CN115228277B - Mineralized sealing CO based on shale vanadium extraction tailings2Is a method of (2) - Google Patents
Mineralized sealing CO based on shale vanadium extraction tailings2Is a method of (2) Download PDFInfo
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- CN115228277B CN115228277B CN202210831958.XA CN202210831958A CN115228277B CN 115228277 B CN115228277 B CN 115228277B CN 202210831958 A CN202210831958 A CN 202210831958A CN 115228277 B CN115228277 B CN 115228277B
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- 238000000034 method Methods 0.000 title claims abstract description 82
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 74
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 238000000605 extraction Methods 0.000 title claims abstract description 69
- 238000007789 sealing Methods 0.000 title claims abstract description 57
- 239000007789 gas Substances 0.000 claims abstract description 61
- 230000001089 mineralizing effect Effects 0.000 claims abstract description 57
- 238000005276 aerator Methods 0.000 claims abstract description 52
- 230000033558 biomineral tissue development Effects 0.000 claims abstract description 51
- 239000002912 waste gas Substances 0.000 claims abstract description 51
- 230000014759 maintenance of location Effects 0.000 claims abstract description 35
- 238000003756 stirring Methods 0.000 claims abstract description 28
- 230000008569 process Effects 0.000 claims abstract description 17
- 239000011575 calcium Substances 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims description 39
- 239000002699 waste material Substances 0.000 claims description 33
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 claims description 29
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 15
- 239000002002 slurry Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 230000001105 regulatory effect Effects 0.000 claims description 13
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 11
- 239000000047 product Substances 0.000 claims description 11
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 10
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 10
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 10
- 239000012212 insulator Substances 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 239000006228 supernatant Substances 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- 230000009919 sequestration Effects 0.000 claims description 9
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 8
- 239000000292 calcium oxide Substances 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 235000019270 ammonium chloride Nutrition 0.000 claims description 5
- 239000000908 ammonium hydroxide Substances 0.000 claims description 5
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 claims description 5
- 229910000020 calcium bicarbonate Inorganic materials 0.000 claims description 5
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 5
- 239000000920 calcium hydroxide Substances 0.000 claims description 5
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 5
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 238000004137 mechanical activation Methods 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- 230000008878 coupling Effects 0.000 claims description 2
- 238000010168 coupling process Methods 0.000 claims description 2
- 238000005859 coupling reaction Methods 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 13
- 229910052791 calcium Inorganic materials 0.000 abstract description 13
- 238000005265 energy consumption Methods 0.000 abstract description 10
- 238000007599 discharging Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 description 15
- 239000002893 slag Substances 0.000 description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 235000012255 calcium oxide Nutrition 0.000 description 7
- 238000012544 monitoring process Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 239000013043 chemical agent Substances 0.000 description 4
- 238000006477 desulfuration reaction Methods 0.000 description 4
- 230000023556 desulfurization Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000005431 greenhouse gas Substances 0.000 description 4
- 239000002910 solid waste Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 230000008092 positive effect Effects 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229940058020 2-amino-2-methyl-1-propanol Drugs 0.000 description 1
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229940043430 calcium compound Drugs 0.000 description 1
- 150000001674 calcium compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/80—Semi-solid phase processes, i.e. by using slurries
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/62—Carbon oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0053—Details of the reactor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0053—Details of the reactor
- B01J19/0066—Stirrers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/18—Stationary reactors having moving elements inside
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/40—Alkaline earth metal or magnesium compounds
- B01D2251/404—Alkaline earth metal or magnesium compounds of calcium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention relates to a method for mineralizing and sequestering CO 2 based on shale vanadium extraction tailings. The technical proposal is as follows: two or one 'reactor for mineralizing and sealing CO 2 for extracting vanadium tailings' (hereinafter referred to as a reactor) are adopted for continuous or intermittent mineralizing and sealing. The continuous mineralization and sealing method is as follows: adding mineralizer into the first reactor, setting reaction temperature, stirring the mineralizer, introducing waste gas containing CO 2 into the aerator (13) through the air inlet pipe (9), opening the gas detector (16), and setting the concentration of CO 2 in the mineralized gas. Continuously stirring, and starting a second reactor to perform the step 1.2 when the concentration of CO 2 in the mineralized gas is close to a set value; when the concentration of CO 2 in the mineralized gas reaches a set value, the second reactor executes the steps 1.3-1.8; closing the first reactor and discharging the saturated mineralizer; the mineralization sealing process of the second reactor is the same as that of the first reactor. The batch mineralization seal is the same as the first reactor. The invention is environment-friendly, low in energy consumption and high in calcium utilization rate, and can continuously mineralize and seal CO 2 waste gas, and mineralized products are stable.
Description
Technical Field
The invention belongs to the technical field of mineralized and sequestered CO 2. In particular to a method for mineralizing and sequestering CO 2 based on shale vanadium extraction tailings.
Background
The emission of greenhouse gases continues to increase with the increase of fossil fuel consumption, which is an irreplaceable process in industrial production and people living. The annual increasing emissions of greenhouse gases will lead to more extreme weather and have a wide impact on the environment, economy and mankind. It is important to find a solution on an industrial scale to minimize the concentration of carbon dioxide in the atmosphere. Capturing and storing carbon dioxide using solid waste is a very promising strategy for controlling industrial carbon emissions. The most important reason is that most of the industrial solid waste is generated near the CO 2 emission source, and is not required to be mined, so that the purpose of direct utilization is more easily achieved. Shale vanadium extraction tailings are a main source of industrial solid wastes for extracting vanadium, and each ton of vanadium pentoxide is extracted, 120-150 tons of vanadium tailings are released. The vanadium tailings contain calcium compounds, so that the vanadium tailings have the potential and value of sequestering CO 2.
The patent technology of a method for regenerating CO 2 trapping solvent from desulfurization slag (CN 111298616A) is characterized in that desulfurization slag reacts with CO 2 -loaded trapping solvent, CO 2 in the trapping solvent mineralizes with calcium-containing components in the desulfurization slag, calcium carbonate and fresh trapping solvent are generated by the reaction, and effective utilization of the calcium-containing components in the solid waste desulfurization slag is realized, but the trapping solvent used in the method is organic amine comprising one or more of ethanolamine, diethanolamine, methyldiethanolamine and 2-amino-2-methyl-1 propanol, belongs to dangerous chemicals and has certain toxicity and corrosiveness, so that the method is poor in environmental friendliness.
The patent technology of a method for trapping carbon dioxide in flue gas by using renewable carbide slag (CN201010608692. X) is characterized in that carbide slag is calcined at high temperature to obtain quicklime, and then the quicklime reacts with CO 2 to mineralize and fix the quicklime. The process needs high-temperature calcination of the raw materials, and the highest temperature can reach 1100 ℃, so that the energy consumption in the calcination process is high, and the cost of mineralized CO 2 is high.
The technology of the patent of a method for efficiently capturing carbon dioxide in flue gas by using potassium carbonate (CN 201810688810.9) has the advantages that the technology is simple, the used potassium carbonate solution can be recycled, but the method uses the potassium carbonate solution to absorb CO 2, then another CO 2 collecting and storing device is needed to store the heated and released gas, the CO 2 gas is not stably mineralized, and other treatment means are still needed in the follow-up, so that the risk of CO 2 gas leakage exists.
The patent technology of 'method for mineralizing and fixing CO 2 by using calcium-rich waste liquid' (CN 103521056A) is characterized in that an extractant prepared from insoluble organic amine is added into the calcium-rich waste liquid according to the volume ratio of 1-4:1 to prepare a mineralizer, and mineralizing and fixing CO 2 are carried out.
In summary, the existing method for sequestering CO 2 has the problems of being not friendly to the environment, high in energy consumption, high in cost, unstable in product, low in calcium utilization rate, and the like.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and aims to provide a method for mineralizing and sequestering CO 2 based on shale vanadium extraction tailings, which is environment-friendly, low in energy consumption, low in cost and high in calcium utilization rate, and by the method, continuous mineralization of waste gas containing CO 2 can be realized, so that the method is suitable for various working environments, and mineralization products are stable.
In order to achieve the above purpose, the invention adopts the following technical scheme: the two same reactors for mineralizing and sealing CO 2 of the vanadium extraction tailings are adopted for alternating continuous mineralization sealing, or the independent reactors for mineralizing and sealing CO 2 of the vanadium extraction tailings are adopted for intermittent mineralization sealing.
For convenience of description, the "reactor for mineralizing and sequestering CO 2 from vanadium extraction tailings" is simply referred to as "reactor".
Method for mineralizing and sequestering CO 2
The first mineralized and sequestered CO 2 method is to use two identical reactors to work alternately and continuously:
step 1, mineralization and sealing process of a first reactor
Step 1.1, opening a regulating valve (2) of the reactor, and placing the mineralizer into the reactor body (6) through a feed hopper (1) of the reactor according to the volume ratio of the mineralizer to the volume of the reactor body (6) of 0.2-0.8:1.
And 1.2, starting a temperature control system (21) of the reactor, setting the reaction temperature of the mineralizer, wherein the reaction temperature of the mineralizer is between room temperature and 95 ℃. If the reaction temperature of the mineralizer is set to be room temperature, the step 1.3 is directly carried out. If the reaction temperature of the mineralizer is higher than the room temperature, the C2 end of the normally open contact S2 of the alternating current contactor (23) is connected with the Y2 end of the electric stove wire (8). And (3) obtaining electricity from the electric stove wire (8), and performing step 1.3.
And 1.3, starting a motor (19), and stirring the mineralizing agent by a stirrer (12) at a rotating speed of 150-600 r/min.
When the stirrer (12) starts to work, the first check valve (3) and the second check valve (20) are opened, waste gas containing CO 2 is respectively introduced into the first air inlet pipe (9) and the second air inlet pipe (18), the flow rate of the introduced waste gas containing CO 2 is 1-25L/min, and the introduced waste gas containing CO 2 is mixed with the stirred mineralizer in the reactor body (6) through the aerator (13).
And 1.5, when the waste gas containing CO 2 is introduced, opening a gas detector (16) of the reactor, setting the concentration of CO 2 in the mineralized gas to be 0.1-2 Vol, and monitoring the concentration of CO 2 in the mineralized gas in the reactor body (6) in real time.
And step 1.6, continuously introducing waste gas containing CO 2 under the condition of continuous stirring.
And 1.7, when the gas detector (16) detects that the concentration of CO 2 in the mineralized gas reaches a set value, closing the temperature control system (21), the motor (19), the first check valve (3) and the second check valve (20), and stopping introducing the waste gas containing CO 2.
And 1.8, opening a discharge valve (10) of the reactor, and discharging the saturated mineralizer in the reactor body (6).
Step 2, alternative mineralization and sealing process of two reactors
Step 2.1, the second reactor performs step 1.1 until step 1.2.
The second reactor is operated for the time of step 1.1 when the gas detector (16) detects that the concentration of CO 2 in the gas after mineralization of the first reactor is close to the set value.
Step 2.2, the second reactor executes step 1.3 until step 1.8.
The time for the second reactor to start performing step 1.3 is: when the concentration of CO 2 in the gas after mineralization of the first reactor reaches the set value, the first reactor will perform step 1.7, so as to continuously mineralize and seal the waste gas containing CO 2.
Step 2.3, before the second reactor performs step 1.7, the first reactor repeatedly performs step 1.3 until step 1.8.
And 2.4, repeatedly executing the steps 2.1-2.3.
Second method for mineralizing and sequestering CO 2
The second mineralized and sequestered CO 2 method adopts a reactor to mineralize and sequester intermittently, and the intermittent mineralized and sequestered reactor is the same as the step 1 in the first mineralized and sequestered CO 2 method.
And (3) discharging the saturated mineralizer in the step 1.8 in the two mineralization and sequestration CO 2 methods, and then carrying out solid-liquid separation on the saturated mineralizer to obtain filter residues and filtrate. And drying the filter residues to obtain the calcium carbonate-containing slag for sealing the CO 2. And regulating the pH value of the filtrate to 7-9 by using dilute sulfuric acid, evaporating, crystallizing and drying to obtain an ammonium sulfate product.
The preparation method of the mineralizer in the two methods for mineralizing and sequestering CO 2 comprises the following steps:
Adjusting the pH value of shale vanadium extraction tailing slurry to 7-8 by using an alkaline regulator, oscillating for 0.5-6 h, and carrying out solid-liquid separation to obtain shale vanadium extraction tailing and supernatant.
Step two, drying shale vanadium extraction tailings for 4 to 12 hours at the temperature of between 60 and 120 ℃, and then placing the shale vanadium extraction tailings in grinding equipment for mechanical activation for 5 to 30 seconds to obtain activated tailings; and then mixing the supernatant with the activated tailings according to the liquid-solid ratio of (1-5) m 3/Kg to obtain the activated tailings.
Thirdly, adding the ammonia nitrogen waste liquid into the activated tail slurry according to the ratio of the amount of N in the ammonia nitrogen waste liquid to the amount of S in the activated tail slurry of (0.6-3) to 1, and sealing; and carrying out ultrasonic treatment for 5-50 min under the condition of 40-100 kHz to obtain the CO 2 mineralizer based on shale vanadium extraction tailings and ammonia nitrogen waste liquid, which is called mineralizer for short.
The structure of the reactor in the two methods for mineralizing and sequestering CO 2 is as follows:
the reactor comprises a reactor body, a cover plate, a feed pipe, an electric furnace wire, a stirrer, an aerator, a gas detector, a temperature sensor and a temperature control system.
The reactor body is cylindrical, the port of the reactor body is fixedly connected with the cover plate through a bolt, and a sealing ring is arranged between the port of the reactor body and the cover plate. The outer surfaces of the circular wall and the bottom of the reactor body are coated with insulators, and electric furnace wires are arranged between the insulators and the reactor body.
A motor is arranged at the middle position of the upper surface of the cover plate, a round pipe is vertically fixed at the middle position of the lower surface of the cover plate, and the lower end of the round pipe passes through the aerator and is fixedly connected with the middle position of the bottom plate of the aerator; an output shaft of the motor is connected with an upper end shaft of the stirring shaft through a shaft coupling, the lower end of the stirring shaft penetrates through a lower port of the circular tube to be connected with the stirring shaft, and the upper end of the circular tube and the inner wall of the lower end of the circular tube are respectively and movably connected with the stirring shaft through bearings; the upper end of the circular tube is fixedly connected with the cover plate in a sealing way, and the lower part of the circular tube is fixedly connected with the top plate of the aerator and the bottom plate of the aerator in a sealing way respectively.
The upper flat plate center of the aerator is symmetrically fixed with a first air inlet pipe and a second air inlet pipe, the lower ends of the first air inlet pipe and the second air inlet pipe are respectively communicated with the inner cavity of the aerator, and the upper ends of the first air inlet pipe and the second air inlet pipe penetrate through the cover plate and are respectively communicated with an external air source.
The cover plate is respectively fixed with a temperature sensor and a feeding pipe; the temperature measuring end of the temperature sensor extends to the inner cavity of the reactor body, and the wiring end of the temperature sensor is externally connected with a temperature control system; the upper end of the feed pipe passes through the cover plate and is communicated with the feed hopper, the lower end of the feed pipe extends to the inner cavity of the reactor body, and the upper part of the feed pipe is provided with a regulating valve; the wall surface of the reactor body is provided with a gas detector, the gas inlet of the gas detector is communicated with the inner cavity of the reactor body, and the gas outlet of the gas detector is communicated with the atmosphere.
A discharge pipe is arranged at the bottom close to the reactor body, and is provided with a discharge valve.
The temperature control system comprises a temperature instrument and an alternating current contactor; the power ports L3 and L4 of the temperature instrument are connected with the corresponding live wire and zero line, the L2 end of the normally open contact S1 of the temperature instrument is connected with the live wire, the L1 end of the normally open contact S1 is connected with the T1 end of the alternating current contactor, and the T2 end of the alternating current contactor is connected with the zero line; the end A1 and the end A2 of the temperature instrument are connected with two leads of the non-temperature measuring end of the temperature sensor; the C2 end of the normally open contact S2 of the alternating current contactor is connected with the Y2 end of the electric stove wire, the C1 end of the alternating current contactor is connected with the live wire, and the Y1 end of the electric stove wire is connected with the zero wire.
The technical scheme is as follows:
The liquid-solid ratio of the shale vanadium extraction tailing pulp is (1-5) m 3/Kg; the Ca content in the solids of the shale vanadium extraction tailing pulp is more than 5 weight percent.
The alkaline regulator is one or more of calcium hydroxide, calcium oxide and calcium bicarbonate.
The chemical components of the ammonia nitrogen waste liquid are more than one of ammonium sulfate, ammonium chloride, ammonia water and ammonium hydroxide; the pH value of the ammonia nitrogen waste liquid is more than 7.
The first air inlet pipe and the second air inlet pipe are correspondingly provided with a first check valve and a second check valve.
The distance from the blades of the stirrer to the bottom plate of the reactor body is 0.1-0.2 times of the height of the inner cavity of the reactor body, and the radius of the blades of the stirrer is 0.5-0.7 times of the radius of the inner cavity of the reactor body.
The distance between the lower surface of the aerator and the blades of the stirrer is 0.08-0.15 times of the height of the inner cavity of the reactor, and the distance from the outer side surface of the aerator to the side surface of the inner cavity of the reactor body is 0.15-0.25 times of the diameter of the reactor body.
The lower ports of the first air inlet pipe and the second air inlet pipe are positioned at the position 0.25-0.5 times of the height of the inner cavity of the aerator.
By adopting the technical scheme, compared with the prior art, the invention has the following positive effects:
1. The method adopts the shale vanadium extraction tailings, the ammonia nitrogen waste liquid and the alkaline regulator to prepare the CO 2 mineralizer (mineralizer for short) based on the shale vanadium extraction tailings and the ammonia nitrogen waste liquid, and the raw materials do not contain dangerous chemicals, so that the preparation process is environment-friendly; the shale vanadium extraction tailings and the ammonia nitrogen waste liquid are recycled, and the mineralizer capable of mineralizing and fixing the greenhouse gas CO 2 is prepared, so that not only is the resource recycled, but also carbon emission reduction is realized, and the environment is friendly.
2. The method does not need high-energy-consumption pretreatment operations such as high-temperature roasting, high-temperature leaching, heating concentration and the like on the raw materials before the mineralizer is prepared, and has the characteristic of low energy consumption.
3. The raw materials used for preparing the mineralizer are all wastes generated in the vanadium extraction process. In the process of preparing the mineralizer, the alkaline regulator is only used under the condition that the pH value of the raw material is less than 7, and if the pH value of the raw material is more than 7, the alkaline regulator is not needed. In the process of preparing the mineralizer, other chemical agents are not added, and the raw materials do not need to be pretreated by using the chemical agents. Therefore, the invention has extremely low medicament consumption and extremely low mineralizer preparation cost.
4. The invention mineralizes and fixes the waste gas containing CO 2, and the mineralized and fixed product is calcium carbonate (CaCO 3).CaCO3) which has very stable property under the normal temperature condition, is almost insoluble in water and alcohol, has good thermal stability and does not decompose below 500 ℃, thus the invention can realize stable sealing and storage of CO 2.
5. The structure of the reactor (for short, the reactor) for mineralizing and sealing CO 2 in the vanadium extraction tailings adopted by the invention is as follows: an insulator (7) is coated on the outer surface of the reactor body (6), an electric furnace wire (8) is arranged between the insulator (7) and the reactor body (6), and a gas detector (16) is arranged on the reactor body (6). A circular tube (15) is fixed in the middle of the cover plate (5), and the lower end of the circular tube (15) is fixedly connected with the middle position of the bottom plate of the aerator (13); the upper end of a stirring shaft (14) penetrating through the round tube (15) is connected with an output shaft of a motor (19), and the lower end of the stirring shaft is connected with a stirring paddle (12) in a shaft way. The lower ends of the two air inlet pipes are communicated with the inner cavity of the aerator (13), and the upper ends of the two air inlet pipes are communicated with an external air source. The upper end of the feed pipe (4) is communicated with the feed hopper (1), and the lower end of the feed pipe stretches into the inner cavity of the reactor body (6); the temperature sensor (17) arranged on the cover plate (5) is connected with the temperature control system (21). The reactor has the characteristics of strong raw material adaptability, wide environmental temperature adaptability, high mineralization efficiency and capability of monitoring the content of CO 2 in mineralized gas in real time.
6. According to the invention, the aerator (13) arranged in the reactor body (6) is connected with the first air inlet pipe (9) and the second air inlet pipe (18), so that waste gas containing CO 2 is formed into small bubbles through the aerator (13) to be fully contacted with mineralizer in the reactor body (6), the contact area of gas, solid and liquid phases is increased, and meanwhile, the effects of mixing and stirring are also achieved. According to the invention, the stirrer (12) is arranged in the reactor body (6), so that solid particles in the mineralizer are always in a suspension state, and the mixing effect of the mineralizer and the gas containing CO 2 is enhanced. The combined action of the aerator (13) and the stirrer (12) improves the mineralization fixing efficiency of the mineralizing agent on CO 2 in the waste gas, so that the utilization rate of calcium in the mineralizing agent can reach 99 percent, and the utilization rate of the calcium is high.
7. The invention can adopt two identical reactors to carry out alternating continuous mineralization and sealing of CO 2 waste gas, effectively improves the efficiency of mineralization and sealing of CO 2 waste gas, is easy to realize mechanization and automation, and has the advantages of large industrialization potential and large-scale implementation. The invention can also adopt one reactor to carry out intermittent mineralization and sealing of CO 2 waste gas, can realize periodic batch sealing of CO 2 waste gas, can dynamically adjust various parameters in the mineralization process, and has the characteristics of investment saving and small occupied area. Therefore, the invention can realize continuous mineralization and sealing of CO 2 waste gas and intermittent mineralization and sealing of CO 2 waste gas, and is suitable for different working environments.
Therefore, the invention has the characteristics of environmental protection, low energy consumption, low cost and high calcium utilization rate, can realize continuous or intermittent mineralization and sealing of CO 2 waste gas, is suitable for different working environments, and has stable mineralization products.
Drawings
FIG. 1 is a schematic diagram of a structure of a reactor for mineralizing and sequestering CO 2 from vanadium extraction tailings, which is adopted in the invention;
Fig. 2 is a schematic diagram of the temperature control system 21 of fig. 1.
Detailed Description
The invention is further described in connection with the drawings and the detailed description which follow, without limiting the scope thereof.
In this embodiment:
the Ca content in the solid of the shale vanadium extraction tailing pulp is more than 5wt%;
The pH value of the ammonia nitrogen waste liquid is more than 7.
The first air inlet pipe and the second air inlet pipe are correspondingly provided with a first check valve and a second check valve.
The embodiments are not described in detail.
Example 1
A mineralization and sequestration method of CO 2 based on shale vanadium extraction tailings. The method for mineralizing and sealing CO 2 in the embodiment is to adopt two identical reactors for mineralizing and sealing CO 2 in the vanadium extraction tailings for alternating continuous mineralization and sealing.
For convenience of description, the "reactor for mineralizing and sequestering CO 2 from vanadium extraction tailings" is simply referred to as "reactor".
Method for mineralizing and sequestering CO 2
The first mineralized and sequestered CO 2 method is to use two identical reactors to work alternately and continuously:
step 1, mineralization and sealing process of a first reactor
Step 1.1, opening a regulating valve (2) of the reactor, and placing the mineralizer into the reactor body (6) through a feed hopper (1) of the reactor according to the volume ratio of the mineralizer to the volume of the reactor body (6) of 0.4-0.6:1.
And 1.2, starting a temperature control system (21) of the reactor, setting the reaction temperature of the mineralizer, wherein the reaction temperature of the mineralizer is between room temperature and 65 ℃. The C2 end of the normally open contact S2 of the alternating current contactor (23) is connected with the Y2 end of the electric stove wire (8). The electric stove wire (8) is powered.
And 1.3, starting a motor (19), and stirring the mineralizing agent by a stirrer (12) at a rotating speed of 300-450 r/min.
When the stirrer (12) starts to work, the first check valve (3) and the second check valve (20) are opened, waste gas containing CO 2 is respectively introduced into the first air inlet pipe (9) and the second air inlet pipe (18), the flow rate of the introduced waste gas containing CO 2 is 12-20L/min, and the introduced waste gas containing CO 2 is mixed with the stirred mineralizer in the reactor body (6) through the aerator (13).
And 1.5, when the waste gas containing CO 2 is introduced, opening a gas detector (16) of the reactor, setting the concentration of CO 2 in the mineralized gas to be 0.8-1.5 Vol, and monitoring the concentration of CO 2 in the mineralized gas in the reactor body (6) in real time.
And step 1.6, continuously introducing waste gas containing CO 2 under the condition of continuous stirring.
And 1.7, when the gas detector (16) detects that the concentration of CO 2 in the mineralized gas reaches a set value, closing the temperature control system (21), the motor (19), the first check valve (3) and the second check valve (20), and stopping introducing the waste gas containing CO 2.
And 1.8, opening a discharge valve (10) of the reactor, and discharging the saturated mineralizer in the reactor body (6).
Step 2, alternative mineralization and sealing process of two reactors
Step 2.1, the second reactor performs step 1.1 until step 1.2.
The second reactor is operated for the time of step 1.1 when the gas detector (16) detects that the concentration of CO 2 in the gas after mineralization of the first reactor is close to the set value.
Step 2.2, the second reactor executes step 1.3 until step 1.8.
The time for the second reactor to start performing step 1.3 is: when the concentration of CO 2 in the gas after mineralization of the first reactor reaches the set value, the first reactor will perform step 1.7, so as to continuously mineralize and seal the waste gas containing CO 2.
Step 2.3, before the second reactor performs step 1.7, the first reactor repeatedly performs step 1.3 until step 1.8.
And 2.4, repeatedly executing the steps 2.1-2.3.
And (3) after the saturated mineralizer in the step (1.8) is discharged, carrying out solid-liquid separation on the saturated mineralizer to obtain filter residues and filtrate. And drying the filter residues to obtain the calcium carbonate-containing slag for sealing the CO 2. And regulating the pH value of the filtrate to 8-8.5 by using dilute sulfuric acid, evaporating, crystallizing and drying to obtain an ammonium sulfate product.
The preparation method of the mineralizer in the two methods for mineralizing and sequestering CO 2 comprises the following steps:
Adjusting the pH value of shale vanadium extraction tailing slurry to 7-8 by using an alkaline regulator, oscillating for 2.5-4.5 h, and carrying out solid-liquid separation to obtain shale vanadium extraction tailing and supernatant.
Step two, drying shale vanadium extraction tailings for 6 to 9 hours at the temperature of 80 to 100 ℃, and then placing the shale vanadium extraction tailings in grinding equipment for mechanical activation for 15 to 25 seconds to obtain activated tailings; and then mixing the supernatant with the activated tailings according to the liquid-solid ratio of (1-3) m 3/Kg to obtain the activated tailings.
Thirdly, adding the ammonia nitrogen waste liquid into the activated tail slurry according to the ratio of the amount of N in the ammonia nitrogen waste liquid to the amount of S in the activated tail slurry of (1.2-2) to 1, and sealing; and carrying out ultrasonic treatment for 20-35 min under the condition of 60-80 kHz to obtain the CO 2 mineralizer based on shale vanadium extraction tailings and ammonia nitrogen waste liquid, which is called mineralizer for short.
The structure of the reactor in the two methods for mineralizing and sequestering CO 2 is as follows:
The reactor is shown in fig. 1, and comprises a reactor body 6, a cover plate 5, a feed pipe 4, a wire heater 8, a stirrer 12, an aerator 13, a gas detector 16, a temperature sensor 17 and a temperature control system 21.
As shown in fig. 1, the reactor body 6 is cylindrical, the port of the reactor body 6 is fixedly connected with the cover plate 5 through bolts, and a sealing ring is arranged between the port of the reactor body 6 and the cover plate 5. The outer surfaces of the circular wall and the bottom of the reactor body 6 are coated with insulators 7, and electric furnace wires 8 are arranged between the insulators 7 and the reactor body 6.
As shown in fig. 1, a motor 19 is installed at the middle position of the upper surface of the cover plate 5, a round tube 15 is vertically fixed at the middle position of the lower surface of the cover plate 5, and the lower end of the round tube 15 passes through the aerator 13 and is fixedly connected with the middle position of the bottom plate of the aerator 13. An output shaft of the motor 19 is connected with the upper end shaft of the stirring shaft 14 through a coupler, the lower end of the stirring shaft 14 penetrates through the lower port of the circular tube 15 to be connected with the stirrer 12 through a shaft, and the upper end and the inner wall of the lower end of the circular tube 15 are respectively and movably connected with the stirring shaft 14 through bearings. The upper end of the circular tube 15 is fixedly connected with the cover plate 5 in a sealing way, and the lower part of the circular tube 15 is fixedly connected with the top plate of the aerator 13 and the bottom plate of the aerator 13 in a sealing way respectively.
As shown in fig. 1, a first air inlet pipe 9 and a second air inlet pipe 18 are symmetrically fixed at the center of an upper flat plate of the aerator 13, the lower ends of the first air inlet pipe 9 and the second air inlet pipe 18 are respectively communicated with the inner cavity of the aerator 13, and the upper ends of the first air inlet pipe 9 and the second air inlet pipe 18 penetrate through the cover plate 5 and are respectively communicated with an external air source.
As shown in fig. 1, the cover plate 5 is fixed with a temperature sensor 17 and the feed pipe 4, respectively. The temperature measuring end of the temperature sensor 17 extends to the inner cavity of the reactor body 6, and the wiring end of the temperature sensor 17 is externally connected with a temperature control system 21; the upper end of the feed pipe 4 passes through the cover plate 5 to be communicated with the feed hopper 1, the lower end of the feed pipe 4 extends to the inner cavity of the reactor body 6, and the upper part of the feed pipe 4 is provided with the regulating valve 2.
As shown in fig. 1, a gas detector 16 is installed on the wall surface of the reactor body 6, the gas inlet of the gas detector 16 is communicated with the inner cavity of the reactor body 6, and the gas outlet of the gas detector 16 is communicated with the atmosphere.
As shown in fig. 1, a discharge pipe 11 is installed near the bottom of the reactor body 6, and the discharge pipe 11 is provided with a discharge valve 10.
As shown in fig. 1, the temperature control system 21 includes a temperature meter 22 and an ac contactor 23. The power ports L3 and L4 of the temperature instrument 22 are connected with the corresponding live wire and zero line, the L2 end of the normally open contact S1 of the temperature instrument 22 is connected with the live wire, the L1 end of the normally open contact S1 is connected with the T1 end of the alternating current contactor 23, and the T2 end of the alternating current contactor 23 is connected with the zero line. The A1 end and the A2 end of the temperature meter 22 are connected with two leads of a non-temperature measuring end of the temperature sensor 17. The C2 end of the normally open contact S2 of the alternating current contactor 23 is connected with the Y2 end of the electric stove wire 8, the C1 end of the alternating current contactor 23 is connected with a live wire, and the Y1 end of the electric stove wire 8 is connected with a zero wire.
As shown in fig. 1, the first air inlet pipe 9 and the second air inlet pipe 18 are correspondingly provided with a first check valve 3 and a second check valve 20.
The distance from the blades of the stirrer 12 to the bottom plate of the reactor body 6 is 0.1 time of the height of the inner cavity of the reactor body 6, and the radius of the blades of the stirrer 12 is 0.5 time of the radius of the inner cavity of the reactor body 6.
The distance between the lower surface of the aerator 13 and the blades of the stirrer 12 is 0.08 times of the height of the inner cavity of the reactor, and the distance from the outer side surface of the aerator 13 to the side surface of the inner cavity of the reactor body 6 is 0.15 times of the diameter of the reactor body 6.
The lower ports of the first air inlet pipe 9 and the second air inlet pipe 18 are positioned at 0.25 times of the height of the inner cavity of the aerator 13.
The liquid-solid ratio of the shale vanadium extraction tailing pulp is (1-3) m 3/Kg.
The alkaline regulator is one of calcium hydroxide, calcium oxide and calcium bicarbonate.
The chemical component of the ammonia nitrogen waste liquid is one of ammonium sulfate, ammonium chloride, ammonia water and ammonium hydroxide.
Example 2
A mineralization and sequestration method of CO 2 based on shale vanadium extraction tailings. The method for mineralizing and sequestering CO 2 in this embodiment is the same as that of embodiment 1 except for the following technical parameters:
Step 1.1, opening a regulating valve (2) of the reactor, and placing the mineralizer into the reactor body (6) through a feed hopper (1) of the reactor according to the volume ratio of the mineralizer to the volume of the reactor body (6) of 0.6-0.8:1.
Step 1.2, starting a temperature control system (21) of the reactor, setting the reaction temperature of the mineralizer, wherein the reaction temperature of the mineralizer is 65-95 ℃.
And 1.3, starting a motor (19), and stirring the mineralizing agent by a stirrer (12) at the rotating speed of 450-600 r/min.
And step 1.4, the flow rate of the introduced waste gas containing CO 2 is 1-25L/min, and the introduced waste gas containing CO 2 is mixed with the stirred mineralizer in the reactor body (6) through the aerator (13).
And 1.5, when the waste gas containing CO 2 is introduced, opening a gas detector (16) of the reactor, setting the concentration of CO 2 in the mineralized gas to be 0.1-0.8 Vol, and monitoring the concentration of CO 2 in the mineralized gas in the reactor body (6) in real time.
And regulating the pH value of the filtrate to 8.5-9 by using dilute sulfuric acid, evaporating, crystallizing and drying to obtain an ammonium sulfate product.
The preparation method of the mineralizer in the two methods for mineralizing and sequestering CO 2 comprises the following steps:
Adjusting the pH value of shale vanadium extraction tailing slurry to 7-8 by using an alkaline regulator, oscillating for 4.5-6 h, and carrying out solid-liquid separation to obtain shale vanadium extraction tailing and supernatant.
Step two, drying shale vanadium extraction tailings for 4 to 7 hours at the temperature of between 100 and 120 ℃, and then placing the shale vanadium extraction tailings in grinding equipment for mechanical activation for 22 to 30 seconds to obtain activated tailings; and then mixing the supernatant fluid obtained in the step one with the activated tailings according to the liquid-solid ratio of (4-5) m 3/Kg to obtain the activated tailings.
Thirdly, adding the ammonia nitrogen waste liquid into the activated tail slurry according to the ratio of the amount of N in the ammonia nitrogen waste liquid to the amount of S in the activated tail slurry being (2-3) to 1, sealing, and carrying out ultrasonic treatment for 35-50 min under the condition of 80-100 kHz to obtain the CO 2 mineralizer based on shale vanadium extraction tail slag and the ammonia nitrogen waste liquid, namely the mineralizer.
The reactor in the two methods for mineralizing and sequestering CO 2 described above was the same as in example 1 except for the following technical parameters:
The distance from the blades of the stirrer 12 to the bottom plate of the reactor body 6 is 0.2 times of the height of the inner cavity of the reactor body 6, and the radius of the blades of the stirrer 12 is 0.7 times of the radius of the inner cavity of the reactor body 6.
The distance between the lower surface of the aerator 13 and the blades of the stirrer 12 is 0.15 times of the height of the inner cavity of the reactor, and the distance from the outer side surface of the aerator 13 to the side surface of the inner cavity of the reactor body 6 is 0.25 times of the diameter of the reactor body 6.
The lower ports of the first air inlet pipe 9 and the second air inlet pipe 18 are positioned at 0.5 times of the height of the inner cavity of the aerator 13.
The liquid-solid ratio of the shale vanadium extraction tailing pulp is (2-3) m 3/Kg.
The alkaline regulator is two of calcium hydroxide, calcium oxide and calcium bicarbonate.
The chemical components of the ammonia nitrogen waste liquid are two of ammonium sulfate, ammonium chloride, ammonia water and ammonium hydroxide.
Example 3
A mineralization and sequestration method of CO 2 based on shale vanadium extraction tailings. The method for mineralizing and sequestering CO 2 in this example is to use a separate "reactor for mineralizing and sequestering CO 2 in the tailings of vanadium extraction" to perform intermittent mineralizing and sequestering. The mineralization and sequestration process for the individual reactors is the same as in step 1 of example 1, except for the following technical parameters:
step 1.1, opening a regulating valve (2) of the reactor, and placing the mineralizer into the reactor body (6) through a feed hopper (1) of the reactor according to the volume ratio of the mineralizer to the volume of the reactor body (6) of 0.2-0.4:1.
And 1.2, starting a temperature control system (21) of the reactor, setting the reaction temperature of the mineralizer, wherein the reaction temperature of the mineralizer is room temperature. And 1.3, starting a motor (19), and stirring the mineralizing agent by a stirrer (12) at a rotating speed of 150-300 r/min.
When the stirrer (12) starts to work, the first check valve (3) and the second check valve (20) are opened, waste gas containing CO 2 is respectively introduced into the first air inlet pipe (9) and the second air inlet pipe (18), the flow rate of the introduced waste gas containing CO 2 is 1-12L/min, and the introduced waste gas containing CO 2 is mixed with the stirred mineralizer in the reactor body (6) through the aerator (13).
And 1.5, when the waste gas containing CO 2 is introduced, opening a gas detector (16) of the reactor, setting the concentration of CO 2 in the mineralized gas to be 1.5-2 Vol, and monitoring the concentration of CO 2 in the mineralized gas in the reactor body (6) in real time.
And regulating the pH value of the filtrate to 7-8 by using dilute sulfuric acid, evaporating, crystallizing and drying to obtain an ammonium sulfate product.
The preparation method of the mineralizer in the two methods for mineralizing and sequestering CO 2 comprises the following steps:
adjusting the pH value of shale vanadium extraction tailing slurry to 7-8 by using an alkaline regulator, oscillating for 0.5-2.5 h, and carrying out solid-liquid separation to obtain shale vanadium extraction tailing and supernatant.
Step two, drying shale vanadium extraction tailings for 9 to 12 hours at the temperature of between 60 and 80 ℃, and then placing the shale vanadium extraction tailings in grinding equipment for mechanical activation for 5 to 15 seconds to obtain activated tailings; and then mixing the supernatant with the activated tailings according to the liquid-solid ratio of (3-4) m 3/Kg to obtain the activated tailings.
Thirdly, adding the ammonia nitrogen waste liquid into the activated tail slurry according to the ratio of the amount of N in the ammonia nitrogen waste liquid to the amount of S in the activated tail slurry being (0.6-1.5) to 1, sealing, and carrying out ultrasonic treatment for 5-20 min under the condition of 40-60 kHz to obtain the CO 2 mineralizer based on the shale vanadium extraction tail slag and the ammonia nitrogen waste liquid, which is called mineralizer for short.
The structure of the reactor in the two methods for mineralizing and sequestering CO 2 is as follows:
the reactor was the same as in example 1 except for the following technical parameters:
The distance from the blades of the stirrer 12 to the bottom plate of the reactor body 6 is 0.15 times of the height of the inner cavity of the reactor body 6, and the radius of the blades of the stirrer 12 is 0.60 times of the radius of the inner cavity of the reactor body 6.
The distance between the lower surface of the aerator 13 and the blades of the stirrer 12 is 0.10 times of the height of the inner cavity of the reactor, and the distance from the outer side surface of the aerator 13 to the side surface of the inner cavity of the reactor body 6 is 0.20 times of the diameter of the reactor body 6.
The lower ports of the first air inlet pipe 9 and the second air inlet pipe 18 are positioned at 0.35 times of the height of the inner cavity of the aerator 13.
The liquid-solid ratio of the shale vanadium extraction tailing pulp is (3-4) m 3/Kg.
The alkaline regulator is a compound of three substances of calcium hydroxide, calcium oxide and calcium bicarbonate.
The chemical components of the ammonia nitrogen waste liquid are compounds of three or four substances of ammonium sulfate, ammonium chloride, ammonia water and ammonium hydroxide.
By adopting the technical scheme, compared with the prior art, the invention has the following positive effects:
1. The method adopts the shale vanadium extraction tailings, the ammonia nitrogen waste liquid and the alkaline regulator to prepare the CO 2 mineralizer (mineralizer for short) based on the shale vanadium extraction tailings and the ammonia nitrogen waste liquid, and the raw materials do not contain dangerous chemicals, so that the preparation process is environment-friendly; the shale vanadium extraction tailings and the ammonia nitrogen waste liquid are recycled, and the mineralizer capable of mineralizing and fixing the greenhouse gas CO 2 is prepared, so that not only is the resource recycled, but also carbon emission reduction is realized, and the environment is friendly.
2. The method does not need high-energy-consumption pretreatment operations such as high-temperature roasting, high-temperature leaching, heating concentration and the like on the raw materials before the mineralizer is prepared, and has the characteristic of low energy consumption.
3. The raw materials used for preparing the mineralizer are all wastes generated in the vanadium extraction process. In the process of preparing the mineralizer, the alkaline regulator is only used under the condition that the pH value of the raw material is less than 7, and if the pH value of the raw material is more than 7, the alkaline regulator is not needed. In the process of preparing the mineralizer, other chemical agents are not added, and the raw materials do not need to be pretreated by using the chemical agents. Therefore, the invention has extremely low medicament consumption and extremely low mineralizer preparation cost.
4. The invention mineralizes and fixes the waste gas containing CO 2, and the mineralized and fixed product is calcium carbonate (CaCO 3).CaCO3) which has very stable property under the normal temperature condition, is almost insoluble in water and alcohol, has good thermal stability and does not decompose below 500 ℃, thus the invention can realize stable sealing and storage of CO 2.
5. The structure of the reactor (for short, the reactor) for mineralizing and sealing CO 2 in the vanadium extraction tailings adopted by the invention is as follows: an insulator (7) is coated on the outer surface of the reactor body (6), an electric furnace wire (8) is arranged between the insulator (7) and the reactor body (6), and a gas detector (16) is arranged on the reactor body (6). A circular tube (15) is fixed in the middle of the cover plate (5), and the lower end of the circular tube (15) is fixedly connected with the middle position of the bottom plate of the aerator (13); the upper end of a stirring shaft (14) penetrating through the round tube (15) is connected with an output shaft of a motor (19), and the lower end of the stirring shaft is connected with a stirring paddle (12) in a shaft way. The lower ends of the two air inlet pipes are communicated with the inner cavity of the aerator (13), and the upper ends of the two air inlet pipes are communicated with an external air source. The upper end of the feed pipe (4) is communicated with the feed hopper (1), and the lower end of the feed pipe stretches into the inner cavity of the reactor body (6); the temperature sensor (17) arranged on the cover plate (5) is connected with the temperature control system (21). The reactor has the characteristics of strong raw material adaptability, wide environmental temperature adaptability, high mineralization efficiency and capability of monitoring the content of CO 2 in mineralized gas in real time.
6. According to the invention, the aerator (13) arranged in the reactor body (6) is connected with the first air inlet pipe (9) and the second air inlet pipe (18), so that waste gas containing CO 2 is formed into small bubbles through the aerator (13) to be fully contacted with mineralizer in the reactor body (6), the contact area of gas, solid and liquid phases is increased, and meanwhile, the effects of mixing and stirring are also achieved. According to the invention, the stirrer (12) is arranged in the reactor body (6), so that solid particles in the mineralizer are always in a suspension state, and the mixing effect of the mineralizer and the gas containing CO 2 is enhanced. The combined action of the aerator (13) and the stirrer (12) improves the mineralization fixing efficiency of the mineralizing agent on CO 2 in the waste gas, so that the utilization rate of calcium in the mineralizing agent can reach 99 percent, and the utilization rate of the calcium is high.
7. The invention can adopt two identical reactors to carry out alternating continuous mineralization and sealing of CO 2 waste gas, effectively improves the efficiency of mineralization and sealing of CO 2 waste gas, is easy to realize mechanization and automation, and has the advantages of large industrialization potential and large-scale implementation. The invention can also adopt one reactor to carry out intermittent mineralization and sealing of CO 2 waste gas, can realize periodic batch sealing of CO 2 waste gas, can dynamically adjust various parameters in the mineralization process, and has the characteristics of investment saving and small occupied area. Therefore, the invention can realize continuous mineralization and sealing of CO 2 waste gas and intermittent mineralization and sealing of CO 2 waste gas, and is suitable for different working environments.
Therefore, the invention has the characteristics of environmental protection, low energy consumption, low cost and high calcium utilization rate, can realize continuous or intermittent mineralization and sealing of CO 2 waste gas, is suitable for different working environments, and has stable mineralization products.
Claims (8)
1. A method for mineralizing and sequestering CO 2 based on shale vanadium extraction tailings is characterized by comprising the following steps: the method for mineralizing and sealing CO 2 comprises the steps of adopting two identical reactors for mineralizing and sealing CO 2 of the vanadium extraction tailings to perform alternating continuous mineralization and sealing, or adopting a single reactor for mineralizing and sealing CO 2 of the vanadium extraction tailings to perform intermittent mineralization and sealing;
Method for mineralizing and sequestering CO 2
The first mineralized and sequestered CO 2 method is to use two identical reactors to work alternately and continuously:
step 1, mineralization and sealing process of a first reactor
Step 1.1, opening a regulating valve (2) of the reactor, and placing the mineralizer into the reactor body (6) through a feed hopper (1) of the reactor according to the volume ratio of the mineralizer to the volume of the reactor body (6) of 0.2-0.8:1;
Step 1.2, starting a temperature control system (21) of the reactor, setting the reaction temperature of the mineralizer, wherein the reaction temperature of the mineralizer is room temperature to 95 ℃; if the reaction temperature of the mineralizer is set to be room temperature, directly performing the step 1.3; if the reaction temperature of the mineralizer is higher than the room temperature, the C2 end of the normally open contact S2 of the alternating current contactor (23) is connected with the Y2 end of the electric stove wire (8); the electric furnace wire (8) is powered on, and the step 1.3 is carried out;
Step 1.3, starting a motor (19), and stirring the mineralizing agent by a stirrer (12) at a rotating speed of 150-600 r/min;
step 1.4, when the stirrer (12) starts to work, opening a first check valve (3) and a second check valve (20), respectively introducing waste gas containing CO 2 into a first air inlet pipe (9) and a second air inlet pipe (18), wherein the flow rate of the introduced waste gas containing CO 2 is 1-25L/min, and the introduced waste gas containing CO 2 is mixed with the stirred mineralizer in the reactor body (6) through an aerator (13);
step 1.5, when the waste gas containing CO 2 is introduced, a gas detector (16) of the reactor is opened, the concentration of CO 2 in the mineralized gas is set to be 0.1-2 Vol%, and the concentration of CO 2 in the mineralized gas in the reactor body (6) is monitored in real time;
Step 1.6, continuously introducing waste gas containing CO 2 under the condition of continuous stirring;
Step 1.7, when the concentration of CO 2 in the mineralized gas measured by the gas detector (16) reaches a set value, closing the temperature control system (21), the motor (19), the first check valve (3) and the second check valve (20), and stopping introducing the waste gas containing CO 2;
Step 1.8, opening a discharge valve (10) of the reactor to discharge the saturated mineralizer in the reactor body (6);
Step 2, alternative mineralization and sealing process of two reactors
Step 2.1, the second reactor executes the step 1.1 until the step 1.2;
The second reactor executes the step 1.1 when the gas detector (16) detects that the concentration of CO 2 in the gas mineralized by the first reactor is close to a set value;
Step 2.2, the second reactor executes the step 1.3 until the step 1.8;
The time for the second reactor to start performing step 1.3 is: when the concentration of CO 2 in the gas after mineralization of the first reactor reaches a set value, the first reactor executes the step 1.7 so as to continuously mineralize and seal the waste gas containing CO 2;
Step 2.3, before the second reactor executes step 1.7, the first reactor repeatedly executes step 1.3 until step 1.8;
step 2.4, repeatedly executing the steps 2.1-2.3;
Second method for mineralizing and sequestering CO 2
The second mineralization and sequestration CO 2 method adopts a reactor to mineralize and sequester intermittently, and the intermittent mineralization and sequestration of the reactor is the same as the step 1 in the first mineralization and sequestration CO 2 method;
In the two mineralization and sequestration methods of CO 2, after the saturated mineralizer in the step 1.8 is discharged, solid-liquid separation is carried out on the saturated mineralizer to obtain filter residues and filtrate; drying the filter residues to obtain calcium carbonate-containing residues for storing CO 2; regulating the pH value of the filtrate to 7-9 by using dilute sulfuric acid, evaporating, crystallizing and drying to obtain an ammonium sulfate product;
the preparation method of the mineralizer in the two methods for mineralizing and sequestering CO 2 comprises the following steps:
firstly, adjusting the pH value of shale vanadium extraction tailings pulp to 7-8 by using an alkaline regulator, oscillating for 0.5-6 h, and carrying out solid-liquid separation to obtain shale vanadium extraction tailings and supernatant;
Step two, drying shale vanadium extraction tailings for 4-12 hours at the temperature of 60-120 ℃, and then placing the shale vanadium extraction tailings in grinding equipment for mechanical activation for 5-30 seconds to obtain activated tailings; then mixing the supernatant with the activated tailings according to a liquid-solid ratio of (1-5) m 3/Kg to obtain activated tailings;
Thirdly, adding the ammonia nitrogen waste liquid into the activated tail slurry according to the ratio of the amount of N in the ammonia nitrogen waste liquid to the amount of S in the activated tail slurry of (0.6-3) to 1, and sealing; performing ultrasonic treatment for 5-50 min under the condition of 40-100 kHz to prepare a CO 2 mineralizer based on shale vanadium extraction tailings and ammonia nitrogen waste liquid;
The structure of the reactor in the two methods for mineralizing and sequestering CO 2 is as follows:
the reactor comprises a reactor body (6), a cover plate (5), a feed pipe (4), an electric furnace wire (8), a stirrer (12), an aerator (13), a gas detector (16), a temperature sensor (17) and a temperature control system (21);
The reactor body (6) is cylindrical, the port of the reactor body (6) is fixedly connected with the cover plate (5) through a bolt, a sealing ring is arranged between the port of the reactor body (6) and the cover plate (5), the outer surfaces of the circular wall and the bottom of the reactor body (6) are coated with insulators (7), and electric furnace wires (8) are arranged between the insulators (7) and the reactor body (6);
A motor (19) is arranged at the middle position of the upper surface of the cover plate (5), a round tube (15) is vertically fixed at the middle position of the lower surface of the cover plate (5), and the lower end of the round tube (15) passes through the aerator (13) and is fixedly connected with the middle position of the bottom plate of the aerator (13); an output shaft of the motor (19) is connected with the upper end shaft of the stirring shaft (14) through a shaft coupling, the lower end of the stirring shaft (14) penetrates through the lower port of the circular tube (15) to be connected with the stirrer (12) through a shaft, and the upper end of the circular tube (15) and the inner wall of the lower end of the circular tube are respectively and movably connected with the stirring shaft (14) through bearings; the upper end of the round tube (15) is fixedly connected with the cover plate (5) in a sealing way, and the lower part of the round tube (15) is fixedly connected with the top plate of the aerator (13) and the bottom plate of the aerator (13) in a sealing way respectively;
The upper flat plate center of the aerator (13) is symmetrically fixed with a first air inlet pipe (9) and a second air inlet pipe (18), the lower ends of the first air inlet pipe (9) and the second air inlet pipe (18) are respectively communicated with the inner cavity of the aerator (13), and the upper ends of the first air inlet pipe (9) and the second air inlet pipe (18) penetrate through the cover plate (5) to be respectively communicated with an external air source;
The cover plate (5) is respectively fixed with a temperature sensor (17) and a feeding pipe (4); the temperature measuring end of the temperature sensor (17) extends to the inner cavity of the reactor body (6), and the wiring end of the temperature sensor (17) is externally connected with a temperature control system (21); the upper end of the feed pipe (4) passes through the cover plate (5) to be communicated with the feed hopper (1), the lower end of the feed pipe (4) extends to the inner cavity of the reactor body (6), and the upper part of the feed pipe (4) is provided with the regulating valve (2); a gas detector (16) is arranged on the wall surface of the reactor body (6), an air inlet of the gas detector (16) is communicated with the inner cavity of the reactor body (6), and an air outlet of the gas detector (16) is communicated with the atmosphere;
a discharge pipe (11) is arranged at the bottom close to the reactor body (6), and the discharge pipe (11) is provided with a discharge valve (10);
The temperature control system (21) comprises a temperature meter (22) and an alternating current contactor (23); the power ports L3 and L4 of the temperature instrument (22) are connected with a corresponding live wire and zero line, the L2 end of the normally open contact S1 of the temperature instrument (22) is connected with the live wire, the L1 end of the normally open contact S1 is connected with the T1 end of the alternating current contactor (23), and the T2 end of the alternating current contactor (23) is connected with the zero line; the end A1 and the end A2 of the temperature instrument (22) are connected with two leads at the non-temperature-measuring end of the temperature sensor (17); the C2 end of the normally open contact S2 of the alternating current contactor (23) is connected with the Y2 end of the electric stove wire (8), the C1 end of the alternating current contactor (23) is connected with a live wire, and the Y1 end of the electric stove wire (8) is connected with a zero wire.
2. The method for mineralizing and sequestering CO 2 based on shale vanadium extraction tailings according to claim 1, wherein the method comprises the following steps: the liquid-solid ratio of the shale vanadium extraction tailings pulp is (1-5) m 3/Kg; the Ca content in the solids of the shale vanadium extraction tailings pulp is more than 5 weight percent.
3. The method for mineralizing and sequestering CO 2 based on shale vanadium extraction tailings according to claim 1, wherein the alkaline regulator is one or more of calcium hydroxide, calcium oxide and calcium bicarbonate.
4. The method for mineralizing and sequestering CO 2 based on shale vanadium extraction tailings according to claim 1, wherein the method comprises the following steps: the chemical components of the ammonia nitrogen waste liquid are more than one of ammonium sulfate, ammonium chloride, ammonia water and ammonium hydroxide; the pH value of the ammonia nitrogen waste liquid is more than 7.
5. The method for mineralizing and sequestering CO 2 based on shale vanadium extraction tailings according to claim 1, wherein the method comprises the following steps: the first air inlet pipe (9) and the second air inlet pipe (18) are correspondingly provided with a first check valve (3) and a second check valve (20).
6. The method for mineralizing and sequestering CO 2 based on shale vanadium extraction tailings according to claim 1, wherein the method comprises the following steps: the distance from the blades of the stirrer (12) to the bottom plate of the reactor body (6) is 0.1-0.2 times of the height of the inner cavity of the reactor body (6), and the radius of the blades of the stirrer (12) is 0.5-0.7 times of the radius of the inner cavity of the reactor body (6).
7. The method for mineralizing and sequestering CO 2 based on shale vanadium extraction tailings according to claim 1, wherein the method comprises the following steps: the distance between the lower surface of the aerator (13) and the blades of the stirrer (12) is 0.08-0.15 times of the height of the inner cavity of the reactor, and the distance from the outer side surface of the aerator (13) to the side surface of the inner cavity of the reactor body (6) is 0.15-0.25 times of the diameter of the reactor body (6).
8. The method for mineralizing and sequestering CO 2 based on shale vanadium extraction tailings according to claim 1, wherein the method comprises the following steps: the lower ports of the first air inlet pipe (9) and the second air inlet pipe (18) are positioned at the position 0.25-0.5 times of the height of the inner cavity of the aerator (13).
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| US7919064B2 (en) * | 2008-02-12 | 2011-04-05 | Michigan Technological University | Capture and sequestration of carbon dioxide in flue gases |
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