CN115487659A - CO fixation with calcium silicate-containing substances 2 And method for preparing calcium carbonate - Google Patents
CO fixation with calcium silicate-containing substances 2 And method for preparing calcium carbonate Download PDFInfo
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- CN115487659A CN115487659A CN202211325950.2A CN202211325950A CN115487659A CN 115487659 A CN115487659 A CN 115487659A CN 202211325950 A CN202211325950 A CN 202211325950A CN 115487659 A CN115487659 A CN 115487659A
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 92
- 238000000034 method Methods 0.000 title claims abstract description 43
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 39
- 239000000126 substance Substances 0.000 title claims description 7
- 239000000378 calcium silicate Substances 0.000 title description 4
- 229910052918 calcium silicate Inorganic materials 0.000 title description 4
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 title description 4
- 239000007788 liquid Substances 0.000 claims abstract description 137
- 238000002386 leaching Methods 0.000 claims abstract description 115
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 97
- 238000003795 desorption Methods 0.000 claims abstract description 64
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000011575 calcium Substances 0.000 claims abstract description 50
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 50
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 37
- 239000000463 material Substances 0.000 claims abstract description 35
- 238000000926 separation method Methods 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 24
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 19
- 230000033558 biomineral tissue development Effects 0.000 claims description 73
- 239000007787 solid Substances 0.000 claims description 35
- 239000000203 mixture Substances 0.000 claims description 33
- 239000013067 intermediate product Substances 0.000 claims description 24
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 17
- 239000000376 reactant Substances 0.000 claims description 14
- 239000001569 carbon dioxide Substances 0.000 claims description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 239000002893 slag Substances 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- 239000001110 calcium chloride Substances 0.000 claims description 3
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 239000007921 spray Substances 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 22
- 238000004064 recycling Methods 0.000 abstract description 6
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 abstract description 4
- 229910001424 calcium ion Inorganic materials 0.000 abstract description 4
- 230000008878 coupling Effects 0.000 abstract description 3
- 238000010168 coupling process Methods 0.000 abstract description 3
- 238000005859 coupling reaction Methods 0.000 abstract description 3
- 239000002244 precipitate Substances 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 55
- 239000000243 solution Substances 0.000 description 41
- 238000000605 extraction Methods 0.000 description 15
- 239000011777 magnesium Substances 0.000 description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 12
- 229910052749 magnesium Inorganic materials 0.000 description 12
- 239000002253 acid Substances 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 239000010456 wollastonite Substances 0.000 description 9
- 229910052882 wollastonite Inorganic materials 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 229940088417 precipitated calcium carbonate Drugs 0.000 description 8
- 238000004062 sedimentation Methods 0.000 description 7
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 6
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000003546 flue gas Substances 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 239000002910 solid waste Substances 0.000 description 5
- WYTGDNHDOZPMIW-RCBQFDQVSA-N alstonine Natural products C1=CC2=C3C=CC=CC3=NC2=C2N1C[C@H]1[C@H](C)OC=C(C(=O)OC)[C@H]1C2 WYTGDNHDOZPMIW-RCBQFDQVSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 239000012295 chemical reaction liquid Substances 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 235000019738 Limestone Nutrition 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000012527 feed solution Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 239000006028 limestone Substances 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000001089 mineralizing effect Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 150000004760 silicates Chemical class 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910004762 CaSiO Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000012163 sequencing technique Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000004846 x-ray emission Methods 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/62—Carbon oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/77—Liquid phase processes
- B01D53/78—Liquid phase processes with gas-liquid contact
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/96—Regeneration, reactivation or recycling of reactants
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
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- 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
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
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Abstract
The present disclosure provides a method for fixing CO by using calcium-containing silicate material 2 The system and the method for preparing calcium carbonate use ammonium chloride solution as a circulating extractant, and the ammonium chloride solution is used for leaching calcium ions in a calcium-containing silicate raw material in a leaching device to generate ammonia gas. The method adopts a reaction-separation coupling idea, and separates ammonia generated by reaction from a solution in a gas stripping (desorption) mode while leaching, so as to promote the reaction. Mixing the generated ammonia gas with the leaching solution containing calcium ions to obtain a mineralized solution. Will contain CO 2 Introducing gas into the mineralized solution, reacting under certain conditions to generate calcium carbonate precipitate and obtain chlorinationAmmonium solution, and ammonium chloride solution after solid-liquid separation is used as extractant for recycling.
Description
Technical Field
The disclosure belongs to the field of resource comprehensive utilization and carbon dioxide capture and utilization, and particularly relates to a method for fixing CO by using calcium-containing silicate substances 2 And a system and method for preparing calcium carbonate.
Background
Utilizes calcium and magnesium containing raw materials in the nature and industrial solid wastes and CO discharged by the industry 2 The reaction of (2) to prepare calcium carbonate can realize CO 2 The method can be used for comprehensively utilizing calcium and magnesium resources, can replace the existing industrial process for preparing precipitated calcium carbonate by decomposing limestone, and reduces the carbon emission in the process of limestone mining.
Calcium-containing materials in nature and industrial solid waste, where calcium is mainly present in the form of oxides (including hydroxides) and silicates. The former is typically carbide slag (mainly calcium oxide/calcium hydroxide), which has strong alkalinity and reactivity, and calcium and magnesium in the carbide slag are easy to extract and CO is easy to produce 2 The reaction is carried out. There have been a number of patents reporting the use of calcium oxide/calcium hydroxide-containing materials such as carbide slag with CO 2 The invention discloses a process for preparing precipitated calcium carbonate by reaction, such as Chinese invention patents CN104229852B, CN102602973B, CN1854069A and the like.
In more calcium-containing raw materials in nature and industrial solid wastes, calcium mainly exists in the form of silicate, such as olivine, serpentine and the like rich in magnesium, wollastonite rich in calcium; steel slag, coal slag, waste concrete and the like in industrial solid waste. However, due to the chemical stability of silicates, the CO emitted industrially 2 The calcium carbonate is difficult to directly react with the raw materials to obtain the calcium carbonate, and the carbonate obtained by directly reacting is mixed in the raw materials and is difficult to separate to obtain a truly valuable product.
Utilizes calcium and magnesium containing silicate raw materials in nature and industrial solid wastes and industrial discharged CO 2 The precipitated calcium carbonate is prepared by reaction, and one feasible technical route is as follows: firstly, extracting calcium and magnesium in raw materials into solution, and then discharging CO industrially 2 Introducing the calcium carbonate into the extracting solution to perform gas-liquid absorption reaction to obtain precipitated calcium carbonate. This route is also known as the "liquid phase indirect mineralization" route. There is a great deal of literature and expertiseThe calcium and magnesium components and CO in different extraction raw materials are reported 2 The specific technical scheme of the reaction. These solutions can be broadly classified into the following three types.
First, acid dissolution is used to extract calcium and magnesium components, and alkali is used to assist CO 2 Reacting with calcium and magnesium. Representative examples are CN101134155A, ding W, fu L, ouyang J, et al. (2014) CO 2 mineral acids (HCl, H) were used as reported by mineral sequencing by inorganic Chemistry, physics and Chemistry of Minerals 41 (7): 489-496 2 SO4、HNO 3 ) And organic acids (HCOOH, CH) 3 COOH) as an auxiliary agent to leach serpentine and mineralize CO under alkaline conditions 2 . Taking sulfuric acid as an example, serpentine is first leached at 70 ℃ with 2mol/L sulfuric acid, and almost all of the Mg is extracted into the leach solution, while about 65% of Fe and 3% of Si are extracted. Further adopting NaOH to adjust the pH of the solution to remove Fe in the leaching solution, and then carrying out carbonation reaction, wherein the carbonation rate of Mg reaches 94%. The main problem with this type of technical route is the consumption of excessive acid and base, for example one ton of CO per net emission reduction of the process described above 2 2-4 tons of acid (sulfuric acid) and 2.4 tons of base (sodium hydroxide) are required.
Secondly, decomposing salt to obtain acid and alkali, extracting calcium and magnesium components with acid solution, and assisting CO with alkali 2 Reacting with calcium and magnesium, and pyrolyzing the regenerated salt for recycling. Typically, the pyrolysis of hydrated magnesium chloride to hydrochloric acid and basic magnesium chloride/hydroxide as reported in patent CN104284707A, the extraction of the calcium magnesium component of the silicate with hydrochloric acid, the adjustment of the basicity of the solution with basic magnesium chloride/hydroxide for CO 2 Reaction to form carbonate. Also, as reported by the Gretta Larisa Aurora Aree Ferroufino team of Brazil space research institute, serpentine is used as a raw material, hydrochloric acid is used as a leaching agent, and ammonia water is used as a precipitator to mineralize CO 2 The obtained mineralized mother liquor is NH 4 The HCl and NH can be recovered by thermal decomposition of Cl aqueous solution and mother liquor after high-temperature evaporation, concentration and crystallization 3 . The main problems with this type of route are: the salt usually needs to be pyrolyzed or electrolyzed to prepare acid and alkali, the energy consumption is high, the pyrolysis temperature is usually higher, and the requirements on the performances of equipment corrosion prevention and the like are highAnd involve extensive solid/molten salt handling, the process is complex and difficult to engineer.
Thirdly, the recyclable solvent and the recyclable solution are adopted for extracting and dissolving calcium and magnesium components. The solvent and solution can be mixed with CO 2 And regenerating during reaction. The circulating solvent is mainly a weak acid solution with acidity higher than silicic acid but lower than carbonic acid or a solution of a strong acid weak base salt. Typically, patent CN101134155A proposes leaching calcium-containing silicate with acetic acid to obtain a calcium acetate solution, further in CO 2 Mineralizing in atmosphere to generate calcium carbonate and acetic acid, adding organic solvent such as tributyl phosphate (TBP) to extract acetic acid to promote forward mineralization reaction, and recycling the acetic acid after back extraction. Also, as reported in patents CN106745146A, CN105197975A, CN108840362A, etc., a route for extracting calcium contained in calcium silicate in steel slag by using ammonium chloride solution as circulating solution is disclosed. The process flow of the route is relatively simple, the consumption of acid and alkali is solved by using a circulating solvent and a solution, and the route has great industrial practical value, but the main problems of the prior patents and the literature reports are as follows: the extraction rate of calcium is low, and the engineering difficulty is increased by adopting microwave and other means for improving the extraction rate; with CO 2 The mineralization rate is also relatively low.
Disclosure of Invention
The purpose of the present disclosure is to overcome the defects of low calcium extraction rate and CO existing in the prior art adopting a circulation auxiliary agent technology 2 The problem of low absorption and mineralization rate, provides a method for fixing CO by using calcium-containing silicate material 2 And a system and method for preparing calcium carbonate.
In one aspect, a system provided by an embodiment of the present disclosure includes: the device comprises a leaching container, a desorption device, a mineralization reactor and a solid-liquid separation device, wherein the leaching container comprises a solid inlet, a circulating material inlet and a circulating material outlet, the desorption device comprises a material liquid inlet, a material liquid outlet, a gas inlet and a gas outlet, the mineralization reactor comprises a mineralization liquid inlet, a solid-liquid mixture outlet, a gas inlet and a gas outlet, the solid-liquid separation device comprises a solid-liquid mixture inlet, a clear liquid outlet and a solid outlet, the material liquid inlet of the desorption device is communicated with the circulating material outlet of the leaching container, the material liquid outlet of the desorption device is communicated with the circulating material inlet of the leaching container, the gas outlet of the desorption device is communicated with the gas inlet of the mineralization reactor, the mineralization liquid inlet of the mineralization reactor is communicated with the circulating material outlet of the leaching container, the solid-liquid mixture outlet of the mineralization reactor is communicated with the solid-liquid mixture inlet of the solid-liquid separation device, and the clear liquid outlet of the solid-liquid separation device are communicated with the circulating material inlet leached by the leaching container; the method comprises the following steps that a solid reactant and a circulating extracting agent respectively enter a leaching container from a solid inlet and a circulating material inlet of the leaching container and react to obtain an intermediate product containing ammonia, the solid reactant comprises a calcium-containing silicate substance, the circulating extracting agent comprises an ammonium chloride solution, a part of the intermediate product containing ammonia enters a desorption device through a circulating material outlet and a feed liquid inlet, and desorption gas enters a gas inlet of the desorption device to desorb at least part of ammonia and then enters a mineralization reactor; the desorbed intermediate product returns to the leaching container through the circulating material inlet, and the other part of the intermediate product containing ammonia enters the mineralization reactor through the circulating material outlet and the mineralization liquid inlet; and carbon dioxide gas and ammonia gas desorbed by the desorption device enter the mineralization reactor through a gas inlet of the mineralization reactor and react with an intermediate product to generate calcium carbonate, the calcium carbonate is output from the solid-liquid mixture outlet, enters the solid-liquid separation device through a solid-liquid mixture inlet of the solid-liquid separation device, is separated from the calcium carbonate and is discharged from the solid outlet, and the residual solution is discharged from the clear liquid outlet and returns to the leaching container through a circulating material inlet of the leaching container.
Optionally, the desorption gas is a gas that does not react with ammonia chloride, ammonia and calcium chloride or absorbs CO via the mineralization reactor 2 And then the purified gas is discharged through the gas outlet.
Optionally, the leach vessel further comprises a residue outlet for discharging leach residue produced by reaction of the solid reactant with the recycled extractant in the leach vessel, the leach residue comprising silica solids.
Optionally, the extraction vessel further comprises: agitating unit and baffling, baffling will the cavity longitudinal separation of leaching container becomes to leach regional and solid-liquid settlement region, agitating unit is located leach in the region, wherein, leach regional with the bottom intercommunication in solid-liquid settlement region, the sediment liquid export is located solid-liquid settlement region bottom, the circulation material export is located solid-liquid settlement region upper portion.
Optionally, the desorption apparatus comprises a bubble column, a spray column, a tray column, or a packed column.
Optionally, the mineralization reactor comprises a bubble reactor, a stirred reactor.
Optionally, the mineralization reactor comprises an airlift loop bubble reactor.
Optionally, the solid-liquid separation device comprises a settling tank, a filter, and a centrifuge.
In another aspect, the method provided by the embodiments of the present disclosure fixes CO using the system as described above 2 And preparing calcium carbonate, the method comprising: feeding a solid reactant and a recycle extractant into the leach vessel via a solids inlet and a recycle inlet of the leach vessel, respectively, such that the solid reactant and the recycle extractant react in the leach vessel to obtain an intermediate product comprising the ammonia gas; feeding a part of the intermediate product containing ammonia gas and the desorption gas into the desorption device through a feed liquid inlet and a gas inlet of the desorption device respectively so as to enable the desorption gas to desorb at least part of the ammonia gas in the part of the intermediate product and feed the part of the ammonia gas into the mineralization reactor, and simultaneously returning the desorbed part of the intermediate product to the leaching container; adding desorbed gas after ammonia gas desorption and carbon dioxide gas into the mineralization reactor through a gas inlet of the mineralization reactor, and adding another part of the intermediate product containing ammonia gas into the mineralization reactor through a mineralization liquid inlet of the mineralization reactor so as to enable the carbon dioxide gas, the ammonia gas and the part of the intermediate product to react to generate a solid-liquid mixture containing calcium carbonate; from said solid-liquid separation deviceA solid-liquid mixture inlet is used for adding the solid-liquid mixture containing the calcium carbonate into the solid-liquid separation device so as to facilitate the solid-liquid separation of the solid-liquid mixture to obtain separated calcium carbonate and a residual solution; the residual solution is discharged from the clear solution outlet and returned to the leaching vessel via the recycle inlet of the leaching vessel.
Optionally, the recycling extractant comprises ammonia chloride, ammonia and water, wherein the mass fraction of the ammonium chloride is 10-20%, and the mass fraction of the ammonia is not higher than 1%.
Optionally, the solid reactant has a particle size of 50-300 mesh.
Optionally, the mass ratio of the recycled extractant to the solid reactant is from 8.
Optionally, in the leaching vessel, the leaching temperature is 60-95 ℃.
Optionally, in the leaching vessel, the leaching time is 1-6 h.
Optionally, the ammonia-containing intermediate circulation flow in the leaching vessel and the desorption device is measured as a solution volume flow, with a circulation flow per minute of 1% to 10% of the total solution volume in the leaching vessel.
Optionally, in the mineralization reactor, the ratio of the flow rate of carbon dioxide gas to the flow rate of the intermediate product is such that: CO contained in the gas 2 The ratio of the molar flow of the mineral to the molar flow of the calcium contained in the mineralized liquid is 1.9-1.
According to the system and the method for preparing the precipitated calcium carbonate by using the calcium-containing silicate raw material, an ammonium chloride solution is used as a circulating extracting agent, and calcium ions in the calcium-containing silicate raw material are leached by the ammonium chloride solution in a leaching device to generate ammonia gas. The reaction-separation coupling concept is adopted in the method, and ammonia generated by the reaction is separated from the solution in a gas stripping (desorption) mode while leaching, so that the reaction is promoted. The generated ammonia gas is mixed with the calcium ion-containing leaching solution to obtain a mineralized solution. CO is introduced into 2 Introducing gas into the mineralized solution, reacting under certain conditions to generate calcium carbonate precipitate and obtain ammonium chloride solution again, and performing solid-liquid separation to obtain the ammonium chloride solutionCan be used as extractant for recycling.
Compared with the prior art, the process route and the method provided by the disclosure have the following advantages:
1) Utilization of calcium-containing silicate feedstock and industrial emissions of CO provided by use of the present disclosure 2 The system and the method for preparing the precipitated calcium carbonate utilize the circulating extractant containing the ammonium chloride solution to react with the calcium-containing silicate raw material, thereby not only realizing the extraction of calcium in the insoluble raw material silicate, but also avoiding the problems of equipment corrosion and acid-base consumption caused by using strong acids such as hydrochloric acid, sulfuric acid and the like.
2) In the technical process disclosed by the invention, the cyclic extractant does not need to be extracted and separated by virtue of an organic reagent, and the cyclic utilization of the cyclic extractant is realized without operations such as pyrolysis and the like, so that the process is simple and easy to amplify.
3) The leaching process disclosed by the invention adopts a reaction-separation coupling mode, and through the special design of the leaching reactor, ammonia gas generated by reaction is separated from a solution in a gas stripping (desorption) mode during leaching, so that the reaction is promoted, and the leaching rate of calcium in the calcium-containing silicate is improved.
Drawings
FIG. 1 is a schematic diagram of the system and a process flow of the present disclosure;
FIG. 2 is a schematic view of another process flow of the present disclosure;
FIG. 3 is a schematic diagram of a particular embodiment of the leaching vessel 1 according to the present disclosure.
Detailed Description
The present disclosure will be described in more detail below with reference to the accompanying drawings. Numerous specific details of the present disclosure are set forth below in order to provide a more thorough understanding of the present disclosure. However, as will be understood by those skilled in the art, the present disclosure may be practiced without these specific details.
The chemical equation involved in the embodiments of the present disclosure is as follows:
CaSiO 3 (s)+2NH 4 Cl(aq)＝CaCl 2 (aq)+SiO 2 (s)+2NH 3 ↑+H 2 o reaction 1
CaCl 2 (aq)+CO 2 (g)+2NH 3 (g)+H 2 O(l)＝CaCO 3 (s)+2NH 4 Cl (aq) reaction 2
As shown in fig. 1 and 2, the present disclosure provides a system for preparing precipitated calcium carbonate from calcium-containing silicate raw materials, comprising the following components:
a) A leaching container 1 and a desorption device 2 communicated with the leaching container 1; the leaching container 1 is provided with a solid inlet 11, circulating feed liquid inlets and outlets 12 and 13 and a slag liquid outlet 14; the desorption device 2 is provided with feed liquid inlet and outlet ports 21 and 22 and gas inlet and outlet ports 23 and 24; feed liquid inlet and outlet ports 21 and 22 are in communication with the circulating feed liquid inlet and outlet ports 12 and 13, respectively, of the leaching vessel 1, and feed liquid can circulate in the leaching vessel 1 and the desorption unit 2.
b) The mineralization reactor 3 is provided with a gas inlet 31, a mineralization liquid inlet 32, a gas outlet 33 and a solid-liquid mixture outlet 34. The mineralization liquid inlet 32 is communicated with the circulating feed liquid outlet 12 of the leaching vessel 1.
c) A solids separation device 4 having a solid-liquid mixture inlet 41, a clear liquid outlet 42 and a solids outlet 43; the solid-liquid mixture inlet 41 is communicated with the solid-liquid mixture outlet 34 of the mineralization reactor 3, and the clear liquid outlet 42 is communicated with the circulating feed liquid inlet 13 of the leaching vessel 1.
The leaching container 1 comprises a leaching area 1A containing a stirring device 16 and a solid-liquid settling area 1B, the two areas are separated by a baffling baffle 15, and a circulating material outlet 12 is positioned at the upper part of the solid-liquid settling area 1B and is used for flowing out settled clear liquid; the bottom of the solid-liquid sedimentation area 1B is communicated with the leaching area 1A, and the sedimentation magma can flow into the leaching area 1A due to gravity. In some particular embodiments, the baffle 15 takes the form of a baffle sleeve.
The desorption apparatus 2 may be a bubble column, a spray column, a tray column or a packed column. The mineralization reactor 3 can be a bubbling reactor or a stirring reactor; preferably, a bubble reactor; further preferably, it is an airlift loop bubble reactor. The solid-liquid separation device 4 can be a sedimentation tank, a filter and a centrifuge.
The embodiment of the present disclosure also provides a method for preparing precipitated calcium carbonate by using calcium-containing silicate raw materials based on the above system, which comprises a cyclic process consisting of the following steps:
step a) adding a calcium-containing silicate raw material into a leaching container 1 from a solid inlet 11 of the leaching container 1, merging a circulating extracting agent into a circulating feed liquid, flowing into the leaching container 1 from a circulating feed liquid inlet 13, and performing leaching reaction (reaction 1) under the stirring condition of a leaching area 1A; during the leaching reaction, the reaction liquid continuously passes through the sedimentation region 1B to separate solids and then flows out of the circulating liquid outlet 12, one part of the reaction liquid is cooled and then is sent to the mineralization reactor 3, and the other part of the reaction liquid flows into the desorption device 2 through the liquid inlet 21 of the desorption device 2.
Step b) introducing inert gas into the desorption device 2 through a gas inlet 23 to desorb ammonia contained in the reaction feed liquid into the inert gas; the desorbed reaction liquid returns to the leaching container 1 through the circulating liquid inlet 13 to form a circulation.
The ammonia-containing gas flowing out from the gas outlet 24 of the desorption device 2 in the step c) passes through the gas inlet 31 of the mineralization reactor 3 and the CO 2 The gas is passed into the mineralization reactor 3 together. And (3) allowing the solid-liquid mixed feed liquid containing calcium carbonate generated by the mineralization reaction (reaction 2) to flow out of the solid-liquid mixture outlet 34 to the solid-liquid separation device 4, separating to obtain a crude product of calcium carbonate, and returning clear liquid to the step a) to be used as a circulating extractant to finish the whole circulation process.
In some specific embodiments, the extractant recycled in step a) contains ammonia chloride and ammonia, wherein the mass fraction of the ammonium chloride is 10-20%, and the mass fraction of the ammonia is not higher than 1%.
The inert gas in step b) is a gas which does not react with ammonia chloride, ammonia and calcium chloride, and specifically can be air or nitrogen.
In step a), the particle size of the calcium-containing silicate raw material is 50-300 meshes.
In the step a), the mass ratio of the circulating extractant to the calcium-containing silicate raw material is 8.
In step a), the leaching temperature is 60-95 ℃, preferably 80-95 ℃.
In the step a), the leaching time is 1-6 h, preferably 2-4 h.
In steps a) and b), the circulation flow rate (in terms of a solution volume flow meter) of the feed liquid circulating in the leaching vessel 1 and the desorption unit 2 is: the circulation flow rate per minute is between 1% and 10%, preferably between 2% and 6%, of the total solution volume in the leaching vessel.
In step c), CO 2 The ratio of the gas flow to the mineralized liquid flow satisfies: CO contained in the gas 2 Flow (in CO) 2 Molar flow meter of (1) and the molar flow rate of calcium contained in the mineralized liquid is 1.
The steps further include: replenishing ammonia chloride in the circulating extractant obtained in the step c) to make up for the loss in the circulating process.
Example 2 the apparatus described in example 1 was used and the procedure is shown in FIG. 1. Wollastonite is selected as a calcium-containing silicate mineralizing raw material and ground to 100 meshes. Wollastonite was collected from Hubei von domestic area and its main composition was determined by melting X-ray fluorescence spectroscopy as shown in Table 1.
TABLE 1 wollastonite principal element composition
The wollastonite is added into a leaching container at a flow rate of 200g/h, a circulating extractant (wherein the mass fraction of the ammonia chloride is 18.4 percent and the mass fraction of the ammonia is 0.6 percent) flows into the leaching container at a flow rate of 1.8kg/h, the stirring speed is 200rpm, and a leaching temperature is maintained at 80 ℃ by an electric heater arranged on the wall surface of the leaching container 1. The feed solution in the leaching vessel 1 was circulated between the leaching vessel 1 and the desorption apparatus 2 at a flow rate of 0.5L/min. In the desorption device 2, ammonia in the feed liquid is desorbed by air, the air flow is 0.8L/min (standard state), when the extraction device is in steady state operation, the mass fraction of the ammonia in the extracting solution discharged from the extraction container 1 is 0.5%, and the ammonia desorbed into the air in the desorption device 2 accounts for 69.2% of the ammonia generated by the reaction. The total Hydraulic Retention Time (HRT) of the reaction raw materials in the leaching container 1 is 4h, the mass fraction of calcium in the extracting solution extracted from the leaching container 1 is measured to be 8.9%, and the extraction rate of calcium in wollastonite is calculated to be 52%.
The air containing ammonia and the simulated flue gas flowing out of the desorption device 2 are sent into the mineralization reactor 3 through a gas inlet 31 of the mineralization reactor 3. The mineralized liquid is fed into the mineralization reactor 3 from the mineralization liquid inlet 32 of the mineralization reactor 3. Simulation of flue gas (from CO) 2 Is mixed with air to form a mixture, wherein CO 2 15%) of the gas flow rate of 210g/h, reacted with the mineralized liquid and discharged out of the mineralization reactor 3, and CO in the effluent gas is measured 2 Calculating the content of CO 2 Has an absorption of 95.2%; discharging the mineralized solid-liquid mixture from the reactor to a filter-press filter (solid-liquid separation device 4), separating the generated calcium carbonate, and drying the filter-pressed solid in a converter (150 ℃) to obtain a calcium carbonate product (the yield is 110 g/h). The calcium carbonate obtained by analysis is vaterite type and aragonite type, the median diameter (D50) is 2.2 microns, the whiteness is 95.8, the purity is 99.5 percent, and the sedimentation volume is 2.6ml/g. The solution after filter pressing is circulated to a leaching container to be used as a circulating extractant. The loss rate of the once-circulating ammonium chloride is 3.8 percent, and the ammonium chloride needs to be supplemented in an amount of 13 g/h.
Example 3 the apparatus and wollastonite starting materials were the same as in example 1. The process flow is shown as attached figure 2, and is different from the process flow in the embodiment 1 in that: by absorbing CO with one stream 2 The purified gas is used as desorption gas. Wollastonite is added into the leaching container 1 at a flow rate of 220g/h, a circulating extractant (wherein the mass fraction of ammonia chloride is 21 percent and the mass fraction of ammonia is 0.5 percent) flows into the leaching container 1 at a flow rate of 1.8kg/h, the stirring speed is 300rpm, and the leaching temperature is maintained at 90 ℃ by an electric heater on the wall surface of the leaching container 1. Leaching the content of the container 1The liquor is circulated between the leaching vessel 1 and the desorption unit 2 at a rate of 0.7L/min. In a desorption apparatus 2 for absorbing CO 2 The purified gas was used as a desorption gas at a flow rate of 1.0L/min (standard condition). In steady state operation, the mass fraction of ammonia in the extraction liquid discharged from the leaching vessel 1 was 0.5%, and the ammonia desorbed into the gas by the desorption unit 2 accounted for 72.1% of the ammonia generated by the reaction. The total Hydraulic Retention Time (HRT) of the reaction raw materials in the leaching container 1 is 3.5h, the mass fraction of calcium in the extracting solution is measured to be 10.8%, and the extraction rate of calcium in wollastonite is calculated to be 56%.
The purified gas containing ammonia and the simulated flue gas flowing out of the desorption device 2 are sent into the mineralization reactor 3 from a gas inlet 32 of the mineralization reactor 3. The mineralized liquid is fed into the mineralization reactor 3 from the mineralization liquid inlet 32 of the mineralization reactor 3. Simulated flue gas (from CO) 2 Mixed with air to form a mixture of CO and air 2 30%) of the gas flow rate of 200g/h, reacting with the mineralized liquid, discharging the mineralized liquid out of the mineralization reactor 3, and measuring CO in the effluent gas 2 Content of (2) to calculate CO 2 Has an absorption of 93.1%; discharging the mineralized solid-liquid mixture from the reactor to a filter-press filter (solid-liquid separation device 4), separating the generated calcium carbonate, and drying the filter-pressed solid in a converter (150 ℃) to obtain a calcium carbonate product (the yield is 140 g/h). The calcium carbonate obtained by analysis is vaterite type and aragonite type, the median diameter (D50) is 2.4 microns, the whiteness is 95.8, the purity is 99.3 percent, and the sedimentation volume is 2.4ml/g. The solution after filter pressing is circulated to the leaching container 1 as a circulating extractant. The loss rate of the once-circulating ammonium chloride is 4.6 percent, and the ammonium chloride needs to be supplemented with 17 g/h.
Example 4 the apparatus and procedure were as in example 3. Concrete is selected as a mineralized material containing calcium silicate, the concrete is collected from a certain building site of Beijing, and the main components of the mineralized material are determined by melting X-ray fluorescence spectrum analysis and are shown in table 2.
TABLE 2 major elemental composition of concrete
Grinding the concrete to 100 mesh at a flow rate of 250g/hThe amount of the circulating extractant added into the leaching container 1, the mass fraction of the ammonia chloride in the circulating extractant (16 percent and the mass fraction of the ammonia in the circulating extractant 0.5 percent) flows into the leaching container 1 at a flow rate of 1.8kg/h, the stirring speed is 100rpm, and the leaching temperature is maintained at 90 ℃ by an electric heater arranged on the wall surface of the leaching container 1. The feed solution in the leaching vessel 1 was circulated between the leaching vessel 1 and the desorption apparatus 2 at a flow rate of 0.5L/min. In the desorption apparatus 2 for absorbing CO 2 The purified gas was used as a stripping gas at a flow rate of 0.6L/min (standard condition). In steady state operation, the mass fraction of ammonia in the extraction liquid discharged from the leaching vessel 1 was 0.4%, and the ammonia desorbed into the gas by the desorption unit 2 accounted for 74.1% of the ammonia generated by the reaction. The total Hydraulic Retention Time (HRT) of the reaction raw material in the leaching vessel 1 was 4h, with an extraction of calcium from the waste concrete of 61%.
The purified gas containing ammonia and the simulated flue gas flowing out of the desorption device 2 are sent into the mineralization reactor 3 from a gas inlet 31 of the mineralization reactor 3. The mineralized liquid is fed into the mineralization reactor 3 from the mineralization liquid inlet 32 of the mineralization reactor 3. Simulated flue gas (from CO) 2 Is mixed with air to form a mixture, wherein CO 2 30%) with a flow rate of 110g/h, reacted with the mineralized liquid and discharged out of the mineralization reactor 3, and the CO content in the effluent gas is determined 2 Calculating the content of CO 2 Has an absorption of 94.2%; the mineralized solution is discharged from the reactor to a filter-press type filter (solid-liquid separation device 4), the generated calcium carbonate is separated, and the solid after filter-pressing is dried by a converter (150 ℃) to obtain a calcium carbonate product (the yield is 91 g/h). The obtained calcium carbonate is analyzed to be vaterite type and aragonite type, the median diameter (D50) is 4.1 microns, the whiteness is 91.2, the purity is 95.4 percent, and the sedimentation volume is 2.6ml/g. The solution after pressure filtration is recycled to the leaching vessel 1 as a recycling extractant. The loss rate of the primary circulation ammonium chloride is 3.8 percent, and the ammonia chloride needs to be supplemented in an amount of 11 g/h.
In accordance with the disclosed embodiments, as described above, these embodiments are not exhaustive and do not limit the invention to the precise embodiments described. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the disclosure and the practical application, to thereby enable others skilled in the art to best utilize the disclosure and various modifications as are suited to the particular use contemplated.
Claims (16)
1. CO fixation by using calcium-containing silicate material 2 And a system for producing calcium carbonate, comprising: a leaching container, a desorption device, a mineralization reactor and a solid-liquid separation device,
the leaching vessel comprises a solids inlet, a recycle inlet and a recycle outlet,
the desorption device comprises a feed liquid inlet, a feed liquid outlet, a gas inlet and a gas outlet,
the mineralization reactor comprises a mineralization liquid inlet, a solid-liquid mixture outlet, a gas inlet and a gas outlet,
the solid-liquid separation device comprises a solid-liquid mixture inlet, a clear liquid outlet and a solid outlet,
the feed liquid inlet of the desorption device is communicated with the circulating material outlet of the leaching container,
the feed liquid outlet of the desorption device is communicated with the circulating material inlet of the leaching container, the gas outlet of the desorption device is communicated with the gas inlet of the mineralization reactor,
the mineralized liquid inlet of the mineralized reactor is communicated with the circulating material outlet of the leaching container, the solid-liquid mixture outlet of the mineralized reactor is communicated with the solid-liquid mixture inlet of the solid-liquid separation device,
a clear liquid outlet of the solid-liquid separation device is communicated with a circulating material inlet of the leaching container;
wherein a solid reactant and a circulating extractant respectively enter the leaching container from a solid inlet and a circulating material inlet of the leaching container and react to obtain an intermediate product containing ammonia gas, the solid reactant comprises a calcium-containing silicate substance, the circulating extractant comprises an ammonium chloride solution,
a part of the intermediate product containing ammonia enters the desorption device through the circulating material outlet and the feed liquid inlet, and desorption gas enters the gas inlet of the desorption device to desorb at least part of ammonia and then is sent to the mineralization reactor; the desorbed intermediate product is returned to the leaching container through the circulating material inlet,
the other part of the intermediate product containing ammonia gas enters the mineralization reactor through the circulating material outlet and the mineralization liquid inlet;
and carbon dioxide gas and ammonia gas desorbed by the desorption device enter the mineralization reactor through a gas inlet of the mineralization reactor and react with an intermediate product to generate calcium carbonate, the calcium carbonate is output from the solid-liquid mixture outlet, enters the solid-liquid separation device through a solid-liquid mixture inlet of the solid-liquid separation device, is separated from the calcium carbonate and is discharged from the solid outlet, and the residual solution is discharged from the clear liquid outlet and returns to the leaching container through a circulating material inlet of the leaching container.
2. The system of claim 1, wherein the desorption gas is a gas that does not react with ammonia chloride, ammonia, and calcium chloride or absorb CO via the mineralization reactor 2 And purified gas discharged from the gas outlet.
3. The system of claim 1, wherein the leach vessel further comprises a residue outlet for discharging leach residue produced by reaction of the solid reactant with the recycled extractant in the leach vessel, the leach residue comprising silica solids.
4. The system of any one of claims 1 to 3, wherein the leaching container further comprises: the cavity of the leaching container is longitudinally divided into a leaching area and a solid-liquid settling area by the baffling baffle, the stirring device is positioned in the leaching area,
the leaching area is communicated with the bottom of the solid-liquid settling area, the slag liquid outlet is positioned at the bottom of the solid-liquid settling area, and the circulating material outlet is positioned at the upper part of the solid-liquid settling area.
5. The system of claim 1, wherein the desorption device comprises a bubble column, a spray column, a tray column, or a packed column.
6. The system of claim 1, wherein the mineralization reactor comprises a bubble reactor, an agitated reactor.
7. The system of claim 6, wherein the mineralization reactor comprises an airlift loop bubble reactor.
8. The system of claim 1, wherein the solid-liquid separation device comprises a settling tank, a filter, and a centrifuge.
9. CO fixation by using calcium-containing silicate material 2 And a method for producing calcium carbonate by fixing CO using the system as claimed in any one of claims 1 to 8 2 And preparing calcium carbonate, the method comprising:
feeding a solid reactant and a recycle extractant into the leach vessel via a solids inlet and a recycle inlet of the leach vessel, respectively, such that the solid reactant and the recycle extractant react in the leach vessel to obtain an intermediate product comprising the ammonia gas;
part of the intermediate product containing ammonia gas and the desorption gas are respectively added into the desorption device through a feed liquid inlet and a gas inlet of the desorption device, so that the desorption gas desorbs at least part of the ammonia gas in the part of the intermediate product and sends the part of the ammonia gas into the mineralization reactor, and meanwhile, the part of the intermediate product after desorption is returned to the leaching container;
adding desorption gas after ammonia gas desorption and carbon dioxide gas into the mineralization reactor through a gas inlet of the mineralization reactor, and adding another part of the intermediate product containing ammonia gas into the mineralization reactor through a mineralization liquid inlet of the mineralization reactor so as to enable the carbon dioxide gas, the ammonia gas and the part of the intermediate product to react to generate a solid-liquid mixture containing calcium carbonate;
adding a solid-liquid mixture containing calcium carbonate into the solid-liquid separation device from a solid-liquid mixture inlet of the solid-liquid separation device so as to carry out solid-liquid separation on the solid-liquid mixture to obtain separated calcium carbonate and a residual solution; the residual solution is discharged from the clear solution outlet and returned to the leaching vessel via the recycle inlet of the leaching vessel.
10. The method of claim 9, wherein the recycled extractant comprises ammonia chloride, ammonia and water, wherein the mass fraction of the ammonium chloride is 10-20%, and the mass fraction of the ammonia is not higher than 1%.
11. The method of claim 9, wherein the solid reactant has a particle size of 50-300 mesh.
12. The process according to claim 9, wherein the mass ratio of the circulating extractant to the solid reactant is from 8.
13. The method according to claim 9, wherein the leaching temperature in the leaching vessel is 60-95 ℃.
14. The method according to claim 9, wherein the leaching time in the leaching vessel is between 1 and 6 hours.
15. The process according to claim 9, wherein the ammonia-containing intermediate circulation flow in the leaching vessel and the desorption device is measured as a solution volume flow, the circulation flow per minute being between 1% and 10% of the total solution volume in the leaching vessel.
16. The method according to claim 9, wherein in the mineralization reactor, the ratio of the flow rate of carbon dioxide gas to the flow rate of the intermediate product satisfies: CO contained in the gas 2 The ratio of the molar flow of the calcium to the molar flow of the calcium contained in the mineralized liquid is 1:1.1。
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