CN116253350A - Method for preparing nano calcium carbonate by carbon dioxide trapping in-situ recycling - Google Patents
Method for preparing nano calcium carbonate by carbon dioxide trapping in-situ recycling Download PDFInfo
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- CN116253350A CN116253350A CN202310298876.8A CN202310298876A CN116253350A CN 116253350 A CN116253350 A CN 116253350A CN 202310298876 A CN202310298876 A CN 202310298876A CN 116253350 A CN116253350 A CN 116253350A
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 227
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 157
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 113
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 113
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 78
- 238000000034 method Methods 0.000 title claims abstract description 67
- 238000004064 recycling Methods 0.000 title claims abstract description 38
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 24
- 230000002745 absorbent Effects 0.000 claims abstract description 81
- 239000002250 absorbent Substances 0.000 claims abstract description 81
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 60
- 239000007788 liquid Substances 0.000 claims abstract description 38
- 239000000047 product Substances 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910001868 water Inorganic materials 0.000 claims abstract description 24
- 238000001914 filtration Methods 0.000 claims abstract description 22
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 22
- 239000002244 precipitate Substances 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 230000032683 aging Effects 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 13
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 11
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 10
- 239000011575 calcium Substances 0.000 claims abstract description 10
- 239000000843 powder Substances 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 19
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 13
- 239000000292 calcium oxide Substances 0.000 claims description 13
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 13
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 9
- 239000000920 calcium hydroxide Substances 0.000 claims description 9
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 9
- 230000005587 bubbling Effects 0.000 claims description 8
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 8
- 239000000378 calcium silicate Substances 0.000 claims description 3
- 229910052918 calcium silicate Inorganic materials 0.000 claims description 3
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims description 3
- 239000000839 emulsion Substances 0.000 claims description 3
- 239000004744 fabric Substances 0.000 claims description 3
- 238000003760 magnetic stirring Methods 0.000 claims description 3
- 230000010358 mechanical oscillation Effects 0.000 claims description 3
- 238000010907 mechanical stirring Methods 0.000 claims description 3
- 238000004062 sedimentation Methods 0.000 claims description 3
- 239000006096 absorbing agent Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 23
- 238000005265 energy consumption Methods 0.000 abstract description 15
- 238000010521 absorption reaction Methods 0.000 description 19
- 235000011121 sodium hydroxide Nutrition 0.000 description 18
- 238000003795 desorption Methods 0.000 description 16
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- 239000003546 flue gas Substances 0.000 description 14
- 238000003763 carbonization Methods 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 10
- 239000013078 crystal Substances 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- 239000002245 particle Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 238000001723 curing Methods 0.000 description 5
- 239000002270 dispersing agent Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000007670 refining Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002608 ionic liquid Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000033558 biomineral tissue development Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000029087 digestion Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002918 waste heat Substances 0.000 description 2
- MIJDSYMOBYNHOT-UHFFFAOYSA-N 2-(ethylamino)ethanol Chemical compound CCNCCO MIJDSYMOBYNHOT-UHFFFAOYSA-N 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910021532 Calcite Inorganic materials 0.000 description 1
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 229930195725 Mannitol Natural products 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- -1 disubstituted imidazole amino acid Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229940088417 precipitated calcium carbonate Drugs 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 239000002912 waste gas 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
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
Abstract
The invention relates to a method for preparing nano calcium carbonate by carbon dioxide trapping in-situ recycling, which comprises the following steps: preparing an absorbent: uniformly mixing sodium hydroxide, sodium carbonate and water according to a proportion to obtain an absorbent; introducing carbon dioxide-containing gas into the absorbent, and capturing carbon dioxide to obtain rich liquid; under the condition of stirring, adding a calcium source into the rich liquid, and fully reacting to obtain a precipitate product; and (3) filtering, aging, washing and drying the precipitate to obtain a nano calcium carbonate product, and returning filtered residual liquid to the step (II) for recycling. The method has the advantages of simple production flow, low production cost, low energy consumption, controllable morphology, uniform size and high yield of the obtained nano calcium carbonate.
Description
Technical Field
The invention relates to the technical field of carbon dioxide trapping and nano calcium carbonate manufacturing, in particular to a method for preparing nano calcium carbonate by carbon dioxide trapping in-situ recycling.
Background
The chemical absorption method is an effective method for capturing carbon dioxide, and the core is to develop a high-efficiency stable carbon dioxide absorbent. At present, the processes of organic amine absorbent, ionic liquid absorbent, inorganic salt absorbent and the like are relatively mature, and the method has the advantages of high carbon dioxide absorption rate, good selectivity and the like, but the desorption process has the problems of high equipment requirement, high energy consumption and the like.
The invention patent CN104275072B reports that a chemical-physical composite absorbent traps CO 2 The absorbent rich liquid mentioned in the method needs to be heated to 80-100 ℃ for carbon dioxide desorption, collection, purification and storage and then transported to a downstream factory for a long distance, so that the effective and convenient utilization of carbon dioxide is limited. The invention patent CN101190397B reports an amine absorbent for separating carbon dioxide, which has a high absorption capacity of carbon dioxide units, so that the absorbent has extremely high absorption efficiency. This patent is of great advantage in terms of reducing the energy required to recover the absorbent, however, it requires the use of a high temperature heat source to effect separation of carbon dioxide from the absorbent. Patent CN101804287B reports an amine absorbent for capturing or separating carbon dioxide from a mixed gas, which uses N-ethylethanolamine as an active ingredient, the ingredient has high solubility for low-pressure carbon dioxide, good desorption effect, low reaction heat of absorption reaction, and good application potential. In addition, the addition of sulfolane in the absorbent plays the roles of improving desorption efficiency and reducing desorption energy consumption, but the high-temperature desorption heat energy is input by carbon dioxide, and the defect of high energy consumption limits the process popularization. The invention patent CN112551552A reports a method for preparing sodium hydroxide by using carbon dioxide, which utilizes calcium oxide and sodium sulfate solids to react with carbon dioxide gas to obtain calcium carbonate sediment and a mixed solution of calcium sulfate and sodium hydroxide, and the temperature of the mixed solution of calcium sulfate and sodium hydroxide is adjusted to gradually separate out the calcium sulfate to obtain the sodium hydroxide solution. The method realizes the absorption of carbon dioxide and simultaneously obtains the sodium hydroxide as an additional product. While this approach achieves capture of the dioxide, no efficient carbon conversion is achieved. The invention patent CN112957902A reports a system and a method for absorbing carbon dioxide in flue gas caustic soda solution of a thermal power plant, the system enables convection mixing reaction of sodium hydroxide solution and flue gas by aeration or spray atomization technology, and utilizes low-price sodium hydroxide solution to realize efficient carbon dioxide absorption, namely carbon capture, but the method needs to use a carbon dioxide collecting system to collect the carbon dioxide, and the investment of the related equipment is large。
The carbon dioxide utilization aspect is mainly used for producing chemical raw materials of products such as urea, silicon dioxide, carbon monoxide, barium carbonate, calcium carbonate and the like. The nano calcium carbonate is a medium-high end product in the calcium carbonate industry and is widely applied to the industries of plastics, coatings, printing ink, paint, rubber, papermaking, adhesives, cosmetics and the like. With the development of the nano-scale calcium carbonate technology and the popularization of the general-purpose technology, the market demand for nano-scale calcium carbonate is growing, and the yield of nano-scale calcium carbonate is also increasing. At present, the preparation process of the calcium carbonate generally needs to be subjected to the processes of digestion, refining, carbonization and the like, and a crystal form control agent, a dispersing agent, a modifying agent and the like are required to be added, so that the equipment investment is high, the production process is complex, and the energy consumption is high. The invention patent CN110510650A discloses a method for preparing nano calcium carbonate, which comprises the steps of calcining carbide slag at high temperature, introducing calcined product into water for digestion reaction, adding an auxiliary agent, a dispersing agent and a modifying agent, and preparing precipitated calcium carbonate by carbonization. The method has high energy consumption and complicated steps, in addition, auxiliary agents, dispersing agents and the like are needed, a large amount of water is needed in the production process, the production cost is high, and the economical efficiency is poor. The invention patent CN108314073A reports a preparation process of calcium carbonate, which takes calcium nitrate as a raw material, and obtains the calcium carbonate through steps of refining, carbonization and curing and solid-liquid separation. A large amount of ammonia water is needed in the refining process, so that the strong alkali environment is ensured. Ammonium bicarbonate is added in the carbonization process to carry out carbonization reaction. Secondly, mannitol, cellulose ether and polyacrylic acid with the weight ratio of 1:2:2 are required to be added as stabilizers in the curing process, so that the process is complex and the safety is poor.
The existing domestic nano calcium carbonate has wide particle size distribution, high surface energy and poor compatibility with organic high polymer, and the transparency and the dispersibility of the nano calcium carbonate are affected. Therefore, a crystal form control agent, a dispersing agent and the like are usually required to be introduced into a crystallization system, so that the nucleation, the growth rate and the particle morphology of crystals are regulated and controlled, and the nano calcium carbonate with narrow particle size distribution, relatively stable product quality and less than 100 nm is prepared. The invention patent CN115196663A reports a preparation method for controllably preparing nano calcium carbonate, which utilizes the reaction of introduced carbon dioxide gas and calcium hydroxide, takes disubstituted imidazole amino acid based ionic liquid as a main crystal form control agent, inhibits the growth rate of crystal nuclei based on the adsorption of the ionic liquid on the surface of calcium carbonate crystal, and reduces the agglomeration phenomenon, thereby obtaining nano calcium carbonate with good dispersibility. Patent CN109574057B reports a method for preparing calcium carbonate, which is carried out by carbonization and curing, and the like, and in the preparation stage of raw materials, calcined limestone and aqueous solution of acetone are mixed and added into a supercritical device with the temperature exceeding 360 ℃ and the pressure being more than 15 MPa, and the subsequent curing step also involves supercritical equipment. Although the calcium carbonate prepared by the method has high purity and good dispersibility, the method has the advantages of complex production equipment, higher equipment investment and higher energy consumption.
The industrialized production process of the nano calcium carbonate at the present stage mainly comprises the following steps: intermittent bubbling carbonization, continuous spraying multistage carbonization and supergravity reaction crystallization. The supergravity reaction crystallization method has the advantages of relatively stable product quality and relatively short carbonization time, but is difficult to apply on a large scale due to large production investment and high power consumption in production. The continuous spray multistage carbonization method has the advantages of higher production efficiency, but has the defects of poor operability in the production process, uneven particle size distribution of products, low applicability of the products and the like. The intermittent bubbling carbonization method has relatively less investment and simple operation, but has higher requirements on the concentration and pressure of the carbon dioxide in the raw material gas, and has lower utilization efficiency of the carbon dioxide.
At present, in the carbon dioxide capturing and converting, an intermittent mode is mostly adopted, namely, carbon dioxide is captured firstly, and then the carbon dioxide is desorbed and enriched and then transferred to a downstream industrial end for carbon dioxide conversion and utilization. In the desorption process, a large amount of energy input is needed, and additional production and transportation equipment is also needed for enriching and transporting the carbon dioxide, so that the production cost is greatly increased, and the large-scale application of the product is not facilitated.
In the industry of preparing nano calcium carbonate by utilizing carbon dioxide, the production process of the nano calcium carbonate generally needs steps of refining, carbonizing, curing and the like, and then, a crystal form control agent, a dispersing agent, a modifying agent and the like are added, so that the production energy consumption is high, and the process is complicated. Aiming at the problems, the invention patent CN115350581A reports a method for trapping and comprehensively utilizing carbon dioxide, which takes the flue gas after coarse purification and dust removal as a raw material, firstly traps part of carbon dioxide through a pressure swing adsorption system, and then chemically reacts the residual carbon dioxide in the discharged waste gas with calcium hydroxide to obtain nano calcium carbonate. The method has the defects of high equipment requirement and high equipment investment because the carbon dioxide is required to be concentrated by a pressure swing adsorption device, and the energy consumption of the equipment is increased in the pressure swing adsorption process. In addition, in the process of preparing nano calcium carbonate by utilizing carbon dioxide, a crystal form control agent is also used, so that the production cost is high. The invention patent CN114159936A reports a carbon dioxide trapping and utilizing and energy comprehensive utilizing process, which comprises the following steps: (1) flue gas dust removal in a dust removal device; (2) removing impurities from flue gas in the desulfurization and denitrification device; (3) cooling the flue gas in the first heat exchange device; (4) Carbon dioxide in the flue gas in the carbon trapping device is removed, and carbon trapping absorption liquid is obtained; (5) Heating the carbon trapping absorption liquid in the first heat exchange device and the second heat exchange device and desorbing the carbon trapping absorption liquid in the desorption device to obtain a mixed gas of the desorption liquid and carbon dioxide; (6) Cooling and recycling the desorption liquid in the first heat exchange device; (7) Mineralization of solid waste and carbon dioxide mixed gas in a mineralization reaction device. The method reasonably utilizes the waste heat of the flue gas, and the waste heat is collected and utilized in the desorption of the carbon dioxide through the heat exchange device, so that the energy of the flue gas is utilized to the maximum extent. However, the method still involves a desorption process of carbon dioxide, and even if the energy consumption is reduced, desorption equipment and the like are still used, so that the production steps are more and the cost is higher.
Therefore, the development of the technology integrating carbon dioxide capturing and nano calcium carbonate production with low cost, low energy consumption, simple process steps, strong operability and strong product controllability becomes a problem to be solved urgently.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for preparing nano calcium carbonate by carbon dioxide trapping in-situ recycling, which has the advantages of simple process, low cost and low energy consumption.
In order to solve the problems, the method for preparing nano calcium carbonate by carbon dioxide trapping in-situ recycling comprises the following steps:
preparing an absorbent:
sodium hydroxide, sodium carbonate and water are mixed according to the ratio of 0-20%: 0-20%: mixing 80% by mass to obtain the absorbent;
introducing carbon dioxide-containing gas into the absorbent, and capturing carbon dioxide to obtain rich liquid;
under the condition of stirring, adding a calcium source into the rich liquid, and fully reacting to obtain a precipitate product; the molar metering ratio of the addition amount of the calcium source to the captured carbon dioxide is 0.1:1-1:1;
and (3) filtering, aging, washing and drying the precipitate to obtain a nano calcium carbonate product, and returning filtered residual liquid to the step (II) for recycling.
The carbon dioxide content in the gas containing carbon dioxide in the step II is more than or equal to 400 ppm; the flow rate is 10-25 mL/min.
The trapping mode in the step is that the absorbing agent is introduced in a bubbling mode; the bubbling time is 1-12 h, and the temperature is 0-40 ℃.
The calcium source in the step III is one of calcium oxide powder or block, calcium nitrate powder or block, calcium silicate powder or block, calcium hydroxide powder or block and calcium hydroxide emulsion with the mass concentration of 10-50%.
The stirring mode in the step III refers to one of magnetic stirring, mechanical stirring or mechanical oscillation.
In the step III, the reaction temperature is 20-80 ℃ and the reaction pressure is 0.1-1 MPa; the reaction time is 0.5-24 h.
And in the step IV, the aging time is 1-48 hours.
The filtering mode in the step is one of natural sedimentation, filter cloth filtering and centrifugal filtering.
Compared with the prior art, the invention has the following advantages:
1. the absorbent can effectively capture carbon dioxide, the whole process does not need complex engineering and high-energy-consumption desorption process, and the absorbent residual liquid can be obtained by filtering the precipitated product, can be directly put into the carbon dioxide capture of the next round and can be recycled for multiple times.
2. The absorbent has the function of a crystal form control agent, can guide controllable preparation reaction of nano calcium carbonate, has good reaction effect, and can obtain the nano calcium carbonate with controllable morphology, uniform size and high yield.
3. The invention has simple production flow, low production cost, low energy consumption and wide application field range, and can realize large-scale production.
Drawings
The following describes the embodiments of the present invention in further detail with reference to the drawings.
FIG. 1 is a flow chart of the preparation of nano calcium carbonate according to the present invention.
FIG. 2 is an X-ray diffraction pattern of the chain-shaped nano calcium carbonate particles prepared in example 1 of the present invention.
FIG. 3 is a scanning electron microscope image of the chain-like nano calcium carbonate particles prepared in example 1 of the present invention.
FIG. 4 is a scanning electron microscope image of the spherical nano calcium carbonate particles prepared in example 2 of the present invention.
Detailed Description
As shown in fig. 1, a method for preparing nano calcium carbonate by carbon dioxide capturing in-situ recycling comprises the following steps:
preparing an absorbent:
sodium hydroxide, sodium carbonate and water are mixed according to the ratio of 0-20%: 0-20%: and (3) uniformly mixing 80% of the components in percentage by mass (g/g) to obtain the absorbent.
And (3) introducing carbon dioxide-containing gas with the flow rate of 10-25 mL/min into the absorbent, and capturing the carbon dioxide at the temperature of 0-40 ℃ in a capturing mode, wherein the capturing mode can be introduced into the absorbent in a bubbling mode, and the bubbling time is 1-12 h. After the trapping is completed, a rich solution is obtained.
Wherein: the carbon dioxide content of the carbon dioxide-containing gas (such as natural gas, flue gas, coal gas, air and the like) is more than or equal to 400 ppm.
Under the condition of stirring, adding a calcium source into the rich liquid, wherein the molar metering ratio of the addition amount of the calcium source to the trapped carbon dioxide is 0.1:1-1:1. And fully reacting for 0.5-24 hours at the reaction temperature of 20-80 ℃ and the reaction pressure of 0.1-1 MPa to obtain a precipitation product.
Wherein: the calcium source is one of calcium oxide powder or block, calcium nitrate powder or block, calcium silicate powder or block, and calcium hydroxide emulsion with mass concentration of 10-50%.
The stirring mode refers to one of magnetic stirring, mechanical stirring or mechanical oscillation.
And fourthly, filtering the precipitate by adopting one of natural sedimentation, filter cloth filtration and centrifugal filtration, aging for 1-48 hours, washing with water, and drying to constant weight to obtain the nano calcium carbonate product with good dispersibility. The filtered residual liquid, namely the collected absorbent, can be returned to the step for recycling without complex engineering and high-energy consumption desorption process.
Under the mild reaction condition, the rich liquid can directly carbonize calcium oxide or calcium hydroxide and dynamically drive CO 2 The method can rapidly desorb, does not need complex engineering and high-energy desorption process, and can directly control the preparation of nano calcium carbonate products. Wherein, the sodium hydroxide solution has double functions of a carbon dioxide absorption carrier and a nano calcium carbonate crystal form control agent.
The method can be customized into an intermittent production mode according to different actual production equipment, and can also be converted into a continuous production mode by adjusting corresponding proportion and parameters.
The method can be used for preparing the chain-shaped, spherical and other nano calcium carbonate with different morphologies, and particularly can be used for preparing the functional nano calcium carbonate according to different market demands.
Embodiment 1a method for preparing nano calcium carbonate by carbon dioxide capturing in-situ recycling, comprising the following steps:
preparing an absorbent:
uniformly mixing sodium hydroxide 10 g (mass percent 10%), sodium carbonate 10 g (mass percent 10%) and water 80 g (mass percent 80%) in a container to obtain the absorbent. And adding the prepared absorbent into an absorption bottle for standby.
And (3) introducing the flue gas with the flow rate of 15 mL/min (the carbon dioxide content is about 12%) into the absorbent, capturing the carbon dioxide at 40 ℃, and obtaining the absorbent rich solution enriched with the carbon dioxide after capturing.
Under the stirring condition of 800 rpm, adding 24.5 g calcium oxide powder into the rich liquid, and fully reacting at 60 ℃ and normal pressure for 4 h to obtain a precipitate product.
And (3) filtering and aging the precipitated product by using 2 h, washing with water, and drying to constant weight to obtain the nano calcium carbonate 42.8 g. The filtered residual liquid is the collected absorbent and is returned to the step for recycling.
The X-ray diffraction and scanning electron microscope test of the obtained nano calcium carbonate can be found from fig. 2 to 3: the prepared nano calcium carbonate is calcite phase and is consistent with the standard card PDF 05-0586 correspondingly. The microcosmic appearance is chain-shaped.
Example 2a method for preparing nano calcium carbonate by carbon dioxide capturing in-situ recycling comprises the following steps:
preparing an absorbent:
uniformly mixing sodium hydroxide 10 g (mass percent 10%), sodium carbonate 10 g (mass percent 10%) and water 80 g (mass percent 80%) in a container to obtain the absorbent. And adding the prepared absorbent into an absorption bottle for standby.
And (3) introducing the flue gas with the flow rate of 15 mL/min (the carbon dioxide content is about 12%) into the absorbent, capturing the carbon dioxide at 40 ℃, and obtaining the absorbent rich solution enriched with the carbon dioxide after capturing.
Under the stirring condition of 800 rpm, adding 24.5 g calcium oxide powder into the rich liquid, and fully reacting at 20 ℃ and normal pressure for 4 h to obtain a precipitate product.
And (3) filtering and aging the precipitated product by using 2 h, washing with water, and drying to constant weight to obtain the nano calcium carbonate 42.8 g. The filtered residual liquid is the collected absorbent and is returned to the step for recycling.
The scanning electron microscope test of the obtained nano calcium carbonate can be found from fig. 4: the prepared calcium carbonate is mainly spherical.
Example 3a method for preparing nano calcium carbonate by carbon dioxide capturing in-situ recycling, comprising the following steps:
preparing an absorbent:
and uniformly mixing sodium hydroxide 20 g (mass percent 20%) and water 80 g (mass percent 80%) in a container to obtain the absorbent. And adding the prepared absorbent into an absorption bottle for standby.
And (3) introducing the flue gas with the flow rate of 15 mL/min (the carbon dioxide content is about 12%) into the absorbent, capturing the carbon dioxide at 40 ℃, and obtaining the absorbent rich solution enriched with the carbon dioxide after capturing.
Under the stirring condition of 800 rpm, 28 g calcium oxide powder is added into the rich liquid, and the mixture fully reacts at 60 ℃ and normal pressure for 4 h, so as to obtain a precipitate product.
And (3) filtering and aging the precipitated product by using 2 h, washing with water, and drying to constant weight to obtain the nano calcium carbonate 50 g. The filtered residual liquid is the collected absorbent and is returned to the step for recycling.
Example 4 a method for preparing nano calcium carbonate by carbon dioxide capturing in-situ recycling, comprising the following steps:
preparing an absorbent:
and uniformly mixing 20-g% of sodium carbonate (20% by mass) and 80-g% of water (80% by mass) in a container to obtain the absorbent. And adding the prepared absorbent into an absorption bottle for standby.
And (3) introducing air with the flow rate of 15 mL/min into the absorbent, capturing carbon dioxide at 40 ℃, and obtaining the absorbent rich solution enriched with carbon dioxide after capturing.
Under the stirring condition of 800 rpm, adding 21 g calcium oxide powder into the rich liquid, and fully reacting at 60 ℃ and normal pressure for 4 h to obtain a precipitate product.
And (3) filtering and aging the precipitated product by using 2 h, washing with water, and drying to constant weight to obtain the nano calcium carbonate 37.6 g. The filtered residual liquid is the collected absorbent and is returned to the step for recycling.
Example 5 a method for preparing nano calcium carbonate by carbon dioxide capturing in-situ recycling, comprising the following steps:
preparing an absorbent:
uniformly mixing sodium hydroxide 10 g (mass percent 10%), sodium carbonate 10 g (mass percent 10%) and water 80 g (mass percent 80%) in a container to obtain the absorbent. And adding the prepared absorbent into an absorption bottle for standby.
And (3) introducing air with the flow rate of 15 mL/min into the absorbent, capturing carbon dioxide at 40 ℃, and obtaining the absorbent rich solution enriched with carbon dioxide after capturing.
Under the stirring condition of 800 rpm, adding 24.5 g calcium oxide powder into the rich liquid, and fully reacting at 60 ℃ and normal pressure for 4 h to obtain a precipitate product.
And (3) filtering and aging the precipitated product by using 2 h, washing with water, and drying to constant weight to obtain the nano calcium carbonate 42.8 g. The filtered residual liquid is the collected absorbent and is returned to the step for recycling.
Example 6a method for preparing nano calcium carbonate by carbon dioxide capture in-situ recycling, comprising the following steps:
preparing an absorbent:
uniformly mixing sodium hydroxide 10 g (mass percent 10%), sodium carbonate 10 g (mass percent 10%) and water 80 g (mass percent 80%) in a container to obtain the absorbent. And adding the prepared absorbent into an absorption bottle for standby.
And (3) introducing carbon dioxide (the carbon dioxide content is about 99.99%) with the flow rate of 15 mL/min into the absorbent, capturing the carbon dioxide at 40 ℃, and obtaining the absorbent rich solution enriched with the carbon dioxide after the capturing is finished.
Under the stirring condition of 800 rpm, adding 24.5 g calcium oxide powder into the rich liquid, and fully reacting at 60 ℃ and normal pressure for 4 h to obtain a precipitate product.
And (3) filtering and aging the precipitated product by using 2 h, washing with water, and drying to constant weight to obtain the nano calcium carbonate 42.8 g. The filtered residual liquid is the collected absorbent and is returned to the step for recycling.
Example 7 a method for preparing nano calcium carbonate by carbon dioxide capture in-situ recycling, comprising the following steps:
preparing an absorbent:
uniformly mixing sodium hydroxide 10 g (mass percent 10%), sodium carbonate 10 g (mass percent 10%) and water 80 g (mass percent 80%) in a container to obtain the absorbent. And adding the prepared absorbent into an absorption bottle for standby.
And (3) introducing the flue gas with the flow rate of 15 mL/min (the carbon dioxide content is about 12%) into the absorbent, capturing the carbon dioxide at 40 ℃, and obtaining the absorbent rich solution enriched with the carbon dioxide after capturing.
Under the stirring condition of 800 rpm, 32.4-g calcium hydroxide powder is added into the rich liquid, and the mixture fully reacts at 60 ℃ and normal pressure for 4-h, so as to obtain a precipitate product.
And (3) filtering and aging the precipitated product by using 2 h, washing with water, and drying to constant weight to obtain the nano calcium carbonate 42.8 g. The filtered residual liquid is the collected absorbent and is returned to the step for recycling.
Example 8 a method for preparing nano calcium carbonate by carbon dioxide capture in-situ recycling, comprising the following steps:
preparing an absorbent:
and uniformly mixing sodium hydroxide 100 g (mass percent is 10%), sodium carbonate 100 g (mass percent is 10%) and water 800 g (mass percent is 80%) in a container to obtain the absorbent. And adding the prepared absorbent into an absorption bottle for standby.
And (3) introducing carbon dioxide (the carbon dioxide content is about 99.99%) with the flow rate of 15 mL/min into the absorbent, capturing the carbon dioxide at 40 ℃, and obtaining the absorbent rich solution enriched with the carbon dioxide after the capturing is finished.
Under the stirring condition of 800 rpm, 245 g calcium oxide powder is added into the rich liquid, and the mixture fully reacts at 60 ℃ and normal pressure for 4 h, so as to obtain a precipitate product.
And (3) filtering and aging the precipitated product by using 2 h, washing with water, and drying to constant weight to obtain the nano calcium carbonate 428 g. The filtered residual liquid is the collected absorbent and is returned to the step for recycling.
Example 9 a method for preparing nano calcium carbonate by carbon dioxide capturing in-situ recycling, comprising the following steps:
the carbon dioxide absorbent recycled in example 7.
And (3) introducing carbon dioxide (the carbon dioxide content is about 99.99%) with the flow rate of 15 mL/min into the absorbent, capturing the carbon dioxide at 40 ℃, and obtaining the absorbent rich solution enriched with the carbon dioxide after the capturing is finished.
Under the stirring condition of 800 rpm, 245 g calcium oxide powder is added into the rich liquid, and the mixture fully reacts at 60 ℃ and normal pressure for 4 h, so as to obtain a precipitate product.
And (3) filtering and aging the precipitated product by using 2 h, washing with water, and drying to constant weight to obtain the nano calcium carbonate 428 g. The filtered residual liquid is the collected absorbent and is returned to the step for recycling.
Claims (8)
1. A method for preparing nano calcium carbonate by carbon dioxide trapping in-situ recycling comprises the following steps:
preparing an absorbent:
sodium hydroxide, sodium carbonate and water are mixed according to the ratio of 0-20%: 0-20%: mixing 80% by mass to obtain the absorbent;
introducing carbon dioxide-containing gas into the absorbent, and capturing carbon dioxide to obtain rich liquid;
under the condition of stirring, adding a calcium source into the rich liquid, and fully reacting to obtain a precipitate product; the molar metering ratio of the addition amount of the calcium source to the captured carbon dioxide is 0.1:1-1:1;
and (3) filtering, aging, washing and drying the precipitate to obtain a nano calcium carbonate product, and returning filtered residual liquid to the step (II) for recycling.
2. The method for preparing nano calcium carbonate by carbon dioxide capturing in-situ recycling according to claim 1, which is characterized by comprising the following steps: the carbon dioxide content in the gas containing carbon dioxide in the step II is more than or equal to 400 ppm; the flow rate is 10-25 mL/min.
3. The method for preparing nano calcium carbonate by carbon dioxide capturing in-situ recycling according to claim 1, which is characterized by comprising the following steps: the trapping mode in the step is that the absorbing agent is introduced in a bubbling mode; the bubbling time is 1-12 h, and the temperature is 0-40 ℃.
4. The method for preparing nano calcium carbonate by carbon dioxide capturing in-situ recycling according to claim 1, which is characterized by comprising the following steps: the calcium source in the step III is one of calcium oxide powder or block, calcium nitrate powder or block, calcium silicate powder or block, calcium hydroxide powder or block and calcium hydroxide emulsion with the mass concentration of 10-50%.
5. The method for preparing nano calcium carbonate by carbon dioxide capturing in-situ recycling according to claim 1, which is characterized by comprising the following steps: the stirring mode in the step III refers to one of magnetic stirring, mechanical stirring or mechanical oscillation.
6. The method for preparing nano calcium carbonate by carbon dioxide capturing in-situ recycling according to claim 1, which is characterized by comprising the following steps: in the step III, the reaction temperature is 20-80 ℃ and the reaction pressure is 0.1-1 MPa; the reaction time is 0.5-24 h.
7. The method for preparing nano calcium carbonate by carbon dioxide capturing in-situ recycling according to claim 1, which is characterized by comprising the following steps: and in the step IV, the aging time is 1-48 hours.
8. The method for preparing nano calcium carbonate by carbon dioxide capturing in-situ recycling according to claim 1, which is characterized by comprising the following steps: the filtering mode in the step is one of natural sedimentation, filter cloth filtering and centrifugal filtering.
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| US20060165583A1 (en) * | 2003-02-27 | 2006-07-27 | Okutama Kogyo Co., Ltd. | Spherical calcium carbonate and method for producing thereof |
| CN101967001A (en) * | 2010-09-26 | 2011-02-09 | 河北科技大学 | Method for producing calcium carbonate by using calcium carbide slag and low concentration carbon dioxide-containing waste gas as raw materials |
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| WO2022145380A1 (en) * | 2020-12-28 | 2022-07-07 | 白石工業株式会社 | Method for producing calcium carbonate, and calcium carbonate |
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| US20060165583A1 (en) * | 2003-02-27 | 2006-07-27 | Okutama Kogyo Co., Ltd. | Spherical calcium carbonate and method for producing thereof |
| CN101967001A (en) * | 2010-09-26 | 2011-02-09 | 河北科技大学 | Method for producing calcium carbonate by using calcium carbide slag and low concentration carbon dioxide-containing waste gas as raw materials |
| KR101568616B1 (en) * | 2014-12-03 | 2015-11-12 | 연세대학교 산학협력단 | Method of absorbent recycle in carbon fixation through inorganic carbonation using industrial waste |
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Effective date of registration: 20240407 Address after: 256200 Sun Zhen Shi Jia Cun Nan, Zouping City, Binzhou City, Shandong Province Applicant after: Zouping Shengchang calcium Industry Co.,Ltd. Country or region after: China Address before: 730000 No. 18 Tianshui Middle Road, Chengguan District, Gansu, Lanzhou Applicant before: Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences Country or region before: China |