000008394 flocculating agent Substances 0.000 claims abstract description 7
- 239000011435 rock Substances 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical class [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 229920002401 polyacrylamide Polymers 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 238000003763 carbonization Methods 0.000 abstract description 6
- 238000002360 preparation method Methods 0.000 abstract description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052791 calcium Inorganic materials 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000011084 recovery Methods 0.000 abstract description 2
- 230000001276 controlling effect Effects 0.000 description 19
- 238000002441 X-ray diffraction Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 239000007788 liquid Substances 0.000 description 8
- 238000000926 separation method Methods 0.000 description 8
- 229910021532 Calcite Inorganic materials 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 3
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000004626 scanning electron microscopy Methods 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 239000002243 precursor Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/18—Carbonates
- C01F11/181—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by control of the carbonation conditions
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention discloses a method for preparing vaterite type calcium carbonate from rock salt brine at room temperature, which comprises the following steps: 1) introducing CO into rock salt brine serving as a raw material2Stirring and reacting at room temperature to obtain a reaction solution, and adjusting the pH value of rock salt brine to 9.3-9.7 in the stirring process; 2) adding a flocculating agent into the reaction liquid, stirring at a rotating speed of 50-100 r/min for 10-30 min, standing and settling to obtain a solid product A; 3) and washing the solid product A with deionized water to obtain a solid product B, and drying the solid product B to obtain the vaterite-type calcium carbonate powder. The preparation method solves the problem of CO existing in the process of preparing calcium carbonate by a direct carbonization method2Low utilization rate and low product yield, realizes the resource utilization of calcium in rock brine and CO2The comprehensive recovery of the process. The method has the advantages of wide raw material source, low price, simple and easy operation of the preparation method, reaction which can be carried out at room temperature, green and environment-friendly process, environment-friendly reaction, continuous and controllable operation procedure and easy expanded production.
Description
Technical Field
The invention belongs to the technical field of material chemical industry, and particularly relates to a method for preparing vaterite-type calcium carbonate from rock salt brine at room temperature.
Background
Calcite (Calcite), Aragonite (Aragonite) and Vaterite (Vaterite) are three common anhydrous crystal forms of calcium carbonate, and the difference of crystal forms causes the difference of physicochemical properties and purposes. Calcite-type calcium carbonate is thermodynamically the most stable, aragonitic and vaterite the least stable. Vaterite-type calcium carbonate has wider and special uses than calcite-type and aragonite-type due to its thermodynamic characteristics. Such as paint, paper making, life science and other fields. The vaterite has the special qualities of large specific surface area, spherical distribution, good dispersibility, double refraction and the like, can obviously improve the filling performance of printing ink, plastics, coating and the like, and has huge application potential in the aspects of improving the glossiness, the fluidity, the physical property, the printing property and the like of products. Therefore, it is of great importance to develop a simple method for preparing the vaterite-type calcium carbonate.
At present, the methods for producing vaterite-type calcium carbonate are mainly a carbonization method and a double decomposition method. Carbonisation of Fassima Ca2+-H2O-CO2System, using added CO2With Ca in solution2+And reacting to generate calcium carbonate. But CO2The solubility in water is low, and CO is at 20-40 DEG C2The solubility of (A) is only 0.16-0.12 g/100g H2And O. Thus, calcium carbonate is prepared by conventional carbonization processes in the presence of CO2The utilization rate and the yield of calcium carbonate are low.
Therefore, research on the method for effectively improving CO2The method for preparing the vaterite-type calcium carbonate by the carbonization method is extremely important in the utilization rate and the yield of the calcium carbonate.
Disclosure of Invention
The invention aims to provide a method for preparing vaterite-type calcium carbonate from rock salt brine at room temperature.
The invention aims to realize the method for preparing the vaterite-type calcium carbonate from rock salt brine at room temperature, which comprises the following steps:
1) introducing CO into rock salt brine serving as a raw material2Stirring to react to obtain reaction liquid, and adjusting and controlling the pH value of the rock salt brine to be 9.3-9.7 in the stirring process;
2) adding a flocculating agent into the reaction liquid, stirring at a rotating speed of 50-100 r/min for 10-30 min, standing and settling to obtain a solid product A;
3) and washing the solid product A with deionized water to obtain a solid product B, and drying the solid product B to obtain the vaterite-type calcium carbonate powder.
The invention adopts the method of introducing CO into rock salt brine2And the vaterite-type calcium carbonate is prepared by a method of regulating and controlling the pH of the brine within a certain range by NaOH regulation. The method utilizes the introduced CO2The NaCl and the Ca which are rich in the rock salt brine2+Reaction to form Na2CO3And CaCO3NaCl as CO3 2-The carrier plays a role in slowly releasing CO2Has the effect of increasing CO2The utilization rate of the calcium carbonate precursor and the yield of the calcium carbonate precursor are improved; by means of Mg contained in the brine2+And continuously adding NaOH solution to regulate the pH value of the brine, and jointly regulating and controlling the crystal form of the calcium carbonate without adding NaOH solutionAdding impurity elements to prepare the high-yield vaterite-type calcium carbonate.
Compared with the prior art, the invention has the following advantages: (1) the preparation method solves the problem of CO existing in the process of preparing calcium carbonate by a direct carbonization method2Low utilization rate and low product yield, realizes the resource utilization of calcium in rock brine and CO2The comprehensive recovery of the process. (2) The invention takes rock salt brine as raw material, and the raw material has wide source and low price; 3) the preparation method is simple and easy to operate, has low requirements on reaction environment and reaction conditions in the reaction process, can be carried out at room temperature, is environment-friendly in the process of preparing the vaterite-type calcium carbonate, is environment-friendly in the reaction, is continuously controllable in operation procedure, and is easy for expanded production.
Drawings
FIG. 1 is an XRD pattern of vaterite-type calcium carbonate prepared in example 1 of the present invention;
FIG. 2 is an SEM photograph of vaterite-type calcium carbonate prepared in example 1 of the present invention, wherein FIGS. 2 (a) and 2 (b) are SEM photographs on the scale of 5 μm and 2 μm, respectively;
FIG. 3 is an EDS spectrum of vaterite-type calcium carbonate prepared in example 1 of the present invention;
FIG. 4 is an XRD pattern of aragonite-type calcium carbonate prepared in comparative example 1 of the present invention;
FIG. 5 is an SEM photograph of the aragonite-type calcium carbonate prepared in comparative example 1 of the present invention, wherein FIGS. 5 (a) and 5 (b) are SEM photographs on a scale of 5 μm and 2 μm, respectively;
FIG. 6 is an EDS spectrum of an aragonite-type calcium carbonate prepared in comparative example 1 of the present invention;
fig. 7 is an XRD pattern of calcite-type calcium carbonate prepared in comparative example 2 of the present invention;
fig. 8 is an SEM image of calcite-type calcium carbonate prepared in comparative example 2 of the present invention, wherein fig. 8 (a) and 8 (b) are SEM images on the scales of 5 μm and 2 μm, respectively;
fig. 9 (a) and (b) are EDS spectra of calcite-type calcium carbonate prepared according to comparative example 2 of the present invention.
Detailed Description
The present invention is not limited to the embodiments described below, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.
The invention relates to a method for preparing vaterite type calcium carbonate from rock salt brine at room temperature, which comprises the following steps:
1) introducing CO into rock salt brine serving as a raw material2Stirring at room temperature to obtain reaction solution, and adjusting and controlling the pH value of rock salt brine to 9.3-9.7 during stirring;
2) adding a flocculating agent into the reaction liquid, stirring at a rotating speed of 50-100 r/min for 10-30 min, standing and settling to obtain a solid product A;
3) and washing the solid product A with deionized water to obtain a solid product B, and drying the solid product B to obtain the vaterite-type calcium carbonate powder.
In the step 1, CO is introduced2The flow rate of (2) is 0.02 to 0.06Nm3/h。
In the step 1, the rotating speed of the stirring reaction is 600-1000 r/min, and the stirring time is 60-120 min.
In the step 1, the room temperature is 0-30 ℃. Preferably, the room temperature is 25-30 ℃.
In the step 1, the pH value of the rock salt brine is regulated and controlled by adding a saturated NaOH solution.
In the step 2, the flocculating agent is polyacrylamide, polyaluminium chloride or polyferric sulfate.
The addition amount of the flocculant is 5-15 mg/L.
In the step 3, the pH of the deionized water is = 7-9, and the solid product B is dried at 50-60 ℃ for 10-14h to obtain the target product.
The mass concentration of NaCl in the rock salt brine is 295-305 g/L, and the mass concentration of Ca is Ca2+The mass concentration of (A) is 400-800 Mg/L, Mg2+The mass concentration of (A) is 20-50 g/L.
The rock salt brine used in the following examples and comparative examples was provided by Yunnan salt industries, and had a NaCl content of 295-305 g/L and Ca content2+400-800 Mg/L of Mg2+The content is 20-50 mg/L;CO2NaOH and NaOH are analytically pure or industrial grade raw materials; the flocculants used were all polyacrylamide, purchased from epson (china) flocculants ltd.
Example 1
Taking rock salt brine (NaCl 298.41 g/L, Na)2SO4 21.51g/L，Ca2+ 462.1 mg/L，Mg2+24.02 mg/L) 1L was added to a beaker and CO was added2Introducing into brine, and controlling gas flow rate to be 0.02Nm by a gas flowmeter3And h, stirring at the rotation speed of 500r/min, stirring for 60min at the temperature of 30 ℃ to obtain a reaction solution, and slowly adding a saturated NaOH solution to regulate the pH value of the brine to 9.5 in the stirring process. 5mg of polyacrylamide flocculant is added into the reaction liquid, the rotating speed is controlled to be 50r/min, and the reaction liquid is stirred for 10min in a timing manner.
And after the reaction is finished, taking out the product A, washing the product A for 2 times by using deionized water with the pH =7, carrying out solid-liquid separation to obtain a product B, and drying the product B at the constant temperature of 50 ℃ for 12 hours to obtain powder, namely the vaterite type calcium carbonate.
The collected powder was stored in a silica gel dryer for XRD phase analysis, SEM and EDS analysis, and the results are shown in fig. 1, fig. 2 and fig. 3, respectively. XRD results show that the product is mainly the diffraction peak of the vaterite type calcium carbonate, and the peak shape is intact; SEM results show that the powder particles in the product are all in a regular spherical geometric shape; the SEM-EDS and XRD detection results prove that the obtained product is relatively pure vaterite type calcium carbonate. The vaterite-type calcium carbonate content in the product was found to be 99.4% by EDS chemical composition analysis.
Example 2
Taking rock salt brine (NaCl 298.41 g/L, Na)2SO4 21.51g/L，Ca2+ 462.1 mg/L，Mg2+24.02 mg/L) 1L was added to a beaker and CO was added2Introducing into brine, and controlling gas flow rate to be 0.04Nm by a gas flowmeter3And h, stirring at the rotation speed of 750r/min, stirring for 90min at 25 ℃ to obtain a reaction solution, and slowly adding a saturated NaOH solution to regulate the pH value of the brine to 9.3 in the stirring process. And adding 10mg of polyacrylamide flocculant into the reaction solution, controlling the rotating speed to be 75r/min, and stirring for 20min in a timing manner.
And after the reaction is finished, taking out the product A, washing the product A for 3 times by using deionized water with the pH =8, carrying out solid-liquid separation to obtain a product B, and drying the product B at the constant temperature of 55 ℃ for 14 hours to obtain powder, namely the vaterite type calcium carbonate.
Example 3
Taking rock salt brine (NaCl 298.41 g/L, Na)2SO4 21.51g/L，Ca2+ 462.1 mg/L，Mg2+24.02 mg/L) 1L was added to a beaker and CO was added2Introducing into brine, and controlling gas flow rate to be 0.06Nm by a gas flowmeter3And h, stirring at the rotation speed of 1000r/min, stirring for 120min at 20 ℃ to obtain a reaction solution, and slowly adding a saturated NaOH solution to regulate the pH value of the brine to 9.7 in the stirring process. Adding 15mg of polyacrylamide flocculant into the reaction solution, controlling the rotating speed at 100r/min, and stirring for 30min in a timing manner.
And after the reaction is finished, taking out the product A, washing the product A for 1 time by using deionized water with the pH =9, carrying out solid-liquid separation to obtain a product B, and drying the product B at the constant temperature of 60 ℃ for 10 hours to obtain powder, namely the vaterite type calcium carbonate.
Example 4
Taking rock salt brine (NaCl 298.41 g/L, Na)2SO4 21.51g/L，Ca2+ 462.1 mg/L，Mg2+24.02 mg/L) 1L was added to a beaker and CO was added2Introducing into brine, and controlling gas flow rate to be 0.03Nm by a gas flowmeter3And h, stirring at the rotation speed of 700r/min, stirring for 80min at the temperature of 20 ℃ to obtain a reaction solution, and slowly adding a saturated NaOH solution to regulate the pH value of the brine to 9.4 in the stirring process. Adding 8mg of polyacrylamide flocculant into the reaction solution, controlling the rotating speed to be 60r/min, and stirring for 15min in a timing manner.
And after the reaction is finished, taking out the product A, washing the product A for 1 time by using deionized water with the pH =7, carrying out solid-liquid separation to obtain a product B, and drying the product B at the constant temperature of 52 ℃ for 12 hours to obtain powder, namely the vaterite type calcium carbonate.
Example 5
Taking rock salt brine (NaCl 298.41 g/L, Na)2SO4 21.51g/L，Ca2+ 462.1 mg/L，Mg2+24.02 mg/L) 1L was added to a beaker and CO was added2Introducing into brine, and controlling by gas flowmeterGas flow rate of 0.05Nm3And h, stirring at the rotation speed of 900r/min, stirring for 90min at the temperature of 10 ℃ to obtain a reaction solution, and slowly adding a saturated NaOH solution to regulate the pH value of the brine to 9.6 in the stirring process. Adding 12mg of polyacrylamide flocculant into the reaction solution, controlling the rotating speed to be 80r/min, and stirring for 25min in a timing manner.
And after the reaction is finished, taking out the product A, washing the product A for 1 time by using deionized water with the pH =8, carrying out solid-liquid separation to obtain a product B, and drying the product B at the constant temperature of 56 ℃ for 13 hours to obtain powder, namely the vaterite type calcium carbonate.
Example 6
Taking rock salt brine (NaCl 298.41 g/L, Na)2SO4 21.51g/L，Ca2+ 462.1 mg/L，Mg2+24.02 mg/L) 1L was added to a beaker and CO was added2Introducing into brine, and controlling gas flow rate to be 0.06Nm by a gas flowmeter3And h, stirring at the temperature of 0 ℃ and the rotating speed of 800r/min, stirring for 110min at a timing to obtain a reaction solution, and slowly adding a saturated NaOH solution during stirring to control the pH value of the brine to be 9.5. Adding 14mg of polyacrylamide flocculant into the reaction solution, controlling the rotating speed to be 90r/min, and stirring for 28min in a timing manner.
And after the reaction is finished, taking out the product A, washing the product A for 1 time by using deionized water with the pH =9, carrying out solid-liquid separation to obtain a product B, and drying the product B at the constant temperature of 58 ℃ for 11 hours to obtain powder, namely the vaterite type calcium carbonate.
Comparative example 1
Taking rock salt brine (NaCl 302.88 g/L, Na)2SO4 21.41g/L，Ca2+ 576 mg/L，Mg2+32 mg/L) 1L was added to a beaker, and CO was added2Introducing into brine, and controlling gas flow rate to be 0.04Nm by a gas flowmeter3And h, stirring at the rotation speed of 750r/min for 45min to obtain a reaction solution, and slowly adding a saturated NaOH solution to regulate the pH value of the brine to 10 in the stirring process. And adding 10mg of polyacrylamide flocculant into the reaction solution, controlling the rotating speed to be 75r/min, and stirring for 20min in a timing manner.
And after the reaction is finished, taking out the precipitated product A, washing the precipitated product A for 3 times by using deionized water with the pH =8, carrying out solid-liquid separation to obtain a product B, and drying the product B at the constant temperature of 55 ℃ for 10 hours to obtain powder, namely aragonite calcium carbonate.
The collected powder was stored in a silica gel dryer for XRD phase analysis, SEM and EDS analysis, and the results are shown in fig. 4, fig. 5 and fig. 6, respectively. XRD results show that the product mainly contains diffraction peaks of aragonite calcium carbonate, has complete peak shapes and contains a small amount of NaCl. SEM results show that all the powder particles in the product are in a regular oval geometric shape. SEM-EDS and XRD detection results prove that the obtained product is relatively pure aragonite calcium carbonate; the content of the calcium carbonate with the stone type in the product is 98.3 percent through EDS chemical composition analysis.
Comparative example 2
Taking Yunnan rock salt brine (NaCl 305.3g/L, Na)2SO4 21.56g/L，Ca2+ 486mg/L，Mg 2+30 mg/L) 1L was added to a beaker, and CO was added2Introducing into brine, and controlling gas flow rate to be 0.08Nm by a gas flowmeter3And h, stirring at the rotation speed of 1000r/min for 60min to obtain a reaction solution, and slowly adding a saturated NaOH solution during stirring to regulate the pH value of the brine to be 11. Adding 15mg of polyacrylamide flocculant into the reaction solution, controlling the rotating speed at 100r/min, and stirring for 30min in a timing manner. And (3) after the reaction time is ended, taking out the precipitated product A, washing the precipitated product A for 1 time by using deionized water with the pH =9, performing solid-liquid separation to obtain a product B, and drying the product B at the constant temperature of 60 ℃ for 10 hours to obtain powder, namely calcite type calcium carbonate.
The collected powder was stored in a silica gel dryer for XRD phase analysis, SEM and EDS analysis, and the results are shown in fig. 7, fig. 8 and fig. 9, respectively. XRD results show that the product mainly contains diffraction peaks of calcite type calcium carbonate, and the peaks are intact; SEM results show that the powder particles in the product are a mixture of spherical geometry and square geometry; SEM-EDS and XRD detection results prove that the obtained product is spherical and cubic calcite type calcium carbonate; the content of calcite type calcium carbonate in the product is 97.69 percent according to EDS chemical composition analysis.
As can be seen from the preparation methods, XRD (X-ray diffraction) spectrums, SEM (scanning Electron microscope) charts and EDS (electronic Desorption) spectrums of the comparative examples 1-6, the comparative example 1 and the comparative example 2, the products prepared from different brine pH values are different in the preparation process: when pH =9.3-9.7, the product is vaterite-type calcium carbonate; as can be seen from comparative example 1, when pH =10, the product was aragonite-type calcium carbonate; when pH =11, the product is calcite-type calcium carbonate. Therefore, in the present invention, the pH of the brine for preparing the vaterite type calcium carbonate is controlled to be 9.3-9.7.
Claims (10)
1. A method for preparing vaterite type calcium carbonate from rock salt brine at room temperature is characterized by comprising the following steps:
1) introducing CO into rock salt brine serving as a raw material2Stirring and reacting at room temperature to obtain a reaction solution, and adjusting and controlling the pH value of the rock salt brine to be 9.3-9.7 in the stirring process;
2) adding a flocculating agent into the reaction liquid, stirring at a rotating speed of 50-100 r/min for 10-30 min, standing and settling to obtain a solid product A;
3) and washing the solid product A with deionized water to obtain a solid product B, and drying the solid product B to obtain the vaterite-type calcium carbonate powder.
2. The method for preparing vaterite-type calcium carbonate from rock brine at room temperature according to claim 1, wherein in the step 1, CO is introduced2The flow rate of (2) is 0.02 to 0.06Nm3/h。
3. The method for preparing the vaterite-type calcium carbonate from the rock-salt brine at room temperature according to claim 1, wherein in the step 1, the rotation speed of the stirring reaction is 600-1000 r/min, and the stirring time is 60-120 min.
4. The method for preparing vaterite-type calcium carbonate from rock brine at room temperature according to claim 1, wherein the room temperature is 0-30 ℃.
5. The method for preparing vaterite-type calcium carbonate from rock brine at room temperature according to claim 4, wherein the room temperature is 25-30 ℃.
6. The method for preparing vaterite-type calcium carbonate from rock-salt brine at room temperature as claimed in claim 1, wherein in the step 1, the pH value of rock-salt brine is controlled by adding saturated NaOH solution.
7. The method for preparing vaterite type calcium carbonate from rock brine at room temperature as claimed in claim 1, wherein in the step 2, the flocculant is polyacrylamide, polyaluminium chloride or polyferric sulfate.
8. The method for preparing the vaterite-type calcium carbonate from the rock-salt brine at room temperature according to any one of claims 1 or 7, wherein the addition amount of the flocculant is 5-15 mg/L.
9. The method for preparing the vaterite-type calcium carbonate from the rock-salt brine at room temperature according to claim 1, wherein in the step 3, the pH of the deionized water is = 7-9, and the solid product B is dried at 50-60 ℃ for 10-14h to obtain the target product.
10. The method of claim 1, wherein the mass concentration of NaCl in the rock-brine is 295-305 g/L and Ca is contained in the rock-brine2+The mass concentration of (A) is 400-800 Mg/L, Mg2+The mass concentration of (A) is 20-50 g/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011472842.9A CN112723401A (en) | 2020-12-15 | 2020-12-15 | Method for preparing vaterite type calcium carbonate from rock salt brine at room temperature |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011472842.9A CN112723401A (en) | 2020-12-15 | 2020-12-15 | Method for preparing vaterite type calcium carbonate from rock salt brine at room temperature |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112723401A true CN112723401A (en) | 2021-04-30 |
Family
ID=75602051
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011472842.9A Pending CN112723401A (en) | 2020-12-15 | 2020-12-15 | Method for preparing vaterite type calcium carbonate from rock salt brine at room temperature |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112723401A (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004238232A (en) * | 2003-02-04 | 2004-08-26 | Nippon Paper Industries Co Ltd | Method for producing calcium carbonate |
| AU2007101174A4 (en) * | 2007-12-10 | 2008-01-31 | Green, Kenneth Mr | Improved method of capturing carbon dioxide and converting to carbonate anions and then combining with calcium cations to form calcium carbonate |
| CN101289200A (en) * | 2007-04-16 | 2008-10-22 | 中国盐业总公司 | Technological process for purifying bittern |
| CN101570342A (en) * | 2009-06-11 | 2009-11-04 | 福建省万旗非金属材料有限公司 | Method for preparing high-whiteness nanometer calcium carbonate special for silicone sealant by utilizing low-grade limestone by wet method |
| CN104118895A (en) * | 2014-07-24 | 2014-10-29 | 北京化工大学 | Method for preparing homogenous nano vaterite type calcium carbonate through limestone acidolysis |
| KR20180137206A (en) * | 2017-06-16 | 2018-12-27 | 한국해양대학교 산학협력단 | A method for producing high purity calcium carbonate using indirect carbonation of alkaline industrial by-products and seawater |
| CN109607572A (en) * | 2019-02-02 | 2019-04-12 | 中国科学院海洋研究所 | A method of comprehensive utilization subsurface brine production refined brine and calcium and magnesium compound |
| CN111333095A (en) * | 2020-03-10 | 2020-06-26 | 广东玉峰粉体材料股份有限公司 | Method for producing superfine calcium carbonate from industrial alkaline residue white mud |
| CN111727173A (en) * | 2018-03-30 | 2020-09-29 | 韩国海洋大学校产学协力团 | Preparation method of high-purity vaterite-type and calcite-type calcium carbonate by utilizing seawater indirect carbonation |
-
2020
- 2020-12-15 CN CN202011472842.9A patent/CN112723401A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004238232A (en) * | 2003-02-04 | 2004-08-26 | Nippon Paper Industries Co Ltd | Method for producing calcium carbonate |
| CN101289200A (en) * | 2007-04-16 | 2008-10-22 | 中国盐业总公司 | Technological process for purifying bittern |
| AU2007101174A4 (en) * | 2007-12-10 | 2008-01-31 | Green, Kenneth Mr | Improved method of capturing carbon dioxide and converting to carbonate anions and then combining with calcium cations to form calcium carbonate |
| CN101570342A (en) * | 2009-06-11 | 2009-11-04 | 福建省万旗非金属材料有限公司 | Method for preparing high-whiteness nanometer calcium carbonate special for silicone sealant by utilizing low-grade limestone by wet method |
| CN104118895A (en) * | 2014-07-24 | 2014-10-29 | 北京化工大学 | Method for preparing homogenous nano vaterite type calcium carbonate through limestone acidolysis |
| KR20180137206A (en) * | 2017-06-16 | 2018-12-27 | 한국해양대학교 산학협력단 | A method for producing high purity calcium carbonate using indirect carbonation of alkaline industrial by-products and seawater |
| CN111727173A (en) * | 2018-03-30 | 2020-09-29 | 韩国海洋大学校产学协力团 | Preparation method of high-purity vaterite-type and calcite-type calcium carbonate by utilizing seawater indirect carbonation |
| CN109607572A (en) * | 2019-02-02 | 2019-04-12 | 中国科学院海洋研究所 | A method of comprehensive utilization subsurface brine production refined brine and calcium and magnesium compound |
| CN111333095A (en) * | 2020-03-10 | 2020-06-26 | 广东玉峰粉体材料股份有限公司 | Method for producing superfine calcium carbonate from industrial alkaline residue white mud |
Non-Patent Citations (3)
| Title |
|---|
| 丁仕强: "碳酸钙悬浮液混凝处理后的流变性", 《过滤与分离》 * |
| 杨文俊等: ""石灰-烟道气法"卤水净化之试验研究", 《中国井矿盐》 * |
| 罗兴国 等: ""NaOH-烟道气法卤水净化中成垢离子的沉降行为"", 《过程工程学报》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109809457B (en) | Regular spherical calcium carbonate and preparation process thereof | |
| CN103466637B (en) | Method for producing precipitate silicon dioxide by using sodium bicarbonate to control supersaturation degree | |
| CN108069451B (en) | Method for preparing ultrafine amorphous calcium carbonate in alcohol-water mixed system | |
| CN106517285A (en) | Method for preparing bar-shaped nanometer calcium carbonate | |
| CN109809458B (en) | Rugby-shaped calcium carbonate and preparation process thereof | |
| Li et al. | Comprehensive use of dolomite-talc ore to prepare talc, nano-MgO and lightweight CaCO3 using an acid leaching method | |
| CN1618998A (en) | Method of preparing high purity magnesiun sand using salt lake bischofite as raw material | |
| CN111453754A (en) | Preparation method of high-purity and high-activity nano calcium carbonate | |
| CN113668060A (en) | Process for continuously preparing semi-hydrated and dihydrate calcium sulfate whiskers by using salt slurry | |
| CN109574056B (en) | Composite inducer for in-situ template-induced synthesis of nano calcium carbonate and application thereof | |
| CN114291835B (en) | Preparation method of large-small cubic dispersion precipitated calcium carbonate | |
| CN112723401A (en) | Method for preparing vaterite type calcium carbonate from rock salt brine at room temperature | |
| Zhang et al. | Efficient magnesium recovery from seawater desalination brine via CO2 mineralization to synthesize hydromagnesite for uranium extraction | |
| Hwang et al. | Preparation of high purity PCC from medium-and low-grade limestones using the strongly acidic cation exchange resin | |
| CN106865565A (en) | A kind of flyash synthesizes the method for X-type zeolite | |
| CN111606343B (en) | Preparation method of modified nano calcium carbonate | |
| CN110775994B (en) | Method for preparing regular cubic light calcium carbonate from carbide slag | |
| CN107445188B (en) | A kind of preparation method of rod-like precipitates calcium carbonate | |
| CN112142063A (en) | Preparation method of X molecular sieve | |
| CN110963520A (en) | Method for producing cubic calcium carbonate from lime foam | |
| CN102674429B (en) | High-whiteness sub-micron spherical barium sulfate and preparation method thereof | |
| JP4157202B2 (en) | Process for producing spindle-shaped calcium carbonate | |
| CN112624170B (en) | Method for preparing spherical calcite type calcium carbonate from high-calcium sodium sulfate type brine | |
| CN110203956B (en) | Method for preparing vaterite-phase-containing calcium carbonate by using calcium ethylene glycol wet ball milling | |
| CN113120935B (en) | Calcium carbonate and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210430 |
|
| RJ01 | Rejection of invention patent application after publication |