CN116988839B - CO is blocked by utilizing waste salt caves for storing alkaline residues2Method for fixing carbon - Google Patents
CO is blocked by utilizing waste salt caves for storing alkaline residues2Method for fixing carbon Download PDFInfo
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- 150000003839 salts Chemical class 0.000 title claims abstract description 129
- 239000002699 waste material Substances 0.000 title claims abstract description 43
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 38
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 235000019994 cava Nutrition 0.000 title claims abstract description 36
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 114
- 239000007789 gas Substances 0.000 claims abstract description 62
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 60
- 238000007789 sealing Methods 0.000 claims abstract description 59
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 54
- 238000000034 method Methods 0.000 claims abstract description 47
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 238000002347 injection Methods 0.000 claims abstract description 29
- 239000007924 injection Substances 0.000 claims abstract description 29
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000003546 flue gas Substances 0.000 claims abstract description 28
- 239000012267 brine Substances 0.000 claims abstract description 27
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims abstract description 27
- 230000008569 process Effects 0.000 claims abstract description 21
- 239000003518 caustics Substances 0.000 claims abstract description 20
- 239000010802 sludge Substances 0.000 claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 claims abstract description 16
- 238000005065 mining Methods 0.000 claims abstract description 9
- 238000001179 sorption measurement Methods 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 5
- 150000002367 halogens Chemical class 0.000 claims abstract description 5
- 238000012545 processing Methods 0.000 claims abstract description 4
- 238000011033 desalting Methods 0.000 claims abstract description 3
- 238000012216 screening Methods 0.000 claims abstract 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 30
- 239000011575 calcium Substances 0.000 claims description 18
- 239000003513 alkali Substances 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 16
- 229910052791 calcium Inorganic materials 0.000 claims description 16
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 14
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 12
- 239000002585 base Substances 0.000 claims description 11
- 230000006835 compression Effects 0.000 claims description 11
- 238000007906 compression Methods 0.000 claims description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- 238000003860 storage Methods 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 239000011800 void material Substances 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 230000009919 sequestration Effects 0.000 claims description 8
- 239000000292 calcium oxide Substances 0.000 claims description 7
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 7
- 238000011049 filling Methods 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 229910000831 Steel Inorganic materials 0.000 claims description 6
- 239000004568 cement Substances 0.000 claims description 6
- 239000010959 steel Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 229910021529 ammonia 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
- 239000000945 filler Substances 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 239000002912 waste gas Substances 0.000 claims description 5
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 4
- 238000010521 absorption reaction Methods 0.000 claims description 4
- 230000002308 calcification Effects 0.000 claims description 4
- 239000001110 calcium chloride Substances 0.000 claims description 4
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 4
- 230000007774 longterm Effects 0.000 claims description 4
- 239000013049 sediment Substances 0.000 claims description 4
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 claims description 3
- 229910000020 calcium bicarbonate Inorganic materials 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 238000012544 monitoring process Methods 0.000 claims description 2
- 238000007711 solidification Methods 0.000 claims description 2
- 230000008023 solidification Effects 0.000 claims description 2
- 230000009466 transformation Effects 0.000 claims description 2
- 230000014759 maintenance of location Effects 0.000 claims 4
- 230000002706 hydrostatic effect Effects 0.000 claims 1
- 235000002639 sodium chloride Nutrition 0.000 description 90
- 238000007599 discharging Methods 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 238000010793 Steam injection (oil industry) Methods 0.000 description 4
- 239000002893 slag Substances 0.000 description 4
- 208000004434 Calcinosis Diseases 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000004891 communication Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000005755 formation reaction Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052925 anhydrite Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- -1 thermal power Chemical compound 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241000282376 Panthera tigris Species 0.000 description 1
- QUWBSOKSBWAQER-UHFFFAOYSA-N [C].O=C=O Chemical compound [C].O=C=O QUWBSOKSBWAQER-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 239000010808 liquid waste Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
Classifications
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21F—SAFETY DEVICES, TRANSPORT, FILLING-UP, RESCUE, VENTILATION, OR DRAINING IN OR OF MINES OR TUNNELS
- E21F17/00—Methods or devices for use in mines or tunnels, not covered elsewhere
- E21F17/16—Modification of mine passages or chambers for storage purposes, especially for liquids or gases
Landscapes
- Engineering & Computer Science (AREA)
- Mining & Mineral Resources (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- Treating Waste Gases (AREA)
Abstract
The invention discloses a method for sealing CO 2 and fixing carbon by utilizing waste salt caves for storing alkaline residues, which specifically comprises the following steps: (1) screening waste salt caves for storing alkaline residues; (2) Collecting low-concentration carbon dioxide flue gas, conveying the low-concentration carbon dioxide flue gas to a target mining area through a pipeline, compressing the low-concentration carbon dioxide flue gas, and injecting the low-concentration carbon dioxide flue gas into a waste salt pit for storing caustic sludge through a high-position gas injection well; (3) In the process of injecting carbon dioxide flue gas into the well, brine in the salt cavern space and the caustic sludge gap is displaced, and the brine is discharged from a low-position well and is sent to a salt production line for processing industrial salt; (4) After the gas injection and halogen discharge are finished, continuing the gas injection and alkaline residue filtering and adsorption reaction in the salt cavern, and dehydrating and desalting the unreacted gas after CO 2 in the flue gas is absorbed by the alkaline residue and then evacuating the gas from a low-position exhaust well; (5) And (3) sealing the low-position exhaust shaft, injecting gas and boosting pressure, and realizing physical sealing. The invention provides a technological process and a method for sealing and storing CO 2 and fixing carbon by utilizing salt caves in combination with the actual condition of disposing alkaline residues by using waste salt caves of domestic mine salt, and provides a new path for sealing and storing CO 2.
Description
Technical Field
The invention belongs to the technical fields of carbon dioxide sealing and carbon fixation and waste salt pit treatment and utilization, relates to a method for physically sealing and chemically fixing carbon to CO 2 by utilizing salt pits, and in particular relates to a method for sealing and storing CO 2 and carbon fixation by utilizing waste salt pits for storing alkaline residues.
Background
In recent years, china has developed economically and rapidly, wherein thermal power, steel, cement and land transportation are basic industries and departments supporting global social and economic development, and the rapid development has been achieved in recent thirty years. The global main energy infrastructure carbon emissions generally have a growing trend, and global thermal power, steel, cement and land transportation departments in 2020 have CO-emissions of about 240 million tons of CO 2, accounting for about 70% of the total global carbon emissions.
In the past, domestic carbon sequestration engineering mainly uses CO 2 for oil displacement by oil and gas enterprises, and improves oil and gas recovery ratio; the method is more prone to be used for carbon sealing of a salty water layer abroad. Recently, the continental united states resource company has been planning to invest in 2.5 million dollar CO 2 capture projects, capturing CO 2 at a scale of 800 ten thousand tons/year, mainly into sandstone formations sequestered underground. Worldwide, about 400 ten thousand tons of CO 2 are sequestered underground each year.
The national institute of science and universities and colleges develop carbon capture and carbon sequestration technical researches, such as the research of underground carbon sequestration technical researches started in 2003 in the early northwest university, the first full-process carbon sequestration demonstration project in China is established by extending petroleum in the early northwest university of 2015, but CO 2 is mainly sequestered by using oilfield sandstone layers, CO 2 is utilized for oil displacement, and the capability of storing 5 ten thousand tons of CO 2 per year is provided at present.
The Chinese engineering institute Qian Qi tiger provides that the permanent underground sealing of CO 2, namely artificial carbon sink, can be realized by utilizing the advantages of the sealing property, the stability and the like of the underground space, and indicates that part of underground space of a coal mine goaf, underground space of a salt cavern and metal and nonmetal mine caverns can be used for sealing CO 2 after being transformed.
In 2021, 8 months, china sea oil announces that the first offshore CO 2 sealing and demonstrating project in China is formally started in the open basin of the south China sea bead, and CO 2 associated with offshore oilfield development is permanently sealed and stored in a 800-meter deep seabed reservoir, and the sealing and storing quantity is about 30 ten thousand tons and a total of more than 146 ten thousand tons each year. The method is an important step for developing green low-carbon transformation of ocean oil gas in China. However, formation sequestration CO 2 has uncertainty, presents leakage and leakage risks, damages formation structure and stability, is affected by geological structures, has severe geological conditions, and is applicable to limited areas.
The rock salt has the characteristics of good rheological property, low void ratio, low permeability and the like, and has the characteristics of high safety coefficient, good sealing property, no leakage and the like, so that salt cavern is one of internationally recognized large underground storage modes. The salt cavern is used for storing oil, compressed air, hydrogen and other gases. Wherein, the treatment of the alkaline residue by using the waste salt cavern is successfully applied to Jiangsu and the like, and the sealing of CO 2 by using the waste salt cavern for storing the alkaline residue is not reported yet.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for sealing CO 2 and fixing carbon by using waste salt caves for storing alkaline residues, the invention uses the waste salt caves for sealing CO 2 for storing the alkaline residues, on one hand, permanent carbon fixing is realized through adsorption chemical reaction, on the other hand, the secondary utilization of the waste salt caves is realized, the spatial resource value of the salt caves is exerted, and the invention provides a new path for sealing CO 2 by combining the actual condition of disposing the alkaline residues by using the salt caves for sealing CO 2 and fixing carbon by using the salt caves. The invention can realize large-scale sealing and storing of CO 2, has low sealing and storing cost, realizes long-term stable sealing and storing to the underground by utilizing the reaction of alkaline calcium liquid, alkaline residue and CO 2 in alkali preparation and the like, reduces carbon emission and releases carbon emission indexes.
The invention is realized by the following technical scheme:
a method for sealing CO 2 and fixing carbon by utilizing waste salt caves for storing alkaline residues comprises the following steps:
(1) Selecting a waste salt pit, wherein the waste salt pit is filled with alkaline residue wet base generated by an alkali-making enterprise, the stability and the tightness of the salt pit are evaluated, and the injection well and the sealing pressure are designed according to the inner cavity volume of the salt pit;
(2) Collecting low-concentration carbon dioxide flue gas, conveying the low-concentration carbon dioxide flue gas to a target mining area through a pipeline, preprocessing to remove solid particle impurities, injecting the low-concentration carbon dioxide flue gas into a waste salt hole through a high-position steam injection well for CO 2 injection and sealing, displacing and discharging brine in a wet base of alkaline residue in the process of sealing CO 2, discharging the brine from a low-position exhaust well, and conveying the brine to a salt production line for processing industrial salt;
The wet base of the alkaline residue produced by the alkali production enterprise is mainly alkaline residue and calcium liquid, CO 2 is subjected to a series of reactions such as main reaction ：CO2+H2O+2NH3→CO3 2-+2NH4 +;CaO+H2O→Ca(OH)2;CO2+2OH-→CO3 2-+H2O;Ca2++CO3 2-→CaCO3↓;CaCO3+CO2+H2O→Ca2++2HCO3 -;CaSO4+CO3 2-→CaCO3↓+SO4 2- and the like with the alkaline calcium liquid produced by the alkali production in the pit, so that the gaseous CO 2 is converted into calcium carbonate and calcium bicarbonate to be sealed in salt holes.
(3) In the process of gas drainage, the non-reactive gas absorbed by CO 2 is dehydrated and desalted and then is drained from a low-position exhaust well; CO 2 is injected into a high-level salt well, gas drives calcium liquid and gas-liquid reaction, gas enters into a caustic sludge gap for gas-solid reaction, brine is discharged from a low-level salt well, and the gas is filtered and purified through insoluble sediment and caustic sludge through the bottom of a salt cavity solution cavity and a communication channel to be discharged after dehydration and desalination treatment of residual gas (mainly N 2、O2) of the low-level salt well and the low-level well.
(4) And after the unreacted gas is exhausted, closing the low-position exhaust well, and closing the high-position steam injection well when the salt cavern pressure reaches the preset pressure.
The process realizes the combination of physical sealing and storage and chemical carbon fixation of alkaline calcium-containing substances by utilizing the physical space of the waste salt cavern for storing the alkaline residue and the calcium liquid.
The physical sealing and storing method utilizes the physical space (the net space at the top of the salt pit and the sediment void space) of the underground salt pit to store CO 2 gas, seals CO 2 in the underground salt pit space through compression, and can compress, liquefy and inject CO 2 into the salt pit for sealing and storing according to the depth and temperature conditions of the salt pit.
In the chemical carbon fixation process, CO 2 is subjected to chemical reaction with an alkaline substance containing Ca 2+; the compressed CO 2 is dissolved in brine in salt caves and reacts with alkaline calcium liquid (containing partial free ammonia, ca 2+、OH- and the like) generated by alkali preparation in the salt caves, and meanwhile CO 2 drives the brine into alkali residue gaps to react with the calcium liquid and alkali residue components to generate calcium carbonate, calcium bicarbonate and the like, so that the underground salt caves are permanently sealed and carbon-fixed. And meanwhile, calcification and solidification of the cemented solid filler are carried out, so that the strength of the solid filler such as the alkali residue is improved, and the purpose of filling and managing salt caves is achieved.
The invention further improves the scheme as follows:
the wet base alkaline residue is from alkali production by an ammonia alkaline method, and the pH value is 9-11.
Further, the wet base alkaline residue contains 40-60wt% of water, wherein the main components of the solid alkaline residue are as follows: 45-50wt% of calcium carbonate, 12-18wt% of calcium chloride, 6-12wt% of calcium sulfate, 4-8wt% of calcium oxide and the balance of other inorganic salts.
Further, the low-concentration carbon dioxide flue gas is from waste gas generated by thermal power enterprises, steel enterprises and cement enterprises, and comprises the following main components: 70-80 v/v% of nitrogen, 10-20 v/v% of carbon dioxide, less than or equal to 10v/v% of oxygen and the balance of impurity gas.
Further, the main components of the non-reactive gas are nitrogen and oxygen.
Further, the calculation method of the system pressure and the carbon dioxide sealing quantity comprises the following steps:
Setting the top depth of a salt pit as H (m), setting the brine density rho 1 (the value of 1.2 g/l) in the salt pit, the stratum average density rho 2 (the value of 2.2-2.6 g/l) of a salt layer, the sediment void ratio c (%) of alkaline residue, the net space volume of the salt pit as V 1 (ten thousand m 3), the average sectional area S (m 2) of the salt pit, the total alkaline residue amount T (ten thousand T) stored in the salt pit, the storage mass m 1（t/m3 of alkaline residue in unit volume, the brine volume V 2 (ten thousand m 3) discharged in the gas injection and brine discharge process, the pressure coefficient k 1 (the value of 1.05-1.5) of a compression device, the sealing pressure coefficient k 2 (the value of 0.6-0.9), the carbon dioxide coefficient k 3 (the value of reaction absorption of alkaline residue in unit mass (the range of 0.3-0.7), the sealing gas compression coefficient k 4 (the value of 1.2-2.0), and the carbon dioxide content w (%) of flue gas;
Brine head pressure (Mpa) in salt caves: p 1=[(V2-V1)/s+H]*ρ1/100;
The caustic sludge void space (ten thousand m 3）：V3 = c T;
Salt cavern storage volume (ten thousand m 3）：V0=V1+V2 or V 0=V1+V3;
salt cavern overburden static pressure (Mpa): p 2=H*ρ2/100;
gas injection compression pressure (Mpa): p 3=k1*P1;
Salt pit sealing pressure (Mpa): p 4=k2*P2;
Amount of chemically absorbed carbon dioxide (ten thousand): m 1=k3 x T;
Physical carbon dioxide amount (ten thousand t): m 2=k4*P4*V0 w/100;
Carbon dioxide sequestration (ten thousand): m 3=M1+M2.
Furthermore, alkaline calcium liquid, alkali slag and CO 2 generated in alkali preparation and the like are reacted to realize long-term stable sealing and storage, and meanwhile, the reaction calcification curing process is carried out, so that the strength of a filler for supporting salt caves is increased, and the filling treatment of the salt caves goaf is realized.
The alkaline residue is mainly alkaline substances (pH is about 9-11), and the main components comprise calcium carbonate, calcium chloride, magnesium hydroxide, calcium sulfate, sodium chloride, calcium oxide, silicon dioxide, aluminum oxide, ferric oxide and the like, wherein the content of the calcium carbonate, the calcium sulfate and the calcium oxide exceeds 60%, the alkaline residue has considerable reaction adsorption capacity with carbon dioxide under alkaline conditions, and CO 2 is blocked by utilizing waste salt caves for storing the alkaline residue, so that on one hand, permanent carbon fixation is realized through adsorption chemical reaction, on the other hand, the secondary utilization of the waste salt caves is realized, and the space resource value of the salt caves is exerted.
At present, the carbon dioxide trapping and utilizing (CCUS) process has the main cost concentrated in trapping and transportation, and is limited in application and market prospect, and the method directly utilizes and collects low-concentration carbon dioxide flue gas such as thermal power, steel, cement and the like, and the upstream of the method collects low-purity CO 2 gas to be directly injected into a well, so that purification and separation are not needed, and alkaline residue and calcium liquid waste salt caves are directly injected and stored through a high-level well, thereby saving trapping cost. The flue gas of low concentration carbon dioxide (the main components are 70% -80% of nitrogen, the carbon dioxide content is about 10% -20% and the oxygen content is about 10% or less) such as thermal power, steel, cement and the like is reinjected into the alkaline residue salt caves of the waste gas, purification and separation are not needed, and the trapping cost is greatly reduced. In the gas flooding process, carbon dioxide fully contacts with part of free ammonia, ca 2+、OH- and the like in waste residues to react, and the tail gas (residual nitrogen and oxygen) after the reaction is discharged from a low-position well after the filtration and adsorption reaction, so that the carbon dioxide carbon fixation purpose is realized. Meanwhile, in the well injection process, after the low-purity CO 2 gas is collected and injected, the waste salt cavern is a large-scale underground reaction filtering device, the CO 2 is fully reacted and absorbed by alkaline residues through paths such as the gas injection well, a communication channel and the like, SO 2、NOX and the like in the captured gas can be removed, environmental pollution caused by external discharge is reduced, and the residual non-reaction gas (nitrogen and oxygen) is exhausted through an exhaust well.
Compared with the prior art, the invention has the beneficial effects that:
(1) The existing underground space of the mine salt cavern is used as a 'warehouse' for storing CO 2, so that the reutilization of the waste salt cavern is realized, the CO 2 sealing cost is reduced, the large-scale storage can be realized, the carbon emission is reduced, and the carbon emission index is released.
(2) The salt cavern seals up and stores CO 2, the system has no waste residue, waste liquid and waste gas discharged, and simultaneously, the brine in the waste salt cavern is recovered, so that the resource saving and the comprehensive utilization are realized.
(3) Chemical sealing and storing are carried out by utilizing alkaline calcium liquid such as alkali preparation and the like, and alkaline residue reacts with CO 2, so that long-term stable sealing and storing into the ground are realized; and meanwhile, the calcification curing process is reacted, the supporting strength of the filler is increased, the filling treatment of the goaf of the salt cavern of the well and the mine is realized, and the stability of the goaf is greatly improved.
(4) The waste salt cavern of the communicating well is used as a storage reaction device, and low-concentration carbon dioxide waste gas is directly reinjected, so that the problem of high cost in a carbon sealing and trapping link is solved.
Drawings
FIG. 1 is a schematic diagram of a process flow.
FIG. 2 is a schematic representation of a abandoned communicating well salt cavern injected with carbon dioxide;
FIG. 3 is a diagram showing a process of discharging brine by injecting carbon dioxide into salt caves;
FIG. 4 is a schematic diagram of the process of discharging tail gas after carbon dioxide injection reaction.
In fig. 2-4, 1 is a waste salt pit gas injection well, 2 is a waste salt pit brine discharge and gas injection reaction post-exhaust well, 3 is a waste salt pit high-position gas injection well solution cavity profile, 4 is a salt pit low-position brine discharge and gas injection reaction post-exhaust well solution cavity profile, and 5 is waste salt pit solution cavity brine; the method comprises the steps of 6, filling alkali slag in a salt cavern, 8, filling alkali slag in a waste slag void space, 9, communicating a communicating channel at the bottom of the salt cavern, 10, discharging halogen in the salt cavern and filling gas after reaction, 11, injecting carbon dioxide into the salt cavern, 12, discharging gas in the side of the exhaust well after reaction, and 13, and indicating the path of injected gas in the communicating well salt cavern.
Detailed Description
The present invention will be described in detail with reference to specific examples.
Example 1
The production scale of the target mining area in Jiangsu Huaian certain salt mine is 120 ten thousand tons per year, the mining elevation is-1030 to-1700 m, the salt mine is mined and produced for more than 15 years, the directional communication well technology is mainly used for brine production, the production time is long, and the underground solution cavity volume is estimated to be larger according to the production.
1 Group of salt wells are selected to carry out deep work and system evaluation is carried out. Firstly, the production condition of the salt well group is investigated, the mining and injection ratio of the well group is stabilized to be about 0.9, the depth of an aquifer is about 300m, the depth of a cavity bottom is 1334m, the position of a cavity top is 1288m, the safe mining depth is 1030m, the clean space of the residual cavity and the void volume of alkaline residue are about 11 square, the salt well group is not communicated with other production well groups in series, the water tightness test is carried out on the well group, the air tightness test is carried out on a well shaft, the air tightness test is carried out on salt caves, and the air tightness is good.
The alkaline residue wet base (alkaline residue and calcium solution) is obtained from an alkaline production process of the well god company, the scale is 52 ten thousand tons/year, the wet base contains about 50 percent of water, the pH value is 9-11, and the alkaline residue mainly comprises: 46.8% of calcium carbonate, 15.4% of calcium chloride, 8.73% of calcium sulfate, 6.51% of calcium oxide and the like, and the alkaline residue calcium liquid is injected into the well through a special well injection device and system after size mixing, and the total amount of the wet base alkaline residue is 38 ten thousand tons (19 ten thousand tons of dry base is converted) in the well group.
CO 2 is sourced from part of flue gas of a self-contained thermal power plant of a company, the scale of the plant is 60 ten thousand tons of standard coal per year, the carbon emission amount is 41.38 ten thousand tons per year, and the emission components are as follows: CO 2 content about 16%, O 2 content about 6%, SO 2≤20ppm,NOX content less than or equal to 50ppm and smoke dust content less than or equal to 10ppm.
The low-concentration carbon dioxide flue gas is partially trapped and conveyed to a target mining area by a pipeline, is compressed by a special compressor and a compression system, is injected into the underground from a high-position steam injection well, and has variable frequency control over gas injection and halogen discharge pressure, and the adjustable pressure range is 15.45-16Mpa.
The salt pit chemical sealing and carbon fixation mainly uses alkaline residue and calcium solution (pH is about 9-11) produced by alkali production of companies, and adopts a series of reactions such as main reaction ：CO2+H2O+2NH3→CO3 2-+2NH4 +;CaO+H2O→Ca(OH)2;CO2+2OH-→CO3 2-+H2O;Ca2++CO3 2-→CaCO3↓;CaCO3+CO2+H2O→Ca2++2HCO3 -;CaSO4+CO3 2-→CaCO3↓+SO4 2-, etc., and the gaseous CO 2 is converted into solid calcium carbonate which is sealed in the salt pit together with the alkaline waste residue. And (3) displacing and discharging brine in the CO 2 sealing process, and conveying the brine to a salt production line for processing industrial salt.
In the gas-driven water process, carbon dioxide is fully contacted with partial free ammonia, ca 2+、OH- and the like contained in waste residues to react, and the carbon dioxide is removed through filtration and adsorption reaction, SO 2、NOX and the like in captured gas can also be removed, and the residual unreacted gas (the main components are nitrogen and oxygen) is dehydrated and desalted and then is discharged. And (3) continuing gas injection after gas injection and halogen removal are finished, filtering and adsorbing low-concentration carbon dioxide flue gas by alkali residues in salt caves, continuing reacting and fixing carbon, evacuating non-reacting gas after desalting and dewatering, monitoring the carbon dioxide content of the evacuating gas, and sealing a low-position exhaust well after the carbon dioxide content of the evacuating gas is increased from 0 to 3%, and sealing a high-position steam injection well when the salt caves reach the preset pressure.
The clean space of the cavity and the void volume of the caustic sludge are about 11 square, the designed pressure range is 16-24.7MPa, the stored CO 2 is about 1.81 ten thousand tons, and the chemical permanent curing and sealing are about 7.125 ten thousand tons. The CO 2 is fixedly stored for more than 5 ten thousand tons each year, the CO 2 emission right is released after the CO 2 is stored, and according to the 40 yuan/ton carbon emission right trade price, 200 ten thousand yuan profits can be created for enterprises each year, and the economic benefit is quite considerable.
The foregoing embodiments are merely illustrative of the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the present invention and to implement the same, not to limit the scope of the present invention. All equivalent changes or modifications made according to the spirit of the present invention should be included in the scope of the present invention.
Claims (5)
1. The method for sealing CO 2 and fixing carbon by using waste salt caves for storing alkaline residues is characterized by comprising the following steps:
(1) Screening waste salt caves, wherein the waste salt caves are filled with wet base caustic sludge generated by alkali-making enterprises, salt well sleeve transformation is completed, and injection wells and sealing pressure are designed according to the depth of the salt caves;
(2) Collecting low-concentration carbon dioxide flue gas, conveying the low-concentration carbon dioxide flue gas to a target mining area through a pipeline, compressing the low-concentration carbon dioxide flue gas, and injecting the low-concentration carbon dioxide flue gas into a waste salt pit for storing caustic sludge through a high-position gas injection well; collecting low-concentration carbon dioxide flue gas, conveying the low-concentration carbon dioxide flue gas to a target mining area through a pipeline, compressing the low-concentration carbon dioxide flue gas through compression equipment, and injecting the low-concentration carbon dioxide flue gas into a waste salt cavern through a high-position gas injection well for CO 2 injection and sealing;
(3) In the process of injecting carbon dioxide flue gas into the well, brine in the salt cavern space and the caustic sludge gap is displaced, and the brine is discharged from a low-position well and is sent to a salt production line for processing industrial salt;
(4) After the gas injection and halogen discharge are finished, continuing to carry out filtration and adsorption reaction on the gas injection and the alkaline residue in the salt cavern, dehydrating and desalting the unreacted gas after absorbing CO 2 in the reaction flue gas by the alkaline residue, evacuating from a low-position exhaust well, continuing to carry out gas injection and absorption reaction until the reaction substances in the salt cavern are fully reacted and consumed, and monitoring that the carbon dioxide content of the evacuated gas is increased from 0 to 3 percent and then entering a step of boosting and sealing;
(5) Sealing the low-position exhaust well, injecting gas for boosting pressure, realizing physical sealing, and sealing the high-position gas injection well when the salt cavern pressure reaches the preset pressure;
the method for calculating the system pressure and the carbon dioxide sealing quantity comprises the following steps:
Setting the top depth of a salt pit as H/m, the brine density rho 1 in the salt pit, the average density rho 2 of an overburden stratum, the void ratio/c of caustic sludge sediments, the net space volume of the salt pit as V 1/ten thousand m 3, the average sectional area S/m 2 of the salt pit, the total amount T/ten thousand T of caustic sludge stored in the salt pit, the storage mass m 1/t/m3 of the caustic sludge in unit volume, the volume V 2/ten thousand m 3 of brine discharged in the gas injection and brine discharge process, the pressure coefficient k 1 of a compression device, the sealing pressure coefficient k 2, the carbon dioxide absorption coefficient k 3 of the reaction of the caustic sludge in unit mass, the sealing gas compression coefficient k 4 and the carbon dioxide content w/%;
Brine head pressure/Mpa in salt caves: p 1＝[(V2-V1)/s+H]*ρ1/100;
caustic sludge void space/wan m 3：V3 = c T;
salt cavern storage volume/ten thousand m 3：V0＝V1+V2 or V 0＝V1+V3;
salt cavern overburden hydrostatic pressure/Mpa: p 2＝H*ρ2/100;
gas injection compression pressure/Mpa: p 3＝k1*P1;
salt cavern sealing pressure/Mpa: p 4＝k2*P2;
Amount of chemically absorbed carbon dioxide/ten thousand t: m 1＝k3 x T;
physical sequestration of carbon dioxide/ten thousand: m 2＝k4*P4*V0 w/100;
carbon dioxide sequestration/ten thousand t: m 3＝M1+M2;
The compression equipment pressure coefficient k 1 takes a value of 1.05-1.5, the sealing pressure coefficient k 2 takes a value of 0.6-0.9, the unit mass alkaline residue reaction absorption carbon dioxide coefficient k 3 takes a value of 0.3-0.7, and the sealing gas compression coefficient k 4 takes a value of 1.2-2.0;
the process utilizes the alkaline calcium liquid and the alkaline residue of the alkali preparation to react with CO 2 to realize long-term stable sealing and storage, and simultaneously, the process of reaction calcification solidification increases the strength of the filler for supporting salt caves, thereby realizing the filling treatment of the salt cavern goaf.
2. The method for sequestering CO 2 and carbon using waste salt caverns storing caustic sludge of claim 1, wherein the method comprises: the wet base alkaline residue is from alkali production by an ammonia alkaline method, the pH value is 9-11, the water content is 40-60 wt%, and the solid alkaline residue comprises the following components: 45-50 wt% of calcium carbonate, 12-18 wt% of calcium chloride, 6-12 wt% of calcium sulfate, 4-8 wt% of calcium oxide and the balance of other inorganic salts.
3. The method for sequestering CO 2 and carbon using waste salt caverns storing caustic sludge of claim 1, wherein the method comprises: the low-concentration carbon dioxide flue gas is from waste gas generated by thermal power enterprises, steel enterprises and cement enterprises, and comprises the following components: 70-80 v/v% of nitrogen, 10-30 v/v% of carbon dioxide, less than or equal to 10v/v% of oxygen and the balance of impurity gas.
4. The method for sequestering CO 2 and carbon using waste salt caverns storing caustic sludge of claim 1, wherein the method comprises: CO 2 in the low-concentration carbon dioxide flue gas is subjected to chemical reaction with alkaline substances containing Ca 2+, and meanwhile CO 2 drives brine into the caustic sludge gaps to react with calcium liquid and caustic sludge components to generate calcium carbonate and calcium bicarbonate, so that the underground salt caves are permanently sealed and carbon-fixed.
5. The method for sequestering CO 2 and carbon using waste salt caverns storing caustic sludge of claim 1, wherein the method comprises: the non-reactive gas components are nitrogen and oxygen, and the non-reactive gas is discharged from the low-level well.
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