CN117902607A - Comprehensive utilization of calcium chloride solution and CO2Is a method of (2) - Google Patents
Comprehensive utilization of calcium chloride solution and CO2Is a method of (2) Download PDFInfo
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- CN117902607A CN117902607A CN202410062063.3A CN202410062063A CN117902607A CN 117902607 A CN117902607 A CN 117902607A CN 202410062063 A CN202410062063 A CN 202410062063A CN 117902607 A CN117902607 A CN 117902607A
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- water
- calcium carbonate
- soluble amine
- calcium chloride
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- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 title claims abstract description 85
- 238000000034 method Methods 0.000 title claims abstract description 59
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 235
- 150000001412 amines Chemical class 0.000 claims abstract description 113
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 112
- 238000006243 chemical reaction Methods 0.000 claims abstract description 70
- 239000000047 product Substances 0.000 claims abstract description 67
- 239000001110 calcium chloride Substances 0.000 claims abstract description 58
- 229910001628 calcium chloride Inorganic materials 0.000 claims abstract description 58
- 239000007788 liquid Substances 0.000 claims abstract description 55
- 239000002699 waste material Substances 0.000 claims abstract description 54
- 230000033558 biomineral tissue development Effects 0.000 claims abstract description 53
- -1 amine hydrochloride Chemical class 0.000 claims abstract description 51
- 239000012528 membrane Substances 0.000 claims abstract description 42
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000000909 electrodialysis Methods 0.000 claims abstract description 33
- 230000008569 process Effects 0.000 claims abstract description 29
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003546 flue gas Substances 0.000 claims abstract description 17
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 239000006227 byproduct Substances 0.000 claims abstract description 6
- 239000007791 liquid phase Substances 0.000 claims abstract description 6
- 230000001172 regenerating effect Effects 0.000 claims abstract description 5
- 150000003839 salts Chemical class 0.000 claims description 25
- 239000002253 acid Substances 0.000 claims description 23
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 16
- 229910021532 Calcite Inorganic materials 0.000 claims description 14
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 7
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 229940058020 2-amino-2-methyl-1-propanol Drugs 0.000 claims description 6
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 6
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 6
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 claims description 6
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 5
- WUWHFEHKUQVYLF-UHFFFAOYSA-M sodium;2-aminoacetate Chemical compound [Na+].NCC([O-])=O WUWHFEHKUQVYLF-UHFFFAOYSA-M 0.000 claims description 5
- DHMQDGOQFOQNFH-UHFFFAOYSA-M Aminoacetate Chemical compound NCC([O-])=O DHMQDGOQFOQNFH-UHFFFAOYSA-M 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 4
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 claims description 4
- 235000013905 glycine and its sodium salt Nutrition 0.000 claims description 4
- 239000004247 glycine and its sodium salt Substances 0.000 claims description 4
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- 229940029258 sodium glycinate Drugs 0.000 claims description 4
- ATHGHQPFGPMSJY-UHFFFAOYSA-N spermidine Chemical compound NCCCCNCCCN ATHGHQPFGPMSJY-UHFFFAOYSA-N 0.000 claims description 4
- PFNFFQXMRSDOHW-UHFFFAOYSA-N spermine Chemical compound NCCCNCCCCNCCCN PFNFFQXMRSDOHW-UHFFFAOYSA-N 0.000 claims description 4
- 239000004475 Arginine Substances 0.000 claims description 3
- 238000009621 Solvay process Methods 0.000 claims description 3
- ODKSFYDXXFIFQN-UHFFFAOYSA-N arginine Natural products OC(=O)C(N)CCCNC(N)=N ODKSFYDXXFIFQN-UHFFFAOYSA-N 0.000 claims description 3
- 239000002367 phosphate rock Substances 0.000 claims description 3
- 229910021420 polycrystalline silicon Inorganic materials 0.000 claims description 3
- 229920005591 polysilicon Polymers 0.000 claims description 3
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 2
- 239000005700 Putrescine Substances 0.000 claims description 2
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 2
- 230000000035 biogenic effect Effects 0.000 claims description 2
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 claims description 2
- 238000003763 carbonization Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 235000019700 dicalcium phosphate Nutrition 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- 239000004571 lime Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229920000768 polyamine Polymers 0.000 claims description 2
- 229940063673 spermidine Drugs 0.000 claims description 2
- 229940063675 spermine Drugs 0.000 claims description 2
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 claims description 2
- 229960001124 trientine Drugs 0.000 claims description 2
- 150000004985 diamines Chemical class 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 9
- 239000000460 chlorine Substances 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052801 chlorine Inorganic materials 0.000 abstract description 6
- 238000004064 recycling Methods 0.000 abstract description 5
- 230000009467 reduction Effects 0.000 abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052799 carbon Inorganic materials 0.000 abstract description 4
- 230000001089 mineralizing effect Effects 0.000 abstract description 4
- 239000002105 nanoparticle Substances 0.000 abstract description 4
- 238000002425 crystallisation Methods 0.000 abstract description 2
- 230000008025 crystallization Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 49
- 239000007789 gas Substances 0.000 description 13
- 230000001276 controlling effect Effects 0.000 description 9
- 230000008929 regeneration Effects 0.000 description 9
- 238000011069 regeneration method Methods 0.000 description 9
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 230000001105 regulatory effect Effects 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000003011 anion exchange membrane Substances 0.000 description 5
- 238000001000 micrograph Methods 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- 238000005341 cation exchange Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 229940031098 ethanolamine Drugs 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 238000000643 oven drying Methods 0.000 description 3
- 238000004626 scanning electron microscopy Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 229910001868 water Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- MSQACBWWAIBWIC-UHFFFAOYSA-N hydron;piperazine;chloride Chemical compound Cl.C1CNCCN1 MSQACBWWAIBWIC-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 229960004418 trolamine Drugs 0.000 description 2
- PMZIUAOBHNJYQT-UHFFFAOYSA-N (1-hydroxy-2-methylpropan-2-yl)azanium;chloride Chemical compound Cl.CC(C)(N)CO PMZIUAOBHNJYQT-UHFFFAOYSA-N 0.000 description 1
- PMUNIMVZCACZBB-UHFFFAOYSA-N 2-hydroxyethylazanium;chloride Chemical compound Cl.NCCO PMUNIMVZCACZBB-UHFFFAOYSA-N 0.000 description 1
- GJMPSRSMBJLKKB-UHFFFAOYSA-N 3-methylphenylacetic acid Chemical compound CC1=CC=CC(CC(O)=O)=C1 GJMPSRSMBJLKKB-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- CMPOVQUVPYXEBN-UHFFFAOYSA-N bis(2-hydroxyethyl)-methylazanium;chloride Chemical compound Cl.OCCN(C)CCO CMPOVQUVPYXEBN-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229940073579 ethanolamine hydrochloride Drugs 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 229940117957 triethanolamine hydrochloride Drugs 0.000 description 1
Landscapes
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention provides a method for comprehensively utilizing calcium chloride solution and CO 2, which takes the calcium chloride solution and CO 2 as raw materials, adds water-soluble amine as an auxiliary agent to promote mineralization reaction to occur, and obtains micron-sized or nano-sized high-value calcium carbonate and water-soluble amine hydrochloride solution with controllable morphology and granularity through reaction crystallization; in order to further realize the recycling of chlorine, the separated liquid phase after the reaction is finished is regenerated into water-soluble amine through bipolar membrane electrodialysis, and dilute hydrochloric acid is produced as a byproduct. The method provides a brand new thought and method for comprehensively utilizing the calcium chloride waste liquid and the flue gas CO 2, has excellent effects of mineralizing the water-soluble amine and regenerating the amine by bipolar membrane electrodialysis, has remarkable advantages compared with the existing method, prepares the high-value calcium carbonate product and dilute hydrochloric acid, has no waste emission in the whole process, has good application prospect, and has important significance in the fields of calcium chloride waste liquid treatment and carbon emission reduction.
Description
Technical Field
The invention belongs to the technical field of industrial waste resource utilization and carbon dioxide mineralization, and in particular relates to a method for comprehensively utilizing calcium chloride waste liquid and flue gas CO 2 to obtain a calcium carbonate product and dilute hydrochloric acid.
Background
The industries of producing sodium carbonate by an ammonia-soda process, producing calcium hydrophosphate by extracting phosphate rock powder by hydrochloric acid, producing potassium chlorate, producing polysilicon and the like all discharge a large amount of waste liquid containing calcium chloride, and the mass fraction of the waste liquid is generally 3-10%. At present, most enterprises except for concentrating and evaporating the calcium chloride to prepare solid calcium chloride have the traditional treatment mode that the calcium chloride is settled and clarified by standing and then is directly discharged into rivers, lakes and seas, so that the environment is greatly damaged and huge waste of resources is caused. So far, no good way is available for treating the calcium chloride waste liquid, and the treatment problem becomes an industry common technical problem.
Meanwhile, the climate of the world is changed drastically, and the emission reduction of CO 2 is not slow. 43% of the CO 2 emitted by human activities is generated by power generation and energy supply of coal-fired power plants, and most chemical production parks are equipped with power plants, and the emitted CO 2 is usually directly emitted after desulfurization and denitrification, so that the greenhouse effect is increased. If the calcium chloride waste liquid discharged by a factory and the CO 2 in the flue gas of a power plant are comprehensively utilized, a product with higher value is produced, and the product with high added value can be obtained while the two wastes are comprehensively utilized, so that the method has multiple benefits such as economic benefit, environmental benefit and social benefit.
At present, a plurality of scholars have conducted research reports on comprehensive utilization of calcium chloride waste liquid and CO 2, and CN113104876A discloses a method for converting calcium chloride and CO 2 into calcium carbonate and oil-soluble amine hydrochloride by adopting a reaction extraction crystallization mode, filtering in a water phase to obtain a calcium carbonate product, regenerating the oil-soluble amine hydrochloride in the oil phase into the oil-soluble amine by adopting a heating desorption mode, recycling and producing HCl gas as a byproduct. However, the method has the advantages that due to the high viscosity of the used oil-soluble amine, a large amount of diluent is needed to be added in the mineralization and pyrolysis processes, the diluent is needed to be further separated in the subsequent process, the energy consumption is high, and the separation is difficult. In addition, because N 2 is introduced in the pyrolysis process to bring out the generated HCl gas as soon as possible, the subsequent obtained HCl gas is mixed with N 2, and is difficult to separate, and high-value high-purity HCl gas cannot be obtained.
Therefore, research on a more feasible method for comprehensively treating the calcium chloride waste liquid and the flue gas CO 2 has important significance in the aspects of calcium chloride waste liquid treatment and carbon emission reduction.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a method for comprehensively utilizing calcium chloride waste liquid and flue gas CO 2 to obtain a calcium carbonate product and dilute hydrochloric acid. In the process, water-soluble amine is used as an auxiliary agent to promote mineralization reaction to generate calcium carbonate and water-soluble amine hydrochloride, then to further obtain chlorine-containing recycling products, chlorine-containing waste liquid is not generated, the water-soluble amine hydrochloride is regenerated by adopting a bipolar membrane electrodialysis mode, the water-soluble amine hydrochloride is regenerated into water-soluble amine and byproducts of dilute hydrochloric acid, the water-soluble amine is recycled to a mineralization section for recycling, and the dilute hydrochloric acid is used for other workshops of a factory. Compared with the existing oil-soluble amine process, the process is simpler, has lower energy consumption and has remarkable advantages.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
A method for comprehensively utilizing a calcium chloride solution and CO 2, the method comprising:
(1) Mineralization: taking a calcium chloride solution and CO 2 as raw materials, adding water-soluble amine as an auxiliary agent to promote mineralization reaction to generate calcium carbonate and water-soluble amine hydrochloride, and carrying out solid-liquid separation to obtain a calcium carbonate product;
(2) Regeneration: the separated liquid phase is regenerated into water-soluble amine through bipolar membrane electrodialysis, and the byproduct dilute hydrochloric acid is recycled back to the mineralization process of the step (1) for reuse, and the dilute hydrochloric acid can be used in other production workshops of factories.
The invention is further provided that the calcium chloride solution is industrial calcium chloride waste liquid, and is calcium chloride waste liquid discharged from industries such as soda ash production by an ammonia-soda process, calcium hydrogen phosphate production by extracting phosphate rock powder with hydrochloric acid, potassium chlorate production or polysilicon production. The concentration of calcium chloride in the calcium chloride solution is 0.1-3 mol/L.
The invention further provides that the CO 2 is flue gas CO 2, and CO 2 is discharged from power plants, lime kilns, carbonization towers and the like.
The invention further provides that the concentration of CO 2 in the flue gas CO 2 is 2% -100%.
The invention is further arranged that the flue gas CO 2 is introduced into a reaction solution system after being subjected to compression treatment or after not being subjected to compression treatment after desulfurization and denitrification. The pressure of the compressed CO 2 is up to 0.8MPa.
The invention further provides that the feeding mode of the CO 2 can be selected as follows: firstly, introducing water-soluble amine solution, and then mixing with calcium chloride waste liquid to carry out mineralization reaction; or introducing the calcium chloride waste liquid into the water-soluble amine solution to be mixed for mineralization reaction; or introducing the mixture of the water-soluble amine solution and the calcium chloride waste liquid to carry out mineralization reaction. The first two feeding modes are that CO 2 is absorbed firstly and then mineralization reaction is carried out, and the last feeding mode is that CO 2 is absorbed and mineralization reaction occurs simultaneously.
The invention further provides that the calcium chloride solution and the water-soluble amine solution are mixed in a manner of direct pouring and mixing or dropwise adding and mixing, and the dropwise adding rate is at least 0.0001ml/min.
The invention is further arranged that the mineralization reaction temperature is 10-80 ℃; the ratio of the amount of the substances of the calcium chloride and the water-soluble amine is 1: (0.4 to 10), preferably 1: (1-4).
The water-soluble amine is one or more selected from water-soluble alcohol amine compounds, amino acid salt compounds, basic amino acid compounds, diamine compounds, polyamine compounds, aliphatic amine compounds, aromatic amine compounds, heterocyclic amine compounds, biogenic amine compounds and the like.
Specifically, the water-soluble amine is one or more selected from ethanolamine (MEA), diethanolamine (DEA), triethanolamine (TEA), N-Methyldiethanolamine (MDEA), 2-amino-2-methyl-1-propanol (AMP), sodium glycinate (GlyNa), arginine (Arg), piperazine (PZ), ethylenediamine (EDA), tetramethyl ethylenediamine (TEMED), triethylene tetramine (TETA), pyridine (PD), cadaverine, putrescine, spermine, spermidine, and the like.
The invention adopts the various water-soluble amines as the auxiliary agents, and can mineralize and react to obtain the calcium carbonate product. However, due to the difference of the group structures of different water-soluble amines, the property difference of the water-soluble amine auxiliary agent as an auxiliary agent is obvious, and the specific type selection and targeted process control of the water-soluble amine auxiliary agent are important in order to obtain a micron-sized or nano-sized calcium carbonate product with high added value and controllable morphology and granularity. For calcium carbonate products, there are three common crystalline forms: aragonite, vaterite, calcite, vaterite-type calcium carbonate often exists in the form of spherical aggregates, calcite-type calcium carbonate often exists in the form of regular rhombohedra, and aragonite-type calcium carbonate is prone to form needle-like forms. The calcium carbonate products with different crystal forms are suitable for different application fields. If the process is improperly regulated and controlled, the calcium carbonate product with the existing polymorphism is easy to prepare, and the morphology is mixed, so that the high-value utilization of the calcium carbonate product is not facilitated. In order to obtain the calcium carbonate product with controllable morphology and granularity and high added value, the mineralization reaction process needs to be further regulated and controlled.
When the water-soluble amine is selected from diamine compounds, namely one or more of Piperazine (PZ), ethylenediamine (EDA), tetramethyl ethylenediamine (TEMED) and the like, the calcium carbonate product prepared in the step (1) is calcite type calcium carbonate with controllable morphology.
When the water-soluble amine is selected from amino acid salt compounds and basic amino acid compounds, namely one or more of sodium glycinate (GlyNa), arginine (Arg) and the like, the calcium carbonate product prepared in the step (1) is vaterite type calcium carbonate with controllable morphology.
When the water-soluble amine is selected from alcohol amine compounds, namely one or More of Ethanolamine (MEA), diethanolamine (DEA), triethanolamine (TEA), N-Methyldiethanolamine (MDEA), 2-amino-2-methyl-1-propanol (AMP) and the like, the mineralization process needs to be further regulated and controlled:
When mineralizing, the ratio of the amount of calcium chloride to the amount of water-soluble amine material is greater than 1:2, namely when the calcium chloride is excessively added, the calcium carbonate product prepared in the step (1) is calcite type calcium carbonate with controllable morphology. The ratio of the amount of calcium chloride to the amount of water-soluble amine material is preferably 1: (0.4-2) or 1: (1-2), none of which includes 1:2.
When the water-soluble amine solution is added into the calcium chloride solution in the mineralization reaction, the feeding mode can be further regulated and controlled according to the feeding mode of CO 2:
CO 2 absorption and mineralization reaction occur simultaneously, namely CO 2 is introduced into a mixed solution of a water-soluble amine solution and a calcium chloride solution to perform mineralization reaction, and the calcium carbonate product prepared in the step (1) is polymorphic calcium carbonate with mixed morphology;
CO 2 is absorbed firstly and then mineralized, namely CO 2 is introduced into a water-soluble amine solution and then mixed with calcium chloride waste liquid, or is introduced into the calcium chloride waste liquid and then mixed with the water-soluble amine solution, and the calcium carbonate product prepared in the step (1) is calcite type calcium carbonate with controllable morphology.
When mineralizing, the ratio of the amount of calcium chloride to the amount of water-soluble amine material is not greater than 1:2, when the calcium chloride solution is added into the water-soluble amine solution, the feeding mode can be further regulated according to the feeding mode of CO 2 and the mineralization reaction temperature:
CO 2 absorption and mineralization reaction occur simultaneously, namely CO 2 is introduced into a mixed solution of a water-soluble amine solution and a calcium chloride solution to perform mineralization reaction, and the calcium carbonate product prepared in the step (1) is polymorphic calcium carbonate with mixed morphology;
CO 2 is firstly absorbed and then mineralized, namely CO 2 is firstly introduced into a water-soluble amine solution and then mixed with calcium chloride waste liquid, or when the CO 2 is firstly introduced into the calcium chloride waste liquid and then mixed with the water-soluble amine solution, the calcium carbonate product prepared by the low-temperature mineralization reaction is vaterite type calcium carbonate with controllable morphology, the mineralization reaction temperature is preferably 10-40 ℃, and more preferably 20-30 ℃; the calcium carbonate product prepared by the high-temperature mineralization reaction is calcite type calcium carbonate with controllable morphology, and the mineralization reaction temperature is preferably 50-80 ℃, more preferably 60-70 ℃.
For the granularity of the calcium carbonate product, the mixing mode of the calcium chloride solution and the water-soluble amine solution (namely, direct pouring mixing or dropwise adding mixing) and the concentration of the raw material solution are important, and the slower the dripping speed is, the lower the concentration of the raw material solution is, the larger the granularity of the calcium carbonate is; the faster the dropping speed, the higher the concentration of the raw material solution, and the smaller the particle size of the calcium carbonate.
When the mixing mode of the calcium chloride solution and the water-soluble amine solution is direct pouring and mixing, the calcium carbonate product prepared in the step (1) is small-particle-size calcium carbonate, and the average particle size of the calcium carbonate product is specifically smaller than 20 microns, preferably smaller than 10 microns, and more preferably 2-10 microns; when the calcium chloride solution and the water-soluble amine solution are mixed in a dropwise manner, the calcium carbonate product prepared in the step (1) is large-particle-size calcium carbonate, and the average particle size thereof is specifically more than 10 μm, preferably more than 20 μm, and more preferably 20 to 30 μm.
The invention is further provided that the calcium carbonate product is obtained by filtering after the mineralization reaction is finished, the liquid phase water-soluble amine hydrochloride solution is regenerated and recycled by a bipolar membrane electrodialysis mode, and the dilute hydrochloric acid is a byproduct.
Furthermore, the bipolar membrane electrodialysis device adopts a three-compartment structure of a salt chamber, an acid chamber and an alkali chamber, which is formed by interlacing and combining bipolar membranes, cation exchange membranes and anion exchange membranes, or a two-compartment structure of a salt chamber, an acid chamber, which is formed by interlacing and combining bipolar membranes and anion exchange membranes.
For a bipolar membrane electrodialysis process of a three-compartment structure of a salt chamber, an acid chamber and a base chamber, after direct current is conducted to two sides of a bipolar membrane electrodialysis membrane stack, H 2 O is electrolyzed into H + and OH-in an intermediate catalytic layer of a bipolar membrane, H + migrates to a cathode through a cation exchange membrane and enters the acid chamber, and Cl - in the salt chamber also enters the acid chamber through an anion exchange membrane, so that HCl is generated in the acid chamber; OH - migrates to the anode through the anion exchange membrane and enters the base compartment where the protic amine in the salt compartment also enters the base compartment through the cation exchange membrane, thereby regenerating into a water soluble amine. For the bipolar membrane electrodialysis process of a two-compartment structure of a salt chamber and an acid chamber, after direct current is conducted to two sides of a bipolar membrane electrodialysis membrane stack, H 2 O is electrolyzed into H + and OH - in an intermediate catalytic layer of the bipolar membrane, OH < - > is generated on one side of the salt chamber, H + is generated on one side of the acid chamber, cl - in the salt chamber enters the acid chamber through an anion exchange membrane, HCl is generated by combining the acid chamber with H +, OH - is combined with proton amine trapped in the salt chamber, and water-soluble amine is regenerated in the salt chamber. The bipolar membrane electrodialysis technology can obtain dilute hydrochloric acid and regenerated water-soluble amine solution in an acid chamber and an alkali chamber (or a salt chamber) at the same time.
The bipolar membrane electrodialysis device is further characterized in that when the bipolar membrane electrodialysis device starts to operate, an acid chamber is 0.01-2.00 mol/L of HCl solution, an alkali chamber is 0.01-2.00 mol/L of NaOH solution, a salt chamber is liquid-phase water-soluble amine hydrochloride solution after solid-liquid separation, and an polar liquid chamber is 0.01-10% of Na 2SO4 solution.
The invention further provides that the flow rate of each compartment of the bipolar membrane electrodialysis is preferably 10-200L/h. The intensity of the constant current applied is preferably 0.1 to 5.0A.
Compared with the prior art, the invention has the beneficial effects that:
The invention provides a method for comprehensively utilizing calcium chloride waste liquid and flue gas CO 2, under the condition of adding water-soluble amine as an auxiliary agent, the mineralization reaction is optimized and regulated by a process to obtain a micron-sized or nano-sized calcium carbonate product with controllable morphology and granularity, and the mineralization rate can reach 99% or more; in order to further fully utilize chlorine resources and regenerate water-soluble amine, a bipolar membrane electrodialysis mode is adopted, the amine regeneration rate can reach 90% or more, regenerated and recyclable water-soluble amine is obtained in a salt chamber or an alkali chamber, and dilute hydrochloric acid is obtained in an acid chamber for other workshops of a factory. Compared with the existing oil-soluble amine process, the process flow is simpler, the energy consumption cost is lower, and the mineralization and amine regeneration effects are more excellent.
The invention converts the calcium chloride waste liquid and the flue gas CO 2 into high-value calcium carbonate products and dilute hydrochloric acid by adopting a brand new mode of mineralizing CO 2 by water-soluble amine and regenerating amine by bipolar membrane electrodialysis, thereby realizing the comprehensive utilization of the two wastes, obtaining the products with high added value, assisting carbon emission reduction, and having no waste emission in the whole process, and having remarkable advantages compared with the prior art.
Drawings
FIG. 1 is a process flow diagram of the invention for the integrated utilization of calcium chloride waste liquid and flue gas CO 2;
FIG. 2 is an XRD pattern of the calcium carbonate product prepared in example 1-1;
FIG. 3 is a scanning electron microscope image of the calcium carbonate product prepared in example 1-1;
FIG. 4 is an XRD pattern of the calcium carbonate product prepared in example 2-1;
FIG. 5 is a scanning electron microscope image of the calcium carbonate product prepared in example 2-1;
FIG. 6 is an XRD pattern for the calcium carbonate product prepared in example 3-1;
FIG. 7 is a scanning electron microscope image of the calcium carbonate product prepared in example 3-1;
FIG. 8 is an XRD pattern for the calcium carbonate product prepared in example 3-2;
FIG. 9 is a scanning electron microscope image of the calcium carbonate product prepared in example 3-2;
FIG. 10 is an XRD pattern for the calcium carbonate product prepared in examples 3-5;
FIG. 11 is a scanning electron microscope image of the calcium carbonate product prepared in examples 3-5;
FIG. 12 is a graph showing the mobility change of the acid compartment Cl - after bipolar membrane electrodialysis with different water-soluble amine hydrochlorides;
FIG. 13 is a graph showing the change in residual rate of salt compartment Cl - after bipolar membrane electrodialysis with different water-soluble amine hydrochlorides;
fig. 14 is a graph showing the change in the regeneration rate of salt chamber amine after bipolar membrane electrodialysis of different water-soluble amine hydrochlorides.
Detailed Description
The technical scheme of the invention is clearly and completely described in the following by specific embodiments. It is to be understood that the described embodiments are only some, but not all, of the embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to fall within the scope of the invention. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art.
According to the process flow diagram shown in fig. 1, the calcium chloride waste liquid and the flue gas CO 2 are comprehensively utilized, the calcium chloride waste liquid and the flue gas CO 2 are taken as raw materials, water-soluble amine is added as an auxiliary agent to promote mineralization reaction, filtering is carried out, calcium carbonate solid products and filtrate water-soluble amine hydrochloride are obtained, in order to further recycle the water-soluble amine and realize the recycling of chlorine, chlorine-containing waste liquid is not generated, the water-soluble amine hydrochloride is regenerated by adopting a bipolar membrane electrodialysis mode, the filtrate water-soluble amine hydrochloride is added into a salt chamber, then regenerated water-soluble amine and dilute hydrochloric acid are respectively obtained in the salt chamber (or an alkali chamber) and an acid chamber, the regenerated water-soluble amine is recycled to the mineralization section for reuse, the dilute hydrochloric acid is used in other workshops of a factory, and the obtained high-value nano-level or micron-level calcium carbonate with controllable morphology granularity is used in selling or other workshops of the factory.
The reaction equations of the water-soluble amine mineralized CO 2 section and the bipolar membrane electrodialysis regeneration amine section are respectively shown as follows:
CaCl2+2RNH2+CO2+H2O→CaCo3↓+2RNH2·HCl
RNH2·HCl→RNH2+HCl
example 1
Taking 100ml of 1mol/L Piperazine (PZ) solution in a jacketed reactor, controlling the stirring rotation speed to be 200r/min, controlling the reaction temperature to be 25 ℃, introducing 15% CO 2 gas into the reaction system, and controlling the gas inlet rate to be 500ml/min; after 1h of reaction, the water-soluble amine solution absorbs CO 2 to saturation, stopping introducing CO 2; 50ml of CaCl 2 waste liquid containing 1mol/LCaCl 2 is added into a jacketed reactor dropwise, the dropping speed is 1.667ml/min, the stirring rotation speed is 200r/min, the reaction temperature is 25 ℃, and the reaction is finished after 0.5 h. Filtering, washing the filter cake with deionized water and ethanol for multiple times, and oven drying at 110deg.C to obtain calcium carbonate product, labeled as example 1-1. ICP test shows that the conversion rate of the primary reaction of calcium chloride is 98.87%, and the yield of calcium carbonate is 95.59%; the calcium carbonate product was a cubic calcite-type calcium carbonate with an average particle size of 16.65 μm as shown in fig. 2-3 by XRD and scanning electron microscope analysis.
The operations of examples 1-2 to 1-5 were identical to those described above, and the process conditions and reaction results, which are specific to those of example 1-1, are shown in the following table. XRD and scanning electron microscopy of examples 1-2 to 1-5 are consistent with the results of example 1-1. The mark a is that CO 2 gas is introduced into the water-soluble amine solution and then mixed with CaCl 2 waste liquid, and the mark b is that the water-soluble amine solution is mixed with CaCl 2 waste liquid and then introduced with CO 2 gas; c, dropwise adding the CaCl 2 waste liquid into the water-soluble amine solution; d "pouring" means pouring CaCl 2 waste liquid directly into the water-soluble amine solution; e "calcium amine ratio" is expressed as the ratio of the amount of calcium chloride to the amount of water-soluble amine material in the reaction raw material. The explanation applies equally hereinafter.
According to the results of examples 1-1 to 1-5, when the water-soluble amine is selected from the diamine compounds, the mineralized calcium carbonate product is calcite type calcium carbonate with controllable morphology, and is not limited by other process conditions.
Example 2
Taking 100ml of 1mol/L sodium glycinate (GlyNa) solution in a jacketed reactor, controlling the stirring rotation speed to be 200r/min, controlling the reaction temperature to be 25 ℃, introducing 15% CO 2 gas into the reaction system, and controlling the gas inlet rate to be 500ml/min; after 1h of reaction, the water-soluble amine solution absorbs CO 2 to saturation, stopping introducing CO 2; 50ml of CaCl 2 waste liquid containing 1mol/L CaCl 2 is dropwise added into a jacketed reactor, the dropping speed is 1.667ml/min, the stirring rotation speed is 200r/min, the reaction temperature is 25 ℃, and the reaction is finished after 0.5 h. Filtering, washing the filter cake with deionized water and ethanol for multiple times, and oven drying at 110deg.C to obtain calcium carbonate product, labeled as example 2-1. ICP test shows that the conversion rate of the calcium chloride in one reaction is 98.30%, and the yield of the calcium carbonate is 96.48%; the calcium carbonate product was spherical vaterite type calcium carbonate with an average particle size of 34.6 μm as shown in fig. 4-5 by XRD and scanning electron microscope analysis.
The operations of examples 2-2 to 2-5 were identical to those described above, and the process conditions and reaction results, which are specific to those of example 2-1, are shown in the following table. XRD and scanning electron microscopy of examples 2-2 to 2-5 are consistent with the results of example 2-1.
According to the results of examples 2-1 to 2-5, when the water-soluble amine is selected from the group consisting of amino acid salt compounds and basic amino acid compounds, the mineralized calcium carbonate product is the vaterite type calcium carbonate with controllable morphology, and is not limited by other process conditions.
Example 3
Taking 100ml of 1mol/L ethanolamine (MEA) solution in a jacketed reactor, controlling the stirring rotation speed to be 200r/min, controlling the reaction temperature to be 25 ℃, introducing 15% CO 2 gas into the reaction system, and controlling the air inlet rate to be 500ml/min; after 1h of reaction, the water-soluble amine solution absorbs CO 2 to saturation, stopping introducing CO 2; 50ml of CaCl 2 waste liquid containing 1mol/L CaCl 2 is dropwise added into a jacketed reactor, the dropping speed is 1.667ml/min, the stirring rotation speed is 200r/min, the reaction temperature is 25 ℃, and the reaction is finished after 0.5 h. Filtering, washing the filter cake with deionized water and ethanol for multiple times, and oven drying at 110deg.C to obtain calcium carbonate product, labeled as example 3-1. ICP test shows that the conversion rate of the primary reaction of the calcium chloride is 99.18%, and the yield of the calcium carbonate is 97.52%; the calcium carbonate product was spherical vaterite type calcium carbonate with an average particle size of 7.6 μm as shown in fig. 6-7 by XRD and scanning electron microscopy analysis.
The procedure of each of examples 3-2 to 3-16 was substantially identical to that described above using the alcohol amine type water-soluble amine, and the process conditions and the reaction results differing from those of example 3-1 are shown in the following table.
XRD and scanning electron microscope analyses of the products prepared in example 3-2 are shown in FIGS. 8-9, and the XRD and scanning electron microscope analyses of examples 3-3 to 3-4 are consistent with those of example 3-2, based on the results of examples 3-1 to 3-4. When the ratio of the amount of calcium chloride to the amount of water-soluble amine material is greater than 1:2, namely when the calcium chloride is excessively added, the prepared calcium carbonate product is calcite type calcium carbonate with controllable morphology.
According to the results of examples 3-5 to 3-11, when the ratio of the amounts of calcium chloride to the water-soluble amine substance is not more than 1:2, i.e. when the water-soluble amine is added excessively or in equal amount, if CO 2 absorption and mineralization reaction occur simultaneously, i.e. when CO 2 is introduced into a mixed solution of a water-soluble amine solution and a calcium chloride solution to perform mineralization reaction, the prepared calcium carbonate product is polycrystalline calcium carbonate, and referring to the results of examples 3-5 to 3-6, fig. 10-11 are XRD and scanning electron microscope analyses of the prepared products of examples 3-5.
If CO 2 is absorbed and then mineralized, namely CO 2 is introduced into a water-soluble amine solution and then mixed with calcium chloride waste liquid, the calcium carbonate product prepared by the low-temperature mineralization reaction is vaterite type calcium carbonate with controllable morphology, the calcium carbonate product prepared by the high-temperature mineralization reaction is calcite type calcium carbonate with controllable morphology, and the results of examples 3-7 to 3-11 are referred to, the morphologies of examples 3-7 to 3-8 are similar to those of example 3-1, and the morphologies of examples 3-9 to 3-10 are similar to those of example 3-2.
Examples 3-12 to 3-16 differ from example 3-1 in that: the water-soluble amine solution and the CaCl 2 waste liquid are sequentially exchanged, namely, firstly, the CaCl 2 waste liquid is taken in a jacketed reactor, CO 2 gas is introduced into a reaction system to be saturated, and then, the water-soluble amine solution is dropwise added into the jacketed reactor for mineralization reaction; the term "mineral absorption simultaneously" means that the water-soluble amine solution is added into the CaCl 2 waste liquid to be mixed and then CO 2 gas is introduced. Other operational controls were consistent with example 3-1.
According to the results of examples 3-12 to 3-16, when the calcium chloride solution was added to the aqueous amine solution in the order of addition, if CO 2 was absorbed and then mineralized, that is, CO 2 was introduced into the calcium chloride waste solution and then mixed with the aqueous amine solution, the prepared calcium carbonate product was calcite type calcium carbonate with a controllable morphology, which was similar to example 3-2 in morphology without being limited by other process conditions, with reference to the results of examples 3-12 to 3-14. And when the feeding sequence is that CO 2 absorption and mineralization reaction occur simultaneously, namely CO 2 is introduced into a mixed solution of water-soluble amine solution and calcium chloride solution to perform mineralization reaction, the prepared calcium carbonate product is polymorphic calcium carbonate with mixed morphology, and the results of examples 3-15 to 3-16 are referred.
Example 4
The filtrates obtained by filtration in examples 1-1, 2-1, 3-3, 3-4, 3-8 (piperazine hydrochloride, glycine sodium salt, ethanolamine hydrochloride, 2-amino-2 methyl-1-propanol hydrochloride, N-methyldiethanolamine hydrochloride, triethanolamine hydrochloride solution, respectively) were selected, and subjected to bipolar membrane electrodialysis treatment to recover water-soluble amine and prepare dilute hydrochloric acid.
The filtrate is processed by bipolar membrane electrodialysis, a two-compartment structure of a salt compartment and an acid compartment is adopted, the salt compartment is initially 300ml of filtrate solution, the acid compartment is initially 300ml of 0.03mol/L of dilute hydrochloric acid solution, the polar liquid compartment is 300ml of 0.3mol/L of Na 2SO4 solution, a direct current power supply is set for 0.5A constant current operation, the flow rates of the compartments are set to be 500ml/min, and regenerated water-soluble amine and dilute hydrochloric acid are respectively obtained in the salt compartment and the acid compartment after 60-100 min of treatment.
The different water-soluble amine hydrochlorides can be regenerated by bipolar membrane electrodialysis, and the regeneration treatment effect is excellent, and the regeneration rate of each water-soluble amine except piperazine hydrochloride can reach more than 90%. FIG. 12 shows the mobility of acid compartment Cl-after bipolar membrane electrodialysis treatment of various water-soluble amine hydrochlorides; FIG. 13 shows the residual rate of salt compartment Cl-after treatment of different kinds of water-soluble amine hydrochlorides by bipolar membrane electrodialysis; FIG. 14 shows the regeneration rate of salt-chamber amines after bipolar membrane electrodialysis treatment of various water-soluble amine hydrochlorides.
The method for comprehensively utilizing the calcium chloride waste liquid and the flue gas CO 2 by adopting the water-soluble amine mineralization and bipolar membrane electrodialysis to regenerate the amine is applicable to different types of water-soluble amine solutions, the mineralization process is easy to carry out, the mineralization effect is excellent, and micron-sized or nano-sized high-value calcium carbonate with controllable morphology and granularity can be obtained through process regulation and control and is used for selling or other workshops of factories; the obtained different kinds of water-soluble amine hydrochloride filtrate can be regenerated by a bipolar membrane electrodialysis mode to obtain water-soluble amine, dilute hydrochloric acid is formed, and the regeneration treatment effect of the different water-soluble amine hydrochlorides is excellent. The method realizes the comprehensive utilization of the calcium chloride waste liquid and the flue gas CO 2, obtains the high-value calcium carbonate product and the dilute hydrochloric acid, has remarkable advantages compared with the prior art, provides a brand new thought and method for the field of treating the calcium chloride and the carbon emission reduction, has high process feasibility and has good application prospect.
The present application has been described in detail with the purpose of enabling those skilled in the art to understand the contents of the present application and to implement the same, but not to limit the scope of the present application, and all equivalent changes or modifications made according to the spirit of the present application should be covered in the scope of the present application.
Claims (10)
1. A method for comprehensively utilizing a calcium chloride solution and CO 2, the method comprising:
(1) Taking a calcium chloride solution and CO 2 as raw materials, adding water-soluble amine as an auxiliary agent to promote mineralization reaction to generate calcium carbonate and water-soluble amine hydrochloride, and carrying out solid-liquid separation to obtain a calcium carbonate product;
(2) The separated liquid phase is regenerated into water-soluble amine through bipolar membrane electrodialysis, and dilute hydrochloric acid is produced as a byproduct.
2. The method according to claim 1, wherein the calcium chloride solution is derived from soda ash production by an ammonia-soda process, calcium hydrogen phosphate and potassium chlorate production by extraction of ground phosphate rock with hydrochloric acid, or calcium chloride waste liquid discharged from production of polysilicon; the concentration of the calcium chloride solution is 0.1-3 mol/L;
The CO 2 is from flue gas CO 2 discharged by a power plant, a lime kiln or a carbonization tower; the concentration of CO 2 in the flue gas CO 2 is 2% -100%.
3. The method of claim 1, wherein the mineralization reaction is at a temperature of 10 to 80 ℃;
the ratio of the amount of the substances of the calcium chloride and the water-soluble amine is 1: (0.4 to 10), preferably 1: (1-4);
The feeding mode of the CO 2 is as follows: firstly, introducing water-soluble amine solution, and then mixing with calcium chloride waste liquid to carry out mineralization reaction; or introducing the calcium chloride waste liquid into the water-soluble amine solution to be mixed for mineralization reaction; or introducing the mixture of the water-soluble amine solution and the calcium chloride waste liquid to carry out mineralization reaction.
4. The method of claim 1, wherein the water-soluble amine is selected from one or more of an alcohol amine compound, an amino acid salt compound, a basic amino acid compound, a diamine compound, a polyamine compound, an aliphatic amine compound, an aromatic amine compound, a heterocyclic amine compound, and a biogenic amine compound.
5. The method of claim 4, wherein the water-soluble amine is selected from one or More of Ethanolamine (MEA), diethanolamine (DEA), triethanolamine (TEA), N-Methyldiethanolamine (MDEA), 2-amino-2 methyl-1-propanol (AMP), sodium glycinate (GlyNa), arginine (Arg), piperazine (PZ), ethylenediamine (EDA), tetramethyl ethylenediamine (TEMED), triethylene tetramine (TETA), pyridine (PD), cadaverine, putrescine, spermine, spermidine, and the like.
6. The method of claim 4, wherein when the water-soluble amine is selected from the group consisting of diamines, the calcium carbonate product produced in step (1) is calcite-type calcium carbonate;
when the water-soluble amine is selected from amino acid salt compounds and basic amino acid compounds, the calcium carbonate product prepared in the step (1) is vaterite type calcium carbonate.
7. The method of claim 4, wherein when the water-soluble amine is selected from the group consisting of alcohol amine compounds, the modulation is performed according to the following mineralization process:
When the ratio of the amount of calcium chloride to the amount of water-soluble amine material is greater than 1:2, the calcium carbonate product prepared in the step (1) is calcite type calcium carbonate, and the ratio of the calcite type calcium carbonate to the calcite type calcium carbonate is preferably 1: (0.4 to 2), excluding 1:2;
When the feeding mode is that the water-soluble amine solution is added with the calcium chloride solution, and the feeding mode of CO 2 is that CO 2 is firstly introduced into the water-soluble amine solution and then mixed with the calcium chloride waste liquid, or is firstly introduced into the calcium chloride waste liquid and then mixed with the water-soluble amine solution, the calcium carbonate product prepared in the step (1) is calcite type calcium carbonate;
When the ratio of the amount of calcium chloride to the amount of water-soluble amine material is not greater than 1:2, adding a water-soluble amine solution into a calcium chloride solution in a feeding manner, and adding CO 2 in a feeding manner that CO 2 is firstly introduced into the water-soluble amine solution and then mixed with a calcium chloride waste liquid, or is firstly introduced into the calcium chloride waste liquid and then mixed with the water-soluble amine solution: the calcium carbonate product prepared by the low-temperature mineralization reaction is vaterite type calcium carbonate, and the temperature of the low-temperature mineralization reaction is 10-40 ℃, preferably 20-30 ℃; the calcium carbonate product prepared by the high-temperature mineralization reaction is calcite type calcium carbonate, and the temperature of the high-temperature mineralization reaction is 50-80 ℃, preferably 60-70 ℃.
8. The method according to claim 1, wherein when the calcium chloride solution and the water-soluble amine solution are mixed in such a manner that they are directly poured into and mixed, the calcium carbonate product obtained in the step (1) is small-particle-size calcium carbonate, that is, calcium carbonate having an average particle size of less than 20 μm, preferably calcium carbonate having an average particle size of less than 10 μm;
When the calcium chloride solution and the water-soluble amine solution are mixed in a dropwise manner, the calcium carbonate product prepared in the step (1) is large-particle-size calcium carbonate, that is, calcium carbonate with an average particle size of more than 10 μm, preferably calcium carbonate with an average particle size of more than 20 μm.
9. The method of claim 1, wherein the bipolar membrane electrodialysis device adopts a three-compartment structure of salt compartment-acid compartment-base compartment or a two-compartment structure of salt compartment-acid compartment; and (3) by-producing dilute hydrochloric acid in an acid chamber, and regenerating in an alkali chamber (or a salt chamber) to obtain a water-soluble amine solution, wherein the water-soluble amine solution is recycled to the mineralization process of the step (1) for reuse.
10. The method according to claim 9, wherein when the bipolar membrane electrodialysis device starts to operate, the acid chamber is 0.01-2.00 mol/L HCl solution, the alkali chamber is 0.01-2.00 mol/L NaOH solution, the salt chamber is liquid phase solution after solid-liquid separation, and the polar liquid chamber is 0.01% -10% Na 2SO4 solution; the flow rate of each compartment of the bipolar membrane electrodialysis device is 10-200L/h, and the intensity of the applied constant current is 0.1-5.0A.
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