CN114835142A - Method for recovering carbon dioxide from industrial kiln tail gas and producing lithium carbonate - Google Patents
Method for recovering carbon dioxide from industrial kiln tail gas and producing lithium carbonate Download PDFInfo
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- CN114835142A CN114835142A CN202210532811.0A CN202210532811A CN114835142A CN 114835142 A CN114835142 A CN 114835142A CN 202210532811 A CN202210532811 A CN 202210532811A CN 114835142 A CN114835142 A CN 114835142A
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 47
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 47
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 title claims abstract description 39
- 229910052808 lithium carbonate Inorganic materials 0.000 title claims abstract description 39
- 239000007789 gas Substances 0.000 claims abstract description 95
- 238000001179 sorption measurement Methods 0.000 claims abstract description 67
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 27
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims abstract description 24
- 230000008569 process Effects 0.000 claims abstract description 13
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 11
- 230000023556 desulfurization Effects 0.000 claims abstract description 11
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000002245 particle Substances 0.000 claims abstract description 4
- 238000000926 separation method Methods 0.000 claims description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 23
- 239000003463 adsorbent Substances 0.000 claims description 22
- 238000000746 purification Methods 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000003546 flue gas Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000002808 molecular sieve Substances 0.000 claims description 6
- 238000011069 regeneration method Methods 0.000 claims description 6
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 230000008929 regeneration Effects 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 230000018044 dehydration Effects 0.000 claims description 4
- 238000006297 dehydration reaction Methods 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 3
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 239000003638 chemical reducing agent Substances 0.000 claims description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical class O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
- 239000000428 dust Substances 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- 239000011630 iodine Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 238000010926 purge Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 239000010881 fly ash Substances 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052680 mordenite Inorganic materials 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 2
- 238000003763 carbonization Methods 0.000 abstract description 2
- 229910052744 lithium Inorganic materials 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 7
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- 230000008901 benefit Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000011010 flushing procedure Methods 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
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- 230000005494 condensation Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
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- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
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- 238000012986 modification Methods 0.000 description 2
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- 239000002002 slurry Substances 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 239000002918 waste heat Substances 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- PUAQLLVFLMYYJJ-UHFFFAOYSA-N 2-aminopropiophenone Chemical compound CC(N)C(=O)C1=CC=CC=C1 PUAQLLVFLMYYJJ-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
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- 238000007906 compression Methods 0.000 description 1
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- 239000012153 distilled water Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 1
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 1
- -1 machinery Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
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- 150000004767 nitrides Chemical class 0.000 description 1
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- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/08—Carbonates; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/50—Carbon dioxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention relates to a method for recovering carbon dioxide from industrial kiln tail gas and producing lithium carbonate, which comprises the steps of removing particles from the industrial kiln tail gas, carrying out denitration and desulfurization treatment, pressurizing the treated tail gas to 0.1-0.7 MPa, dehydrating, and carrying out NOx and SO by using a double-tower temperature swing adsorption device 2 And (3) removing to obtain purified tail gas, introducing the purified tail gas into a four-tower pressure swing adsorption device to separate carbon dioxide, and finally introducing the obtained carbon dioxide into a lithium hydroxide solution to prepare lithium carbonate. The invention removes trace sulfide and nitrogen oxide in the tail gas by using a temperature swing adsorption method, SO that SO in the tail gas 2 And total concentration of NOx<1ppm, the invention also adopts a pressure swing adsorption method to recover carbon dioxide, the obtained carbon dioxide gas has high purity, high recovery rate and large handling capacity, and the separated and refined high-purity carbon dioxide can be used as raw material for producing battery-grade lithium carbonate in the carbonization process, thereby realizing that the tail gas of the industrial kiln furnace can be used as raw material for producing battery-grade lithium carbonateAnd (5) resource utilization of medium carbon dioxide.
Description
Technical Field
The invention relates to a method for recovering carbon dioxide from industrial kiln tail gas and producing lithium carbonate, belonging to the technical field of environmental engineering.
Background
World CO over the last 10 years 2 The emission amount is increased year by year, resulting in CO in the air 2 The concentration is too high and the greenhouse effect is increasingly obvious, which poses serious threats to the living safety of human beings and the sustainable development of social economy; worldwide, 60 hundred million tons of CO must be reduced each year 2 The emission can effectively prevent global climate change, and how to control CO 2 Has become a serious problem worldwide. In the near 40 years in the future, China's CO 2 The net emission is reduced from about 100 hundred million tons per year to almost zero, and CO is reduced 2 The pressure is high.
At present, about 13 ten thousand industrial furnaces (burning) are used in four industries of metallurgy, building materials, machinery, chemical industry and the like in China, the total amount of the furnaces is 85 percent, and CO is discharged from kiln flue gas 2 Approximately accounts for industrial waste gas CO 2 30% of the discharge amount. The fuel of industrial kiln (combustion) is mostly natural gas, and the flue gas CO of natural gas kiln 2 Low concentration (5-15%), low partial pressure (0.10-1 bar), complex composition, and CO 2 The capture and recovery efficiency is relatively low. At the same time, CO 2 Large amount of compression energy is consumed before transportation and storage, and carbon capture is carried outHigh energy consumption and cost of the collection, and CO 2 Is an important renewable resource of kiln tail gas, develops industrial kiln flue gas CO 2 Recovery and utilization of CO 2 The discharge is of great significance.
In the prior art, CO 2 The recovery and separation technology mainly comprises an absorption method, a low-temperature condensation method, a membrane separation method and an adsorption method. Low temperature condensation process only for CO 2 Under the working condition that the concentration is higher than 60 percent, the method needs more equipment, has large investment, high energy consumption and poor separation effect and is generally only suitable for oil field exploitation sites; the membrane separation method has the advantages of simple process, convenient operation and low energy consumption, and has the defects of frequent need of pretreatment, dehydration and filtration and difficult obtainment of high-purity CO 2 (ii) a At present, CO 2 The recovery and capture mostly adopt a chemical absorption method which can be used for CO in gas 2 In the case of a lower content, CO after concentration 2 The concentration can reach 99.99%, but the process has the disadvantages of high investment cost, high chemical absorbent loss, serious equipment corrosion, high energy consumption and high separation and recovery cost.
Separation and purification of CO by adsorption method 2 The method has the advantages of low energy consumption, long service life of the adsorbent, simple process flow, high automation degree, good environmental benefit, no pollution and the like, the key of the adsorption method lies in the performance of the adsorbent, but the concentration of the carbon dioxide in the kiln tail gas is low, the performance of the adsorbent is easily influenced by nitrogen oxides, sulfides, moisture and the like, so that the adsorption capacity of the adsorbent is low, the recycling treatment cost is high, and the selectivity of the adsorbent used in the existing industry to the carbon dioxide is low. Recently, it is reported that the method can be used for purifying and separating CO from the tail gas of an industrial furnace 2 The adsorbent is zeolite material-13X molecular sieve and carbon-based material-activated carbon, and other materials do not enter the adsorbent production stage. The 13X molecular sieve has strong hydrophilicity, and the smoke contains components such as water, sulfide and nitride and CO on the surface of the smoke 2 Has strong competitive adsorption and seriously influences the separation and purification of CO 2 (ii) a Activated carbon has low sensitivity to moisture, but at low pressure, activated carbon is sensitive to CO 2 The adsorption capacity is lower than that of zeolites. On the other hand, in the prior art, the PSA purification separation recovery of CO is involved 2 Only study ofThe flue gas is limited to simulated flue gas, the components are few, the actual industrial kiln tail gas has complex components and more impurities, and therefore CO in the industrial kiln tail gas 2 When recycling is carried out, the method faces more challenges, and research and improvement are needed on the basis of the prior art.
Disclosure of Invention
The invention aims to solve the defects of the prior art and provides a method for recovering carbon dioxide from industrial kiln tail gas and producing lithium carbonate.
In order to achieve the above purpose, the invention provides the following technical scheme:
a method for recovering carbon dioxide from industrial kiln tail gas and producing lithium carbonate comprises the following steps:
(1) pretreatment:
removing particles from the industrial kiln tail gas through a cyclone dust collector, and then performing denitration treatment and desulfurization treatment to obtain pretreated tail gas;
(2) adsorption and purification of trace sulfide and nitrogen oxide:
pressurizing the tail gas pretreated in the step (1) to 0.1-0.7 MPa through a compressor, then introducing the tail gas into a water-gas separation tank for dehydration, and then performing NOx and SO by adopting a double-tower temperature swing adsorption device 2 Removing to obtain purified tail gas;
the double-tower temperature swing adsorption device comprises two adsorption towers, and adsorbents are contained in the two adsorption towers;
(3) separation and purification of carbon dioxide:
introducing the purified tail gas into a four-tower pressure swing adsorption device for separating carbon dioxide, wherein the four-tower pressure swing adsorption device comprises 4 pressure swing adsorption towers which are sequentially connected, and adsorbents are filled in the 4 pressure swing adsorption towers and used for absorbing CO in the tail gas of the flue gas purification 2 The rest components which are difficult to be adsorbed flow out from the tower top and are directly emptied; finally, desorbing the adsorbents in the four pressure swing adsorption towers to obtain carbon dioxide gas;
(4) preparation of lithium carbonate:
and (4) introducing the carbon dioxide gas obtained in the step (3) into a lithium hydroxide solution, stirring and mixing uniformly, stopping introducing the carbon dioxide gas when a large amount of solids appear in the solution, heating to 90-110 ℃, keeping the temperature for 10-60 minutes, carrying out hot centrifugal separation to obtain a crude lithium carbonate product, and purifying to obtain the battery-grade lithium carbonate.
Further, in the step (1), the denitration treatment adopts a high-temperature SCR process, is carried out in an SCR denitration catalytic reactor, takes ammonia water as a reducing agent, and V 2 O 5 -WO 3 -MoO 3 /TiO 2 Is a denitration catalyst, and the reaction temperature is 300-400 ℃.
Further, in the step (2), the adsorbent is one or a combination of more than two of activated carbon, modified silica gel, modified fly ash, activated zeolite or mordenite with an iodine value of more than 1000 in any proportion.
Further, in the step (2), after the two adsorption towers of the double-tower temperature swing adsorption device are subjected to adsorption saturation, the temperature is increased to 80-150 ℃, hot nitrogen is adopted for purging and regeneration for 1-20min, the adsorbent can be recycled and reused, and the purged tail gas enters the step (1) for denitration treatment and desulfurization treatment.
Further, in the step (3), the adsorbent is any one or a combination of more than two of nitrogen-doped activated carbon, carbon fiber, carbon nanotube, graphene, high-hydrophobicity 13X, high-silicon ZSM-5, all-silicon ZSM molecular sieve or mesoporous silica in any proportion.
Further, in the step (4), the concentration of the lithium hydroxide solution is 50-90 g/L.
Further, in the step (4), the purification method comprises the following steps: and adding water into the crude lithium carbonate product, controlling the solid-to-liquid ratio to be 1: 1-1: 5, stirring and heating to 90-95 ℃, carrying out centrifugal separation while the lithium carbonate product is hot, repeating the centrifugal separation for 1-3 times, and then carrying out vacuum drying.
The invention has the beneficial effects that:
the invention provides a method for recovering carbon dioxide from industrial kiln tail gas and producing lithium carbonate, which can recover the carbon dioxide in the industrial kiln tail gas to the maximum extent and has no generation of three wastes 2 And total concentration of NOx<1 ppm; the invention adopts the pressure swing adsorption method to recover the carbon dioxide, and the obtained carbon dioxide gas has high purity (volume concentration of the carbon dioxide)>99%) and has high recovery rate and large treatment capacity; the separated and refined high-purity carbon dioxide is used as a raw material in the carbonization process to produce battery-grade lithium carbonate, so that the resource utilization of the carbon dioxide in the tail gas of the industrial kiln is realized, and the method has important significance for reducing carbon emission reduction and carbon neutralization.
Description of the drawings:
FIG. 1 is a process flow diagram of a process for recovering carbon dioxide and producing lithium carbonate from industrial kiln tail gas in example 1;
FIG. 2 is a flow chart showing the steps of adsorption purification of trace amounts of sulfur compounds and nitrogen oxides and separation purification of carbon dioxide in example 1;
wherein, 1-compressor; 2-a water-gas separation tank; 3-a double-tower temperature swing adsorption device; 4-four-tower pressure swing adsorption device.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below with reference to the accompanying drawings, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments that can be derived by one of ordinary skill in the art from the embodiments given herein are intended to be within the scope of the present invention.
Example 1
In the embodiment, the kiln tail gas is natural gas oxygen-enriched combustion kiln tail gas, and through analysis, the water vapor content is 4.70-6.78 v%, and the content of O is 4.70-6.78 v% 2 Concentration of 13.90-15.10 v%, CO 2 2.51 to 4.39 v%, NOx concentration of 0.037 to 0.060 v% (500 to 800ppm), and SO 2 Concentration of 0.014 v% (-400 ppm), CO concentration of 0.02-0.6 v%, H 2 The concentration is 0.01-0.06%, and the rest is N 2 . The method for recycling the carbon dioxide in the industrial kiln tail gas is characterized in that the recycled carbon dioxide gas is used for preparing high-purity battery-grade lithium carbonate by an ore lithium extraction enterprise, and comprises the following steps:
as shown in fig. 1-2, a method for recovering carbon dioxide from industrial kiln exhaust gas and producing lithium carbonate comprises the following steps:
(1) pretreatment:
removing particles from the industrial kiln tail gas through a cyclone dust collector, and then performing denitration treatment and desulfurization treatment by using a denitration and desulfurization system to obtain pretreated tail gas;
the denitration and desulfurization system comprises an SCR denitration catalytic reactor, a waste heat boiler and a spray absorption tower which are sequentially connected, wherein the denitration treatment adopts a high-temperature SCR process, ammonia water is used as a reducing agent, and V is carried out in the SCR denitration catalytic reactor 2 O 5 -WO 3 - MoO 3 /TiO 2 The denitration catalyst is used, the reaction temperature is 300-400 ℃, nitrogen oxide NOx in tail gas reacts with ammonia water to produce nitrogen and water, the concentration of the nitrogen oxide in the tail gas is controlled to be 1-10ppm, the tail gas enters a waste heat boiler for heat exchange and cooling, the tail gas enters a spray absorption tower for desulfurization treatment after the temperature is reduced to be lower than 300 ℃, alkaline limestone slurry fog drops sprayed from top to bottom in the spray absorption tower contact with the tail gas in a countercurrent mode, and acidic oxide SO in the tail gas 2 And other pollutants are absorbed, so that the tail gas can be fully purified; absorption of SO 2 The slurry is reacted to generate CaSO 3 In-situ forced oxidation and crystallization to form CaSO 4 ·2H 2 O。
The pretreated tail gas was subjected to composition analysis, and the results are shown in table 1:
TABLE 1
As can be seen, after the denitration treatment and the desulfurization treatment, the NOx in the tail gas is 1-10mg/m 3 ，SO 2 <50mg/m 3 The gauge pressure is only 0.02-0.1 KPa.
(2) Adsorption and purification of trace sulfide and nitrogen oxide:
pressurizing the tail gas pretreated in the step (1) to 0.7MPa through a compressor, then entering a water-gas separation tank for dehydration, and controlling the mass concentration of water in the tail gas<50mg/m 3 The dehydrated tail gas enters a double-tower temperature changing deviceAnd (4) an adsorption device. The double-tower temperature swing adsorption device comprises an adsorption tower A and an adsorption tower B which are connected, and adsorbents (with iodine value of>1400mg/g of organic amine impregnated activated carbon, supplied by national chemical group, ltd), both ends were packed with quartz sand. The dehydrated tail gas enters an adsorption tower A from the upper end at room temperature for carrying out trace NOx and SO 2 Removing, namely obtaining purified tail gas at the lower end of the adsorption tower A, and using the purified tail gas as subsequent CO 2 Separating and refining the raw materials; after adsorption saturation, the adsorption tower A is heated to 150 ℃ (tail gas is switched to the adsorption tower B for adsorption), 150 ℃ hot nitrogen and normal pressure purging regeneration are adopted for 5min, and the purged tail gas directly enters the denitration and desulfurization system in the step (1); after the regeneration of the adsorption tower A is completed, cooling to room temperature and entering the next cycle for adsorption; when the adsorption tower A is used for adsorption, the temperature of the adsorption tower B is raised, nitrogen is blown and the adsorption-regeneration processes of the two towers are alternately carried out.
(3) Separation and purification of carbon dioxide:
introducing the purified tail gas into a four-tower pressure swing adsorption device for separating carbon dioxide, wherein the four-tower pressure swing adsorption device comprises 4 pressure swing adsorption towers C, D, E, F which are sequentially connected, and 13X molecular sieves serving as adsorbents are filled in the 4 pressure swing adsorption towers (synthesized by adopting the method of embodiment 1 in CN 200910183869.3) and are used for absorbing and purifying CO in the tail gas 2 Filling inert alumina at two ends of the absorber for packaging; after tail gas after adsorption and purification enters a C-F four-tower pressure swing adsorption device, the C-F four-tower adsorption process is as follows: one column is in the adsorption stage and the other three are in the pressure reduction, flushing and pressure increase stages, respectively. Taking tower C as an example, firstly, tail gas enters the tower C for adsorption to obtain high-purity CO 2 (volume concentration)>99.9%), directly discharging the purified tail gas; pressure drop equalization: the tower C is placed in the tower D in the forward direction; thirdly, releasing the gas in the-C tower to the E tower in the forward direction; fourthly, reverse pressure relief: reducing the gas to a minimum pressure (normal pressure) to desorb a portion of the adsorbed species; flushing: pure gas discharged in the forward direction of the tower F is used for reversely flushing the tower C so as to achieve the final regeneration; sixthly, pressure equalization and rise: and (3) pressurizing the tower C by using pressure equalizing gas of the tower D: column C is charged to the desired adsorption pressure with column E (now adsorbing) product gas.
CO in the exhaust gas 2 After absorption is finished, desorbing the adsorbents in the four pressure swing adsorption towers to obtain carbon dioxide gas;
(4) preparation of lithium carbonate:
dissolving 600kg of battery-grade lithium hydroxide monohydrate in distilled water, preparing a lithium hydroxide solution with the concentration of 80g/L, placing the lithium hydroxide solution in a reaction kettle, stirring for 100min, and filtering out insoluble impurities through pressure filtration to obtain a lithium hydroxide filtrate; introducing the carbon dioxide gas obtained in the step (3) into lithium hydroxide filtrate, preferably CO 2 The flow rate is 3L/s, the stirring speed is 70 r/min, and when a large amount of solid appears in the solution, the CO introduction is stopped 2 Heating to 100 ℃, keeping the temperature for 30 minutes, and then performing centrifugal separation to obtain a crude lithium carbonate product; adding water into the crude lithium carbonate product according to the solid-to-liquid ratio of 1:3, stirring and heating to 95 ℃, then carrying out centrifugal separation while the lithium carbonate product is hot to obtain a wet lithium carbonate product, repeating the conditions for 1 time, and placing the wet lithium carbonate product into a vacuum box drying box for drying to obtain the lithium carbonate. The purity of the lithium carbonate was measured to be 99.99% by the method in YS/T546-2021 "high purity lithium carbonate".
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. A method for recovering carbon dioxide from industrial kiln tail gas and producing lithium carbonate is characterized by comprising the following steps:
(1) pretreatment:
removing particles from the industrial kiln tail gas through a cyclone dust collector, and then performing denitration treatment and desulfurization treatment to obtain pretreated tail gas;
(2) adsorption and purification of trace sulfide and nitrogen oxide:
pressurizing the tail gas pretreated in the step (1) to 0.1-0.7 MPa through a compressor, then introducing the tail gas into a water-gas separation tank for dehydration, and then performing NOx and SO through a double-tower temperature swing adsorption device 2 Is removed fromObtaining purified tail gas;
the double-tower temperature swing adsorption device comprises two adsorption towers, and adsorbents are contained in the two adsorption towers;
(3) separation and purification of carbon dioxide:
introducing the purified tail gas into a four-tower pressure swing adsorption device for separating carbon dioxide, wherein the four-tower pressure swing adsorption device comprises 4 pressure swing adsorption towers which are sequentially connected, and adsorbents are filled in the 4 pressure swing adsorption towers and used for absorbing CO in the tail gas of the flue gas purification 2 The rest components which are difficult to be adsorbed flow out from the tower top and are directly emptied; finally, desorbing the adsorbents in the four pressure swing adsorption towers to obtain carbon dioxide gas;
(4) preparation of lithium carbonate:
and (4) introducing the carbon dioxide gas obtained in the step (3) into a lithium hydroxide solution, stirring and mixing uniformly, stopping introducing the carbon dioxide gas when a large amount of solids appear in the solution, heating to 90-110 ℃, keeping the temperature for 10-60 minutes, carrying out hot centrifugal separation to obtain a crude lithium carbonate product, and purifying to obtain the lithium carbonate.
2. The method for recovering carbon dioxide and producing lithium carbonate from the tail gas of the industrial kiln as claimed in claim 1, wherein in the step (1), the denitration treatment is performed by a high-temperature SCR process in an SCR denitration catalytic reactor by using ammonia water as a reducing agent, V 2 O 5 -WO 3 -MoO 3 /TiO 2 Is a denitration catalyst, and the reaction temperature is 300-400 ℃.
3. The method for recovering carbon dioxide and producing lithium carbonate from the tail gas of the industrial kiln as claimed in claim 1, wherein in the step (2), the adsorbent is one or a combination of more than two of activated carbon, modified silica gel, modified fly ash, activated zeolite or mordenite with an iodine value of more than 1000.
4. The method for recovering carbon dioxide and producing lithium carbonate from the tail gas of the industrial kiln as claimed in claim 1, wherein in the step (2), after two adsorption towers of the double-tower temperature swing adsorption device are subjected to adsorption saturation, the temperature is raised to 80-150 ℃, hot nitrogen is used for purging and regeneration for 1-20min, the adsorbent is used after being recycled and regenerated, and the purged tail gas enters the step (1) for denitration treatment and desulfurization treatment.
5. The method for recovering carbon dioxide and producing lithium carbonate from the tail gas of the industrial kiln as claimed in claim 1, wherein in the step (3), the adsorbent is any one of nitrogen-doped activated carbon, carbon fiber, carbon nanotube, graphene, 13X molecular sieve, high-silicon ZSM-5, full-silicon ZSM molecular sieve or mesoporous silica or a combination of two or more of the above in any proportion.
6. The method for recovering carbon dioxide and producing lithium carbonate from the off-gas of the industrial kiln as claimed in claim 1, wherein in the step (4), the concentration of the lithium hydroxide solution is 50 to 90 g/L.
7. The method for recovering carbon dioxide and producing lithium carbonate from the tail gas of the industrial kiln as claimed in any one of claims 1 to 6, wherein, in the step (4), the purification method is: and adding water into the crude lithium carbonate product, controlling the solid-to-liquid ratio to be 1: 1-1: 5, stirring and heating to 90-95 ℃, carrying out centrifugal separation while the lithium carbonate product is hot, repeating the centrifugal separation for 1-3 times, and then carrying out vacuum drying.
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