CN112624170B - Method for preparing spherical calcite type calcium carbonate from high-calcium sodium sulfate type brine - Google Patents

Method for preparing spherical calcite type calcium carbonate from high-calcium sodium sulfate type brine Download PDF

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CN112624170B
CN112624170B CN202011421532.4A CN202011421532A CN112624170B CN 112624170 B CN112624170 B CN 112624170B CN 202011421532 A CN202011421532 A CN 202011421532A CN 112624170 B CN112624170 B CN 112624170B
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calcium carbonate
brine
solid product
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sodium sulfate
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CN112624170A (en
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罗兴国
李俊杰
李兴彬
何劲
魏昶
邓志敢
李继东
李旻廷
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Yunnan Salt Industry Co ltd
Kunming University of Science and Technology
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Yunnan Salt Industry Co ltd
Kunming University of Science and Technology
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    • 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
    • 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
    • C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
    • 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
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    • 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
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Abstract

The invention relates to a method for preparing spherical calcite type calcium carbonate from high-calcium sodium sulfate type brine, belonging to the technical field of material chemical industry. To Gao Gailiu sodiumAdding 1.3 to 1.5g/LNa into the brine at the temperature of 20 to 40 DEG C 2 CO 3 And 0.15 to 0.35g/LNaOH, controlling the pH of brine to be =10.5 to 11.5, stirring for 30 to 120min, adding 5 to 15mg/L polyacrylamide flocculant after stirring, continuing stirring for 10 to 30min, and then standing and settling to obtain a solid product A; washing the obtained solid product A with deionized water with the pH of 7~9 to remove sodium, chlorine and magnesium soluble salts to obtain a solid product B, and drying the solid product B to obtain spherical calcite type calcium carbonate. The method has the advantages of simple raw material source, equipment and preparation process, low cost, reaction at room temperature, environmental friendliness, green and environment-friendly process and continuous and controllable operation program.

Description

Method for preparing spherical calcite type calcium carbonate from high-calcium sodium sulfate type brine
Technical Field
The invention relates to a method for preparing spherical calcite type calcium carbonate from high-calcium sodium sulfate type brine, belonging to the technical field of material chemical industry.
Background
Calcite (Calcite), aragonite (Aragonite) and Vaterite (Vaterite) are three common anhydrous crystal forms of calcium carbonate, and Calcite calcium carbonate belongs to one of the three crystal forms with the strongest thermodynamic stability. The spherical calcite calcium carbonate has the outstanding advantages of thermodynamic stability, large specific surface area, small specific gravity, good smoothness and the like, and can obviously improve the filling performance of ink, plastics, paint and the like and the coating property of paper. Therefore, it is very important to develop a simple method for preparing spherical calcite-type calcium carbonate.
At present, the methods for preparing spherical calcite calcium carbonate mainly comprise a carbonization method and a double decomposition method. Carbonisation of French Ca 2+ -H 2 O-CO 2 The shape and crystal form of the light calcium carbonate can be influenced by the direct carbonization process of the system. The double decomposition method is to add Ca 2+ Salt solution and CO-containing 3 2- The salt solution is mixed under certain conditions (concentration of the salt solution, reaction temperature, reaction time and different additives) to prepare the nano calcium carbonate. However, the traditional double decomposition method is complex in system, the added additive is difficult to remove, the physicochemical properties of the spherical calcium carbonate are greatly influenced, and the conditions are extremely harsh, so that the method is difficult to develop industrially. Therefore, the search for a method for directly preparing spherical calcite-type calcium carbonate without additional additives is a development trend of preparing calcium carbonate in the future.
Disclosure of Invention
In order to solve the problems and the defects of the prior art, the invention provides a method for preparing spherical calcite type calcium carbonate from high-calcium sodium sulfate type brine. The high calcium sodium sulfate type brine of the invention mainly comprises NaCl and Na 2 SO 4 And part of CaSO 4 、MgSO 4 And MgCl 2 ，Ca 2+ Concentration of (1) 400 to 800mg/L, mg 2+ The concentration of the calcium carbonate is 20 to 50mg/L, and the calcium carbonate is an ideal raw material for preparing spherical calcite type calcium carbonate. And the content of impurity ions in the brine is low, no additive is added in the preparation process to introduce the impurity ions, the problem that the impurities are difficult to remove in the traditional calcium carbonate preparation process is solved, and the resource utilization of calcium in the high-calcium sodium sulfate brine is realized. Utilizing Ca in high-calcium sodium sulfate type brine 2+ With the addition of CO 3 2- Directly preparing calcium carbonate precursor by using Mg contained in brine 2+ Regulating and controlling the crystal form of the calcium carbonate to finally obtain a spherical calcite type calcium carbonate product. Therefore, the method for directly preparing spherical calcite-type carbonic acid from the high-calcium sodium sulfate type brine is a method with wide application prospect.
A method for preparing spherical calcite-type calcium carbonate from high-calcium sodium sulfate-type brine, comprising the following steps:
(1) Adding 1.3 to 1.5g/LNa into high-calcium sodium sulfate type brine at the temperature of 20 to 40 DEG C 2 CO 3 And 0.15 to 0.35g/LNaOH, controlling the pH of brine to be 10.5 to 11.5, stirring for 30 to 120min, adding 5 to 15mg/L polyacrylamide flocculant after stirring, continuously stirring for 10 to 30min, and standing for settling for 2 to 4h to obtain a solid product A;
(2) Washing the solid product A obtained in the step (1) with deionized water with the pH =7~9 to remove sodium, chlorine and magnesium soluble salts to obtain a solid product B, and drying the solid product B to obtain spherical calcite type calcium carbonate.
The sodium high-calcium sulfate type brine in the step (1) contains NaCl and Na 2 SO 4 、CaSO 4 、MgSO 4 And MgCl 2 Wherein Ca is 2+ The concentration is 400 to 800mg/L, mg 2+ The concentration is 20 to 50mg/L.
The invention has the beneficial effects that:
(1) Utilizing Ca in high-calcium sodium sulfate type brine 2+ With CO 3 2- Directly preparing calcium carbonate precursor by using Mg contained in brine 2+ The crystal form of the calcium carbonate is regulated and controlled to prepare the spherical calcite type calcium carbonate, no additive is added to introduce impurity ions, and the resource utilization of calcium in the high-calcium sodium sulfate type brine is realized.
(2) The method has the advantages of simple raw material source, equipment and preparation process, low cost, reaction at room temperature, environmental friendliness, green and environment-friendly process, continuous and controllable operation program and easy expanded production.
Drawings
FIG. 1 is the XRD patterns of the spherical calcite-type calcium carbonate products prepared in examples 1 to 3 of the present invention, wherein the pattern (a) is the XRD pattern of the product in example 1, the pattern (b) is the XRD pattern of the product in example 2, and the pattern (c) is the XRD pattern of the product in example 3;
FIG. 2 is an infrared spectrum of a spherical calcite-type calcium carbonate product prepared according to examples 1 to 3 of the present invention, wherein FIG. a is an infrared spectrum of the product of example 1, FIG. b is an infrared spectrum of the product of example 2, and FIG. c is an infrared spectrum of the product of example 3;
FIG. 3 is an SEM/EDS diagram of spherical calcite-type calcium carbonate products prepared in examples 1 to 3 according to the present invention, wherein the diagram (a) is an SEM diagram of the product of example 1, the diagram (a-1) is an EDS diagram of the product of example 1, the diagram (b) is an SEM diagram of the product of example 2, the diagram (b-1) is an EDS diagram of the product of example 2, the diagram (c) is an SEM diagram of the product of example 3, and the diagram (c-1) is an EDS diagram of the product of example 3.
Detailed Description
The invention is further described with reference to the following drawings and detailed description.
The high calcium sodium sulfate type brine used in the following examples was supplied by Yunnan, inc., ca 2+ The content is 400 to 800mg/L, mg 2+ The content is 20 to 50mg/L; na (Na) 2 CO 3 And NaOH are both chemically or industrially pure reagents; polyacrylamide flocculants were purchased from epson (china) flocculants ltd.
Example 1
The method for preparing spherical calcite-type calcium carbonate from high-calcium sodium sulfate-type brine comprises the following steps:
(1) Adding 1L of high calcium sodium sulfate type bittern (containing NaCl and Na as ingredients) 2 SO 4 、CaSO 4 、MgSO 4 And MgCl 2 Wherein the concentration of NaCl is 305.71g/L, na 2 SO 4 Concentration 21.42g/L, ca 2+ At a concentration of 486Mg/L, mg 2+ Concentration 30 mg/L), 1.3g of Na was added at a temperature of 20 deg.C 2 CO 3 (Na in brine) 2 CO 3 Concentration of 1.3 g/L) and 0.15g of NaOH (concentration of NaOH in brine is 0.15 g/L), controlling pH =10.5 to 11.5, stirring for 30min under the condition of stirring rotation speed of 300r/min, adding 5mg of polyacrylamide flocculant (concentration of polyacrylamide flocculant in brine is 5 mg/L) after stirring is finished, adjusting rotation speed to 50r/min, continuing stirring for 10min, and then standing and settling for 2h to obtain a solid product A;
(2) And (2) washing 1~2 times by using deionized water with the pH =7~9 to remove sodium, chlorine and magnesium soluble salts to obtain a solid product B, and drying the solid product B at 50 ℃ for 12h to obtain spherical calcite type calcium carbonate.
The XRD pattern of the spherical calcite-type calcium carbonate prepared in the example is shown in figure 1 (a), and from figure 1 (a), the product is calcite-type calcium carbonate as can be seen by comparing the diffraction peak corresponding to 2-Theta/° with XRD standard card (PDF # 05-0586).
The infrared spectrum of the spherical calcite-type calcium carbonate prepared in this example is shown in fig. 2 (a), and it can be seen from fig. 2 (a) that the characteristic absorption peak intensity of the calcite-type calcium carbonate in the product is high.
The SEM diagram of the spherical calcite-type calcium carbonate prepared in the example is shown in a figure 3 (a), and the EDS diagram is shown in a figure 3 (a-1); as shown in FIG. 3 (a), the powder particles in the product were all of regular spherical geometry. SEM/EDS and XRD detection results prove that the obtained product is spherical calcite type calcium carbonate with relatively pure and perfect crystal form. Chemical composition analysis shows that the content of spherical calcite in the product is 99.16%.
Example 2
The method for preparing spherical calcite type calcium carbonate from high-calcium sodium sulfate type brine comprises the following steps:
(1) Adding 1L of high calcium sodium sulfate type bittern (containing NaCl and Na as ingredients) 2 SO 4 、CaSO 4 、MgSO 4 And MgCl 2 Wherein the concentration of NaCl is 305.71g/L, na 2 SO 4 Concentration 21.42g/L, ca 2+ Concentration 587.1 Mg/L, mg 2+ 48.24 mg/L), 1.42g of Na was added at 40 ℃ to the mixture 2 CO 3 (Na in brine) 2 CO 3 Concentration of 1.42 g/L) and 0.21g of NaOH (concentration of NaOH in brine is 0.21 g/L), controlling pH =10.5 to 11.5, stirring for 30min under the condition of stirring rotation speed of 350r/min, adding 10mg of polyacrylamide flocculant (concentration of polyacrylamide flocculant in brine is 10 mg/L) after stirring is finished, adjusting rotation speed to 75r/min, continuing stirring for 20min, and then standing and settling for 2h to obtain a solid product A;
(2) And (2) washing 1~2 times by using deionized water with the pH =7~9 to remove sodium, chlorine and magnesium soluble salts to obtain a solid product B, and drying the solid product B at 55 ℃ for 10h to obtain spherical calcite type calcium carbonate.
The XRD pattern of the spherical calcite-type calcium carbonate prepared in the example is shown in figure 1 (b), and from figure 1 (b), the diffraction peak corresponding to 2-Theta/° in the XRD pattern is compared with XRD standard card (PDF # 05-0586), which indicates that the product is calcite-type calcium carbonate.
The infrared spectrum of the spherical calcite-type calcium carbonate prepared in this example is shown in fig. 2 (b), and it can be seen from fig. 2 (b) that the characteristic absorption peak intensity of the calcite-type calcium carbonate in the product is high.
The SEM diagram of the spherical calcite-type calcium carbonate prepared in the example is shown in a figure 3 (b), and the EDS diagram is shown in a figure 3 (b-1); as shown in fig. 3 (b), the powder particles in the product were all of regular spherical geometry. SEM/EDS and XRD detection results prove that the obtained product is spherical calcite type calcium carbonate which is relatively pure and has a perfect crystal form. The content of the spherical calcite in the product is 99.11 percent according to chemical component analysis.
Example 3
The method for preparing spherical calcite-type calcium carbonate from high-calcium sodium sulfate-type brine comprises the following steps:
(1) Adding 1L of high calcium sodium sulfate type bittern (containing NaCl and Na as ingredients) 2 SO 4 、CaSO 4 、MgSO 4 And MgCl 2 Wherein the concentration of NaCl is 307.18g/L, na 2 SO 4 Concentration 21.27g/L, ca 2+ Concentration 762.8Mg/L, mg 2+ Concentration of 47.1 mg/L), 1.5g of Na was added at 40 ℃ to the mixture 2 CO 3 (Na in brine) 2 CO 3 Concentration of 1.5 g/L) and 0.35g NaOH (concentration of NaOH in brine is 0.35 g/L), controlling pH =10.5 to 11.5, stirring for 120min under the condition of stirring rotation speed of 400r/min, adding 15mg of polyacrylamide flocculant (concentration of polyacrylamide flocculant in brine is 15 mg/L) after stirring is finished, adjusting rotation speed to 100r/min, continuing stirring for 30min, and then standingSettling for 2 hours to obtain a solid product A;
(2) And (2) washing 1~2 times by using deionized water with the pH =7~9 to remove sodium, chlorine and magnesium soluble salts to obtain a solid product B, and drying the solid product B at 60 ℃ for 6h to obtain spherical calcite type calcium carbonate.
The XRD pattern of the spherical calcite-type calcium carbonate prepared in the example is shown in figure 1 (c), and from figure 1 (c), the diffraction peak corresponding to 2-Theta/° in the XRD pattern is compared with XRD standard card (PDF # 05-0586), which indicates that the product is calcite-type calcium carbonate.
The infrared spectrum of the spherical calcite-type calcium carbonate prepared in this example is shown in fig. 2 (c), and it can be seen from fig. 2 (c) that the characteristic absorption peak intensity of the calcite-type calcium carbonate in the product is high.
The SEM picture of the spherical calcite-type calcium carbonate prepared in the example is shown in a figure 3 (c), and the EDS map is shown in a figure 3 (c-1); as shown in FIG. 3 (c), the powder particles in the product were all of regular spherical geometry. SEM/EDS and XRD detection results prove that the obtained product is spherical calcite type calcium carbonate with relatively pure and perfect crystal form. The content of the spherical calcite in the product is 98.86 percent according to chemical composition analysis.
Example 4
The method for preparing spherical calcite type calcium carbonate from high-calcium sodium sulfate type brine comprises the following steps:
(1) Adding 1L of high calcium sodium sulfate type bittern (containing NaCl and Na as ingredients) 2 SO 4 、CaSO 4 、MgSO 4 And MgCl 2 Wherein the concentration of NaCl is 307.18g/L, na 2 SO 4 Concentration 21.27g/L, ca 2+ Concentration 762.8Mg/L, mg 2+ Concentration of 47.1 mg/L), 1.5g of Na was added at 30 ℃ to the mixture 2 CO 3 (Na in brine) 2 CO 3 Concentration of 1.5 g/L) and 0.35g NaOH (concentration of NaOH in brine is 0.35 g/L), controlling pH =10.5 to 11.5, stirring for 100min under the condition of stirring rotation speed of 400r/min, and adding 15mg of polyacrylamide flocculant (concentration of polyacrylamide flocculant in brine is 15)mg/L), regulating the rotating speed to 100r/min, continuing stirring for 30min, and then standing and settling for 4h to obtain a solid product A;
(2) And (2) washing 1~2 times by using deionized water with the pH =7~9 to remove sodium, chlorine and magnesium soluble salts to obtain a solid product B, and drying the solid product B at 60 ℃ for 6h to obtain spherical calcite type calcium carbonate.
While the present invention has been described in detail with reference to the embodiments shown in the drawings, the present invention is not limited to the embodiments, and various changes can be made without departing from the spirit and scope of the present invention.

Claims (1)

1. A method for preparing spherical calcite type calcium carbonate from high-calcium sodium sulfate type brine is characterized by comprising the following steps:
(1) Adding 1.3 to 1.5g/LNa into high-calcium sodium sulfate type brine at the temperature of 20 to 40 DEG C 2 CO 3 And 0.15 to 0.35g/LNaOH, controlling the pH of brine to be =10.5 to 11.5, stirring for 30 to 120min, adding 5 to 15mg/L polyacrylamide flocculant after stirring, continuing stirring for 10 to 30min, and standing and settling for 2 to 4h to obtain a solid product A;
(2) Washing the solid product A obtained in the step (1) with deionized water with the pH =7~9 to remove sodium, chlorine and magnesium soluble salts to obtain a solid product B, and drying the solid product B to obtain spherical calcite type calcium carbonate;
the sodium high-calcium sulfate type brine in the step (1) contains NaCl and Na 2 SO 4 、CaSO 4 、MgSO 4 And MgCl 2 Wherein Ca is 2+ The concentration is 400 to 800mg/L, mg 2+ The concentration is 20 to 50mg/L.
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DE19848731A1 (en) * 1998-10-22 2000-04-27 Degussa Process for cleaning brines, whereby magnesium and calcium are precipitated as Mg (OH) 2 and CaCO3 and separated from the brine
WO2009019709A2 (en) * 2007-08-09 2009-02-12 Sea-Tech Innovations Ltd. Process for recovering substances from high salinity liquids
CN101691239B (en) * 2009-09-30 2013-02-13 达州市恒成能源（集团）有限责任公司 Comprehensive utilization method for bittern
CN109626688A (en) * 2018-12-10 2019-04-16 中盐枣阳盐化有限公司 It is a kind of do not purify under the conditions of middle less salt nitre compare brine concentration method
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

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