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Process for the Remediation of Titanogypsum (Red Gypsum) Using Weak Acid and CaCl2 to Produce Saleable α-Gypsum and FeCl2·4H2O

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Download Hi-Res ImageDownload to MS-PowerPointCite This:Ind. Eng. Chem. Res. 2024, 63, 27, 11790-11799
    Applied Chemistry

    Process for the Remediation of Titanogypsum (Red Gypsum) Using Weak Acid and CaCl2 to Produce Saleable α-Gypsum and FeCl2·4H2O
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    • Shuaifeng Liu
      Shuaifeng Liu
      Key Laboratory of Green Process and Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China
      Institute of Materials Technology Research, HBIS Group Co., Ltd., Shijiazhuang 050023, Hebei Province, China
      More by Shuaifeng Liu
    • Edouard Asselin*
      Edouard Asselin
      Department of Materials Engineering, The University of British Columbia, 309-6350 Stores Road, Vancouver, British Columbia V6T 1Z4, Canada
      *Email: edouard.asselin@ubc.ca
      More by Edouard Asselin
      Orcidhttps://orcid.org/0000-0001-9492-4949
    • Zhibao Li*
      Zhibao Li
      Key Laboratory of Green Process and Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China
      *Email: zhibaoli@ipe.ac.cn
      More by Zhibao Li
      Orcidhttps://orcid.org/0000-0002-5737-1289
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    Industrial & Engineering Chemistry Research

    Cite this: Ind. Eng. Chem. Res. 2024, 63, 27, 11790–11799
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.iecr.4c01190
    Published June 27, 2024
    Copyright © 2024 American Chemical Society
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    Abstract

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    The disposal of titanogypsum, also known as red gypsum, which is generated during the titanium dioxide sulfate process, has become a significant environmental challenge. We propose a new process to recover iron impurities such as FeCl2·4H2O and to convert titanogypsum to saleable hemihydrate gypsum. For this purpose, we use HCl–FeCl2 solution generated via the reaction of H2SO4–FeSO4 with CaCl2 to leach iron hydroxide from titanogypsum. The hemihydrate precipitation and phase-transition kinetics of the reaction of HCl–H2SO4–FeSO4 with CaCl2 are experimentally investigated at 353 K. The common ion effect of CaCl2 in the FeCl2 solution for FeCl2·4H2O crystallization is predicted by NRTL modeling of the solid–liquid equilibria of the FeCl2–CaCl2–H2O system. High-quality, saleable α-gypsum and FeCl2·4H2O solids obtained by treating titanogypsum samples provided by a commercial processing plant further shows that the new process is feasible.

    Copyright © 2024 American Chemical Society

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    Supporting Information

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.iecr.4c01190.

    • Solid–liquid equilibria for the FeCl2(1)–CaCl2(2)–H2O(3) system from 293 to 343 K at 101.3 kPaa; E-NRTL parameters of interaction between species in the system FeCl2–CaCl2–H2O (PDF)

    Process for the Remediation of Titanogypsum (Red Gypsum) Using Weak Acid and CaCl2 to Produce Saleable α‑Gypsum and FeCl2·4H2O

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    1
    SUPPORTING INFORMATION
    Process for the Remediation of Titanogypsum (Red Gypsum) Using Weak
    Acid and CaCl
    2
    to Produce Saleable
    α-Gypsum
    and FeCl
    2
    ·4H
    2
    O
    Shuaifeng Liu
    1,2
    , Edouard Asselin
    3,
    *, Zhibao Li
    1,
    *
    1
    Key Laboratory of Green Process and Engineering, Institute of Process Engineering, Chinese
    Academy of Sciences, Beijing 100190, China
    2
    Institute of Materials Technology Research, HBIS Group Co., Ltd., Shijiazhuang 050023, Hebei
    Province, China
    3
    Department of Materials Engineering, The University of British Columbia, 309 - 6350 Stores
    Road, Vancouver, British Columbia V6T 1Z4, Canada
    * To whom correspondence should be addressed to E-mail:
    zhibaoli@ipe.ac.cn,
    edouard.asselin@ubc.ca
    2
    Table S1. Solid-Liquid Equilibria for the FeCl
    2
    (1)-CaCl
    2
    (2)-H
    2
    O(3) System from 293 to 343
    K at 101.3 kPa
    a
    1
    (mol / kg)
    b
    m
    2
    (mol / kg)
    m
    1
    (wt %)
    c
    w
    2
    (wt %)
    w
    1
    x
    d
    2
    x
    solid phase
    T = 293 K, solid: FeCl
    2
    ·4H
    2
    O
    4.956
    0.000
    0.386
    0.000
    0.082
    0.000
    A
    4.380
    0.487
    0.345
    0.034
    0.073
    0.008
    A
    3.913
    0.951
    0.310
    0.066
    0.065
    0.016
    A
    3.513
    1.408
    0.278
    0.098
    0.058
    0.023
    A
    3.095
    2.004
    0.243
    0.138
    0.051
    0.033
    A
    2.571
    2.587
    0.202
    0.178
    0.042
    0.043
    A
    2.354
    2.929
    0.184
    0.200
    0.039
    0.048
    A
    2.009
    3.502
    0.155
    0.237
    0.033
    0.057
    A
    1.752
    3.866
    0.135
    0.260
    0.029
    0.063
    A
    1.310
    4.652
    0.099
    0.307
    0.021
    0.076
    A
    1.106
    5.504
    0.080
    0.349
    0.018
    0.089
    A
    T = 293 K, solid: CaCl
    2
    ·6H
    2
    O
    1.030
    6.074
    0.072
    0.374
    0.016
    0.097
    B
    0.773
    6.655
    0.053
    0.402
    0.012
    0.106
    B
    0.572
    6.762
    0.040
    0.412
    0.009
    0.108
    B
    0.390
    6.825
    0.027
    0.419
    0.006
    0.109
    B
    0.204
    6.927
    0.014
    0.429
    0.003
    0.111
    B
    0.000
    7.085
    0.000
    0.440
    0.000
    0.113
    B
    T = 318 K, solid: FeCl
    2
    ·4H
    2
    O
    5.703
    0.000
    0.420
    0.000
    0.093
    0.000
    A
    5.244
    0.443
    0.388
    0.029
    0.086
    0.007
    A
    4.750
    0.871
    0.355
    0.057
    0.078
    0.014
    A
    4.454
    1.280
    0.331
    0.083
    0.073
    0.021
    A
    4.038
    1.829
    0.299
    0.118
    0.066
    0.030
    A
    3.679
    2.333
    0.271
    0.150
    0.060
    0.038
    A
    3.277
    2.694
    0.243
    0.174
    0.053
    0.044
    A
    3.004
    3.209
    0.219
    0.205
    0.049
    0.052
    A
    2.658
    3.578
    0.194
    0.229
    0.043
    0.058
    A
    2.122
    4.352
    0.154
    0.276
    0.034
    0.070
    A
    1.867
    5.177
    0.131
    0.317
    0.030
    0.083
    A
    1.751
    6.140
    0.117
    0.358
    0.028
    0.097
    A
    1.483
    7.425
    0.094
    0.410
    0.023
    0.115
    A
    1.508
    8.685
    0.089
    0.447
    0.023
    0.132
    A
    T = 318 K, solid: CaCl
    2
    ·4H
    2
    O
    1.169
    9.746
    0.067
    0.485
    0.018
    0.147
    C
    0.829
    10.295
    0.047
    0.509
    0.012
    0.155
    C
    0.592
    10.703
    0.033
    0.525
    0.009
    0.160
    C
    0.393
    11.034
    0.022
    0.539
    0.006
    0.165
    C
    0.217
    11.361
    0.012
    0.551
    0.003
    0.169
    C

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    Industrial & Engineering Chemistry Research

    Cite this: Ind. Eng. Chem. Res. 2024, 63, 27, 11790–11799
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.iecr.4c01190
    Published June 27, 2024
    Copyright © 2024 American Chemical Society
    Request reuse permissions

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