CN117401703A - High-value utilization and synergistic carbon fixation method for blast furnace slag - Google Patents
High-value utilization and synergistic carbon fixation method for blast furnace slag Download PDFInfo
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- CN117401703A CN117401703A CN202311310099.0A CN202311310099A CN117401703A CN 117401703 A CN117401703 A CN 117401703A CN 202311310099 A CN202311310099 A CN 202311310099A CN 117401703 A CN117401703 A CN 117401703A
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- blast furnace
- furnace slag
- leaching
- molecular sieve
- adsorption
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- 238000000034 method Methods 0.000 title claims abstract description 84
- 239000002893 slag Substances 0.000 title claims abstract description 77
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 23
- 230000002195 synergetic effect Effects 0.000 title claims abstract description 21
- 239000007789 gas Substances 0.000 claims abstract description 120
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 98
- 239000002808 molecular sieve Substances 0.000 claims abstract description 68
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 68
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 49
- 230000033558 biomineral tissue development Effects 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 239000002918 waste heat Substances 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 17
- 238000001179 sorption measurement Methods 0.000 claims description 103
- 238000002386 leaching Methods 0.000 claims description 89
- 239000003463 adsorbent Substances 0.000 claims description 48
- 239000012535 impurity Substances 0.000 claims description 24
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 22
- 239000000920 calcium hydroxide Substances 0.000 claims description 22
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 22
- 239000002253 acid Substances 0.000 claims description 21
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000010335 hydrothermal treatment Methods 0.000 claims description 17
- 238000003795 desorption Methods 0.000 claims description 15
- 230000001089 mineralizing effect Effects 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 abstract description 5
- 239000002910 solid waste Substances 0.000 abstract description 4
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 3
- 238000000746 purification Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 30
- 239000000047 product Substances 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 14
- 239000013078 crystal Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 10
- 235000011121 sodium hydroxide Nutrition 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 230000001105 regulatory effect Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 239000011575 calcium Substances 0.000 description 6
- 229910052791 calcium Inorganic materials 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 238000006477 desulfuration reaction Methods 0.000 description 5
- 230000023556 desulfurization Effects 0.000 description 5
- 239000000428 dust Substances 0.000 description 5
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- 239000001099 ammonium carbonate Substances 0.000 description 4
- 235000012501 ammonium carbonate Nutrition 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000005453 pelletization Methods 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000003546 flue gas Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910001388 sodium aluminate Inorganic materials 0.000 description 3
- 238000010183 spectrum analysis Methods 0.000 description 3
- 238000004876 x-ray fluorescence Methods 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 239000003034 coal gas Substances 0.000 description 2
- 229960004887 ferric hydroxide Drugs 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000005261 decarburization Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/18—Carbonates
- C01F11/181—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by control of the carbonation conditions
-
- 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
- B01D53/02—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 by adsorption, e.g. preparative gas chromatography
- B01D53/04—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 by adsorption, e.g. preparative gas chromatography with stationary adsorbents
- B01D53/047—Pressure swing adsorption
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
- B01J20/28019—Spherical, ellipsoidal or cylindrical
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/50—Carbon dioxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/005—Silicates, i.e. so-called metallosilicalites or metallozeosilites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention provides a method for high-value utilization and synergistic carbon fixation of blast furnace slag, and belongs to the technical field of solid waste resource utilization. The invention takes blast furnace slag as raw material, prepares molecular sieve by hydrothermal method and synthesizes calcium carbonate by carbonating method, the molecular sieve can be used asIs CO in blast furnace gas 2 The prepared calcium carbonate can meet the industrial calcium carbonate standard, can be used in different industries, and generally realizes the high-value utilization of blast furnace slag. The heat required in the molecular sieve synthesis and calcium carbonate preparation processes is from the waste heat of blast furnace gas, an external heat source is not required, the consumption of extra energy sources is reduced, and high-concentration CO is not required to be obtained 2 Product gas which meets the requirement of mineralization reaction for synthesizing calcium carbonate and realizes CO of blast furnace gas 2 Emission reduction, and purification of gas, and realization of rise of the heat value of blast furnace gas.
Description
Technical Field
The invention belongs to the technical field of solid waste resource utilization, and particularly relates to a method for high-value utilization and synergistic carbon fixation of blast furnace slag.
Background
CO 2 Is the main greenhouse gas, CO in the atmosphere 2 The concentration of (3) increased from 278ppm in 1750 to 412ppm in 2020 by nearly 50%, and CO in the atmosphere was expected at the end of 21 st century 2 The greenhouse effect has become a major global challenge facing today's human society with a concentration of up to approximately 700ppm, and thus CO 2 Is not suitable for the reduction of emission. The industrial emission is CO 2 Is the largest carbon emission source in the blast furnace process in the steel production process, and occupies about CO 2 70% of total discharged CO of blast furnace gas 2 Emission reduction is realized by CO in the whole steel industry 2 And the key of emission reduction.
For blast furnace process CO 2 Is a common technique for achieving separation or purification of gases by alternating adsorption and desorption processes with periodic pressure changes, but for pressure swing adsorption the adsorbent used is high in CO 2 Adsorption performance and low cost are key to the overall process. In addition, the iron and steel industry is one of the largest industrial sources of solid waste discharge, wherein blast furnace slag generated in the blast furnace process is the main solid waste, and the blast furnace slag contains CaO (30-50%) and SiO with higher content 2 (25-45%) and a small amount of Al 2 O 3 (1-10%), how to utilize blast furnace slag and to realize the high-value utilization of chemical components contained in the blast furnace slag is an effective method for solving the problem of disposal of the blast furnace slag.
Therefore, the invention develops a method for high-value utilization and synergistic carbon fixation of blast furnace slag.
Disclosure of Invention
In order to solve the technical problems, the invention provides a blast furnaceThe method for high-value utilization and synergistic carbon fixation of slag comprises the steps of preparing molecular sieve adsorbent and calcium carbonate from blast furnace slag, using the prepared molecular sieve adsorbent for carbon capture of blast furnace gas, reducing capture cost of pressure swing adsorption, and adsorbing CO after capture 2 And the high-purity calcium carbonate is synthesized with the calcium-based component, and the waste heat of blast furnace gas is utilized in the process, so that the consumption of other energy sources is reduced.
In order to achieve the above purpose, the present invention provides the following technical solutions:
the invention provides a method for high-value utilization and synergistic carbon fixation of blast furnace slag, which takes blast furnace slag as raw material to prepare calcium carbonate and molecular sieve adsorbent, and uses the obtained molecular sieve adsorbent for CO in blast furnace gas 2 Is trapped by pressure swing adsorption of trapped CO 2 And the method is used for preparing calcium carbonate by mineralizing blast furnace slag.
Further, the method comprises the steps of preparing molecular sieve adsorbent from blast furnace slag and CO in blast furnace gas 2 Three parts of high-purity calcium carbonate prepared by pressure swing adsorption trapping and blast furnace slag comprise the following steps:
grinding blast furnace slag, and leaching with acid to obtain leaching solution and leaching slag;
adjusting the silicon-aluminum ratio of the leaching slag, performing hydrothermal treatment, washing and drying to obtain a molecular sieve adsorbent;
pretreated blast furnace gas is subjected to Pressure Swing Adsorption (PSA) and CO 2 Adsorption trapping, wherein the adsorbent used in the pressure swing adsorption process is a molecular sieve adsorbent prepared from leaching residues;
removing impurities from the leaching solution to obtain calcium hydroxide, and adsorbing and capturing CO with the calcium hydroxide 2 Mineralizing reaction to obtain calcium carbonate.
Further, in the method for high-value utilization and synergistic carbon fixation of the blast furnace slag, the method more specifically comprises the following steps:
grinding blast furnace slag, leaching with acid to extract valuable components and obtain leaching solution with high calcium content and leaching slag with high silicon-aluminum content;
the component analysis is carried out on the leaching slag, and the leaching slag is carried out according to the silicon-aluminum ratio composition of the target molecular sieveRegulating silicon-aluminum content, then feeding into a hydrothermal chamber for hydrothermal treatment to form a molecular sieve specific crystal form, wherein the hydrothermal chamber is provided with heat by blast furnace gas waste heat to ensure the constancy of hydrothermal temperature, washing after the hydrothermal treatment is finished, drying in a drying chamber by utilizing the blast furnace gas waste heat, and finally pelletizing to obtain the catalyst for CO 2 An adsorbed spherical molecular sieve adsorbent;
blast furnace gas enters a PSA unit for pressure swing adsorption after dust removal, TRT (blast furnace gas power generation equipment) and pretreatment, and CO is carried out 2 The adsorbent used in the adsorption and trapping process is molecular sieve adsorbent prepared from leaching residues, and CO with high purity (concentration is 35-95%) is obtained through pressure swing adsorption 2 Product gas and concentrated gas;
removing impurities from the leaching solution to obtain calcium hydroxide, and adsorbing and capturing CO with the calcium hydroxide 2 And (3) carrying out mineralization reaction, wherein the temperature required by mineralization is provided by waste heat of blast furnace gas, and finally, the high-purity calcium carbonate is obtained.
Further, the temperature of the acid leaching is 20-90 ℃ and the time is 1-6h.
Further, the concentration of the acid solution used for acid leaching is 1-6mol/L.
Still further, the acid solution includes one or more of an organic acid or an inorganic acid.
Further, the hydrothermal temperature of the hydrothermal treatment is 50-200 ℃ and the hydrothermal time is 1-20h.
Furthermore, the hydrothermal treatment adopts alkaline substances such as sodium hydroxide, ammonia water, ammonium carbonate and the like to adjust the solution to be in an alkaline environment.
Further, the pretreated blast furnace gas is compressed to 150 to 500kPa (absolute pressure, the same applies hereinafter).
Still further, the pretreatment includes desulfurization and water removal.
Further, the pressure swing adsorption process comprises pressure boost adsorption, tower-to-tower pressure equalization and vacuum desorption;
the adsorption time of the pressurized adsorption is 1-10min, and the adsorption temperature is 10-80 ℃;
the time for equalizing pressure among towers is 10-30s;
the pressure of the vacuum desorption is 10-50kPa, and the time is 1-10min.
Further, the pressure swing adsorption process at least comprises four adsorption towers to ensure CO in blast furnace gas 2 The molecular sieve adsorbent prepared by filling blast furnace slag is filled in the adsorption tower.
Further, the leaching solution impurity removal process is divided into two sections, and the pH value is respectively adjusted to 3-5 and 10-12. The first stage of impurity removal process is to adjust the pH value to 3-5, mainly remove iron in leaching solution, and the stage of impurity removal process is to generate ferric hydroxide sediment for filtration and removal; and in the second stage, the pH value is adjusted to 10-12 in the impurity removal process, impurities such as magnesium, aluminum, titanium and the like in the leaching solution are mainly removed, precipitates such as magnesium hydroxide, aluminum hydroxide, titanium hydroxide and the like are generated in the second stage, the precipitates are removed by filtration, the pH value of the leaching solution is continuously increased to 12-13 after the impurities are removed, and calcium chloride in the solution is completely reacted to generate calcium hydroxide precipitates, so that mineralized reaction raw materials are obtained.
Further, alkaline substances are added in the process of removing impurities from the leaching solution to adjust the pH value, wherein the alkaline substances comprise waste alkali liquor, sodium hydroxide, ammonia water or ammonium carbonate in the preparation step of the molecular sieve adsorbent.
Further, the mass ratio of water to calcium hydroxide in the mineralization reaction is 10-20, the time is 1-10h, and the temperature is 30-60 ℃.
Compared with the prior art, the invention has the following advantages and technical effects:
(1) The invention takes blast furnace slag as raw material, prepares molecular sieve by hydrothermal method and synthesizes calcium carbonate by carbonating method, the molecular sieve can be used as CO in blast furnace gas 2 The prepared calcium carbonate can meet the industrial calcium carbonate standard, can be used in different industries, and generally realizes the high-value utilization of blast furnace slag.
(2) The heat required in the molecular sieve synthesis and calcium carbonate preparation processes is derived from the waste heat of blast furnace gas, an external heat source is not needed, and the consumption of additional energy sources is reduced.
(3) Existing industrial CO 2 Capturing CO in high concentration is required 2 Can meet the requirements of subsequent storage and application, and the invention does not need to obtain high concentrationCO 2 Product gas which meets the requirement of mineralization reaction for synthesizing calcium carbonate and realizes CO of blast furnace gas 2 And emission reduction is carried out, and purified coal gas is obtained after decarburization of the coal gas, wherein the combustible gas component is increased, so that the combustion heat value of the blast furnace gas is increased.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application, illustrate and explain the application and are not to be construed as limiting the application. In the drawings:
FIG. 1 is a schematic diagram of a flow of high value utilization and synergistic carbon fixation of the blast furnace slag of the present invention;
FIG. 2 is a physical diagram of the spherical molecular sieve adsorbent prepared in example 1 of the present invention.
Detailed Description
Various exemplary embodiments of the invention will now be described in detail, which should not be considered as limiting the invention, but rather as more detailed descriptions of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the invention described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present invention. The specification and examples of the present invention are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
The embodiment of the invention provides a method for high-value utilization and synergistic carbon fixation of blast furnace slag (the flow chart is shown in figure 1), wherein the blast furnace slag is used as a raw material to prepare calcium carbonate and a molecular sieve adsorbent, and the obtained molecular sieve adsorbent is used for CO in blast furnace gas 2 Is trapped by pressure swing adsorption of trapped CO 2 The method is used for preparing calcium carbonate by mineralizing the blast furnace slag, and comprises the steps of preparing molecular sieve adsorbent by the blast furnace slag and preparing CO in blast furnace gas 2 Three parts of high-purity calcium carbonate are prepared by pressure swing adsorption trapping and blast furnace slag, and more specifically, the method comprises the following steps:
grinding blast furnace slag, leaching with acid to extract valuable components and obtain leaching solution with high calcium content and leaching slag with high silicon-aluminum content;
the leaching slag is subjected to component analysis, silicon-aluminum content regulation is carried out according to the silicon-aluminum proportion composition of the target molecular sieve, then the leaching slag is fed into a hot water chamber for hydrothermal treatment, a molecular sieve specific crystal form is formed, the hot water chamber provides heat by the waste heat of blast furnace gas, the constant hydrothermal temperature is ensured, the leaching slag is washed after the hydrothermal treatment is finished, the waste heat of blast furnace gas is utilized, the leaching slag is dried in a drying chamber, and finally the leaching slag is pelletized to obtain the product for CO 2 An adsorbed spherical molecular sieve adsorbent;
blast furnace gas enters a PSA unit for pressure swing adsorption after dust removal, TRT (blast furnace gas power generation equipment) and pretreatment, and CO is carried out 2 The adsorption and trapping process includes the steps of changing the molecular sieve adsorbent prepared with leached slag as the adsorbent in the pressure swing adsorption processPressure adsorption to obtain CO with higher purity (concentration of 35-95%) 2 Product gas and concentrated gas;
removing impurities from the leaching solution to obtain calcium hydroxide, and adsorbing and capturing CO with the calcium hydroxide 2 And (3) carrying out mineralization reaction, wherein the temperature required by mineralization is provided by waste heat of blast furnace gas, and finally, the high-purity calcium carbonate is obtained.
The acid leaching temperature may be 20 to 90 ℃, for example, 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃ or 90 ℃ for 1 to 6 hours, for example, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours or 6 hours, but is not limited to the recited values, and other values not recited in the numerical range are equally applicable. The higher the acid leaching temperature, the faster the leaching rate and the shorter the time to reach the leaching completion, but to reach a high leaching temperature, the more heat the blast furnace gas is required to raise, the longer the time required for the process; however, when the leaching time is not changed under other conditions, the longer the leaching time is, the better the leaching effect is, but the longer the time is, the production efficiency of the whole process is affected.
In the preferred embodiment of the present invention, the acid solution used in the acid leaching has a concentration of 1 to 6mol/L, for example, 1mol/L, 2mol/L, 3mol/L, 4mol/L, 5mol/L or 6mol/L, but the acid leaching is not limited to the recited values, and other values not recited in the numerical range are equally applicable. The acid solution comprises one or more of organic acid or inorganic acid, such as hydrochloric acid, sulfuric acid, nitric acid, formic acid, and acetic acid.
In a preferred embodiment of the invention, the liquid-to-material ratio of the acid solution to the blast furnace slag in the acid leaching process is 10-15mL to 1g.
In a preferred embodiment of the present invention, the hydrothermal temperature of the hydrothermal treatment is 50-200 ℃, for example, 50 ℃, 100 ℃, 140 ℃, 160 ℃, 180 ℃ or 200 ℃, and the hydrothermal time is 1-20 hours, for example, 1 hour, 5 hours, 10 hours, 15 hours or 20 hours, but not limited to the recited values, and other non-recited values in the numerical range are equally applicable. Hydrothermal is a necessary condition for molecular sieve preparation, and the hydrothermal process generates specific crystals of molecular sieve and increases gradually. The hydrothermal temperature setting is based on two points, namely, the difference exists between the hydrothermal temperature ranges required by specific molecular sievesSecondly, the hydrothermal temperature influences the crystal generation speed of the molecular sieve, the higher the temperature is, the faster the crystal grows, but the result that the overall crystal form of the molecular sieve is poor due to the overhigh temperature is also present; on the other hand, the hydrothermal time also affects the production of the molecular sieve, firstly, the minimum time is needed for the generation of the molecular sieve crystals, then, the more the crystals are generated along with the increase of the time, but the hydrothermal time is too long, the crystallinity of the molecular sieve is reduced, the purity of the molecular sieve is affected, and the later CO of the molecular sieve is caused 2 The adsorption performance is lowered.
In the preferred embodiment of the invention, the hydrothermal treatment adopts alkaline substances such as sodium hydroxide, ammonia water, ammonium carbonate and the like to adjust the solution to be an alkaline environment, and the hydrothermal treatment is a necessary environment for preparing the molecular sieve in the alkaline environment, and only specific crystals of the molecular sieve can be generated in the alkaline environment.
In a preferred embodiment of the invention, the pretreatment includes desulfurization and water removal, and the pretreated blast furnace gas is compressed to 150-500kPa, such as 150kPa, 200kPa, 300kPa, 400kPa or 500kPa, etc., but not limited to the values recited, and other values not recited in the numerical range are equally applicable.
In a preferred embodiment of the present invention, the pressure swing adsorption process includes pressure swing adsorption, column-to-column pressure equalization and vacuum desorption; the pressure swing adsorption process at least comprises four adsorption towers to ensure CO in blast furnace gas 2 A molecular sieve adsorbent prepared by filling blast furnace slag is filled in the adsorption tower; the states of the 4 columns are: 1 tower is used for adsorption, 1 tower is used for desorption, and two towers are used for equalizing pressure;
the adsorption time of the pressurized adsorption is 1-10min, for example, 0.5min, 1min, 3min, 5min, 7min, 9min or 10min, the adsorption temperature is 10-80 ℃, for example, 10 ℃, 20 ℃, 30 ℃, 40 ℃ or 50 ℃, but the pressurized adsorption is not limited to the recited values, and other non-recited values in the range of values are applicable;
the time for equalizing pressure among the towers is 10-30s, for example, 10s, 15s, 20s, 25s or 30s, but is not limited to the recited values, and other non-recited values in the numerical range are equally applicable;
the vacuum desorption pressure is 10 to 50kPa, for example, 10kPa, 20kPa, 30kPa, 40kPa or 50kPa, and the time is 1 to 10 minutes, for example, 1 minute, 2 minutes, 4 minutes, 6 minutes, 8 minutes or 10 minutes, but not limited to the values recited, and other values not recited in the numerical range are equally applicable.
Pressure swing adsorption process: the adsorption tower is filled with the prepared molecular sieve adsorbent, blast furnace gas is introduced into the adsorption tower, the pressure is set, and the molecular sieve adsorbent is used for adsorbing CO 2 Has good adsorption performance, and CO in gas 2 The other gases are seldom adsorbed on the molecular sieve in the pore canal adsorbed on the molecular sieve, and most of the gases pass through the adsorption tower to be discharged.
The sectional impurity removal is a conventional technical means in the field, and the method has the advantage that the pH value of the impurity removal process of the first section and the second section is limited. In the preferred embodiment of the invention, the leaching solution impurity removal process needs to be divided into two sections to adjust the pH value to be 3-5 and 10-12 respectively, and alkaline substances are added in the leaching solution impurity removal process to adjust the pH value, wherein the alkaline substances comprise waste alkali liquor, sodium hydroxide, ammonia water or ammonium carbonate in the preparation step of the molecular sieve adsorbent. The first stage solution may have a pH of 3, 3.5, 4, 4.5 or 5 and the second stage solution may have a pH of 10, 10.5, 11, 11.5 or 12, but is not limited to the recited values, as other non-recited values within the range of values are equally applicable.
The first stage of impurity removal process is to adjust the pH value to 3-5, mainly remove iron in leaching solution, and the stage of impurity removal process is to generate ferric hydroxide sediment for filtration and removal; and in the second stage, the pH value is adjusted to 10-12 in the impurity removal process, impurities such as magnesium, aluminum, titanium and the like in the leaching solution are mainly removed, precipitates such as magnesium hydroxide, aluminum hydroxide, titanium hydroxide and the like are generated in the second stage, the precipitates are removed by filtration, the pH value of the leaching solution is continuously increased to 12-13 after the impurities are removed, and calcium chloride in the solution is completely reacted to generate calcium hydroxide precipitates, so that mineralized reaction raw materials are obtained.
In a preferred embodiment of the invention, the mass ratio of water to calcium hydroxide in the mineralization reaction is 10-20, for example 10, 12, 14, 16, 18 or 20, for a period of time of 1-10 hours, for example 1 hour, 2 hours, 4 hours, 6 hours, 8 hours or 10 hours, at a temperature of 30-60 ℃, for example 30 ℃, 40 ℃, 50 ℃ or 60 ℃, but is not limited to the recited values, and other non-recited values in the range of values are equally applicable.
The equipment used in the high-value utilization and synergistic carbon fixation process of the blast furnace slag is common equipment in the field, and the regulation and control of the technical parameters can be realized.
The raw materials used in the embodiment of the invention are all purchased commercially, wherein the sources of the blast furnace slag and the blast furnace gas are blast furnace slag and gas generated by iron making in the steel blast furnace process.
The technical scheme of the invention is further described by the following examples.
Example 1
Grinding blast furnace slag to 100 meshes, and then leaching with 4mol/L hydrochloric acid according to a feed liquid ratio of 10mL to 1g at 80 ℃ for 6 hours to obtain leaching solution with high calcium content and leaching slag with high silicon-aluminum content;
component analysis is carried out on leaching slag by adopting X-ray fluorescence spectrum analysis (XRF), the analysis result is shown in table 1, according to the silicon-aluminum ratio composition of a target molecular sieve, sodium aluminate is adopted to adjust the silicon-aluminum ratio to 1.5, then the leaching slag is fed into a hydrothermal chamber for hydrothermal treatment, the hydrothermal temperature is 90 ℃ and the hydrothermal time is 7 hours, a molecular sieve specific crystal form is formed, the hydrothermal chamber is provided with heat by blast furnace gas waste heat, the constancy of the hydrothermal temperature is ensured, the leaching slag is washed after the hydrothermal completion, and is dried in a drying chamber by a machine by utilizing the blast furnace gas waste heat, and finally spherical shape of 2-4mm is obtained by pelletizing and is used for CO 2 The spherical molecular sieve adsorbent is adsorbed, and the physical diagram of the spherical molecular sieve is shown in figure 2;
TABLE 1 composition of leaching residue components
| Sequence number | Composition of the components | Leaching residue composition/wt% |
| 1 | CaO | 1.893 |
| 2 | SiO 2 | 92.627 |
| 3 | TiO 2 | 0.837 |
| 4 | Al 2 O 3 | 0.611 |
| 5 | MgO | 0.355 |
| 6 | SO 3 | 0.259 |
| 7 | Fe 2 O 3 | 0.056 |
| 8 | Cl | 3.391 |
| 9 | K 2 O | 0.029 |
| 10 | SrO | 0.003 |
| 11 | ZrO 2 | 0.031 |
The blast furnace gas (raw material) was fed at 1000Nm 3 Introducing the gas quantity/h to carry out dust removal, TRT and pretreatment (desulfurization and dewatering) to compress the blast furnace gas to 500kPa, then introducing the blast furnace gas into a PSA unit (comprising four pressure swing adsorption towers) to carry out pressure swing adsorption to carry out CO 2 The adsorption and trapping process includes three steps of pressurized adsorption, pressure equalizing between towers and vacuum desorption, the adsorption time is 4min, the adsorption temperature is 10 deg.c, the pressure equalizing between towers is 30s, the vacuum desorption pressure is 10kPa, the time is 4min, and CO is obtained through pressure swing adsorption 2 Product gas and concentrated gas;
removing impurities from the leaching solution, regulating pH value of the first stage to 4 with sodium hydroxide, regulating pH value of the second stage to 12 with sodium hydroxide, continuously increasing pH value until calcium hydroxide is generated, and adsorbing and trapping CO 2 And (3) carrying out mineralization reaction, wherein the mass ratio of water to calcium hydroxide in the mineralization reaction is 20, the time is 2h, the temperature is 60 ℃, and the temperature required by mineralization is provided by waste heat of blast furnace gas, so that the calcium carbonate is finally obtained.
In the treatment process of example 1, a flue gas analyzer was used to detect blast furnace gas (raw material), CO 2 The gas components of the product gas and the concentrated gas are shown in Table 2.
TABLE 2 blast furnace gas (raw materials), CO 2 Gas composition comparison (volume percent) of product gas and concentrated gas
As can be seen from Table 2, the CO produced 2 The volume concentration of the product gas is 90.7%, the gas is purified, and the combustible gases CO and H are obtained 2 The volume concentration reaches 28.1% and 4.3% respectively.
CO in different gases is adsorbed by pressure swing 2 Is calculated by combining the quality of the loaded adsorbent to obtain the CO in the pressure swing adsorption process of the molecular sieve adsorbent prepared in the example 1 2 The adsorption quantity is 100mg/g, CO 2 The trapping amount is 410.5kg/h, the yield of calcium carbonate prepared by mineralizing leaching solution is 933.0kg/h, caCO 3 The purity of (2) is 98.5%, and meets the industrial calcium carbonate standard (the calcium carbonate content is not less than 97%).
Example 2
Grinding blast furnace slag to 100 meshes, and then leaching with hydrochloric acid with the ratio of feed liquid being 10mL to 1g and 1mol/L at the temperature of 20 ℃ for 1h to extract valuable components and obtain leaching solution with high calcium content and leaching slag with high silicon-aluminum content;
performing component analysis on leaching residues by adopting X-ray fluorescence spectrum analysis (XRF), adjusting the silicon-aluminum ratio to 0.5 according to the silicon-aluminum ratio of a target molecular sieve, performing hydrothermal treatment by adopting sodium aluminate, wherein the hydrothermal temperature is 50 ℃, the hydrothermal time is 1h, forming a molecular sieve specific crystal form, the hydrothermal chamber is provided with heat by using blast furnace gas waste heat to ensure the constancy of the hydrothermal temperature, washing after the hydrothermal completion, drying in a drying chamber by using blast furnace gas waste heat, and finally pelletizing to obtain 2-4mm spheres for CO 2 An adsorbed spherical molecular sieve adsorbent;
the blast furnace gas (raw material) was fed at 1000Nm 3 Introducing the gas quantity/h to carry out dust removal, TRT and pretreatment (desulfurization and dewatering) to compress the blast furnace gas to 150kPa, and then introducing the blast furnace gas into a PSA unit (comprising four pressure swing adsorption towers) to carry out pressure swing adsorption to carry out CO 2 The adsorption and trapping, the adsorbent used in the pressure swing adsorption process is a molecular sieve adsorbent prepared from leaching residues,the pressure swing adsorption process comprises three processes of pressure boost adsorption, pressure equalizing between towers and vacuum desorption, wherein the adsorption time is 1min, the adsorption temperature is 10 ℃, the pressure equalizing between towers is 10s, the pressure of vacuum desorption is 10kPa, the time is 1min, and CO is obtained through pressure swing adsorption 2 Product gas and concentrated gas;
removing impurities from the leaching solution, regulating pH value of the first stage to 3 with sodium hydroxide, regulating pH value of the second stage to 11 with sodium hydroxide, continuously increasing pH value until calcium hydroxide is generated, and adsorbing and trapping CO with calcium hydroxide 2 And (3) carrying out mineralization reaction, wherein the mass ratio of water to calcium hydroxide in the mineralization reaction is 10, the time is 1h, the temperature is 30 ℃, and the temperature required by mineralization is provided by blast furnace gas waste heat, so that the calcium carbonate is finally obtained.
In the treatment process of example 2, a flue gas analyzer was used to detect blast furnace gas (raw material), CO 2 The gas components of the product gas and the concentrated gas are shown in Table 3.
TABLE 3 blast furnace gas (raw materials), CO 2 Gas composition comparison (volume percent) of product gas and concentrated gas
As can be seen from Table 3, the CO produced 2 The volume concentration of the product gas is 35.3%, the purification of the gas is realized, and the combustible gases CO and H 2 The volume concentration reaches 28.1% and 4.3% respectively.
CO in pressure swing adsorption process of molecular sieve adsorbent prepared in example 2 2 Adsorption capacity is 40mg/g, CO 2 The trapping amount is 102.6kg/h, and the yield of calcium carbonate prepared by mineralizing leaching solution is 233.3kg/h, caCO 3 The purity of (2) is 97.1%, and meets the industrial calcium carbonate standard.
Example 3
Grinding blast furnace slag to 100 meshes, and then leaching with 6mol/L hydrochloric acid according to a feed-liquid ratio of 10mL to 1g, wherein the temperature of the acid leaching is 90 ℃ and the time is 6 hours, so that extraction of valuable components is realized, and leaching liquid with high calcium content and leaching slag with high silicon-aluminum content are obtained;
component analysis is carried out on leaching slag by adopting X-ray fluorescence spectrum analysis (XRF), the silicon-aluminum ratio is regulated to 4 by adopting sodium aluminate according to the silicon-aluminum ratio composition of a target molecular sieve, then the leaching slag is fed into a hydrothermal chamber for hydrothermal treatment, the hydrothermal temperature is 200 ℃, the hydrothermal time is 20 hours, a molecular sieve specific crystal form is formed, the hydrothermal chamber provides heat by blast furnace gas waste heat, the constancy of the hydrothermal temperature is ensured, the leaching slag is washed after the hydrothermal completion, the blast furnace gas waste heat is utilized, the leaching slag is dried in a drying chamber, and finally spherical shape of 2-4mm is obtained by pelletizing and is used for CO 2 An adsorbed spherical molecular sieve adsorbent;
the blast furnace gas (raw material) was fed at 1000Nm 3 Introducing the gas quantity/h to carry out dust removal, TRT and pretreatment (desulfurization and dewatering) to compress the blast furnace gas to 500kPa, then introducing the blast furnace gas into a PSA unit (comprising four pressure swing adsorption towers) to carry out pressure swing adsorption to carry out CO 2 The adsorption and trapping process includes three steps of pressurized adsorption, pressure equalizing between towers and vacuum desorption, the adsorption time is 10min, the adsorption temperature is 100 deg.c, the pressure equalizing between towers is 30s, the vacuum desorption pressure is 50kPa, the time is 10min, and CO is obtained through pressure swing adsorption 2 Product gas and concentrated gas;
removing impurities from the leaching solution, regulating pH value of the first stage to 5 with sodium hydroxide, regulating pH value of the second stage to 13 with sodium hydroxide, continuously increasing pH value until calcium hydroxide is generated, and adsorbing and trapping CO with calcium hydroxide 2 And (3) carrying out mineralization reaction, wherein the mass ratio of water to calcium hydroxide in the mineralization reaction is 20, the time is 10 hours, the temperature is 60 ℃, and the temperature required by mineralization is provided by the waste heat of blast furnace gas, so that the calcium carbonate is finally obtained.
In the treatment process of example 3, a flue gas analyzer was used to detect blast furnace gas (raw material), CO 2 The gas components of the product gas and the concentrated gas are shown in Table 4.
TABLE 4 blast furnace gas (raw materials), CO 2 Gas composition comparison (volume percent) of product gas and concentrated gas
As can be seen from Table 4, the CO produced 2 The volume concentration of the product gas is 53.5%, the gas is purified, and the combustible gases CO and H are obtained 2 The volume concentration reaches 24.1% and 3.8% respectively.
CO in pressure swing adsorption Process of molecular Screen adsorbent prepared in example 3 2 The adsorption quantity is 60mg/g, CO 2 The trapping amount is 164.0kg/h, the yield of calcium carbonate prepared by mineralizing the leaching solution is 373.2kg/h, caCO 3 The purity of (2) is 97.2%, and meets the industrial calcium carbonate standard.
Comparative example 1
The difference from example 1 is only that the acid leaching temperature is 15℃and the time is 10 hours.
Comparative example 1 CO produced 2 The volume concentration of the product gas is 40.1 percent, and the prepared molecular sieve adsorbent is CO in the pressure swing adsorption process 2 The adsorption capacity is 31.4mg/g, CO 2 The trapping amount is 180.1kg/h, and the yield of calcium carbonate prepared by mineralizing leaching solution is 409.1kg/h, caCO 3 Is 78.2% pure and does not meet the industrial calcium carbonate standard.
Comparative example 2
The only difference from example 1 is that the hydrothermal temperature of the hydrothermal treatment is 300℃and the hydrothermal time is 10 hours.
Comparative example 2 CO produced 2 The volume concentration of the product gas is 50.1%, and the prepared molecular sieve adsorbent is used for CO in the pressure swing adsorption process 2 Adsorption capacity is 40.2mg/g, CO 2 The trapping amount is 256.9kg/h, the yield of calcium carbonate prepared by mineralizing leaching solution is 583.86kg/h, caCO 3 The purity of (2) is 80.2%, and the standard of industrial calcium carbonate is not satisfied.
Comparative example 3
The only difference from example 1 is that the mineralization time is 15h and the temperature is 20 ℃.
The longer the mineralization time, the more complete the mineralization reaction, but the yield of calcium carbonate will decrease. Thus, comparative example 3 produced CO 2 The volume of the product gas is concentratedThe degree of the reaction is 90.7%, and the prepared molecular sieve adsorbent is CO in the pressure swing adsorption process 2 The adsorption quantity is 100mg/g, CO 2 The trapping amount is 410.5kg/h, and the yield of calcium carbonate prepared by mineralizing leaching solution is 310.3kg/h, caCO 3 The purity of (2) was 94.2% and did not meet the industrial calcium carbonate standard.
Comparative example 4
The only difference from example 1 is that the mass ratio of water to calcium hydroxide in the mineralization reaction was 5.
Comparative example 4 CO produced 2 The volume concentration of the product gas is 90.7%, and the prepared molecular sieve adsorbent is used for CO in the pressure swing adsorption process 2 The adsorption quantity is 100mg/g, CO 2 The trapping amount is 410.5kg/h, the yield of calcium carbonate prepared by mineralizing leaching solution is 525.3kg/h, caCO 3 The purity of (2) is 90.2%, and the standard of industrial calcium carbonate is not satisfied.
Comparative example 5
The difference from example 1 is that the adsorption time of the pressure-increasing adsorption is 30min and the adsorption temperature is 90 ℃.
Comparative example 5 CO produced 2 The volume concentration of the product gas is 31.5%, and the prepared molecular sieve adsorbent is used for CO in the pressure swing adsorption process 2 Adsorption capacity is 40.1mg/g, CO 2 The trapping amount is 210.2kg/h, and the yield of calcium carbonate prepared by mineralizing leaching solution is 477.2kg/h, caCO 3 The purity of (2) is 88.7%, and the standard of industrial calcium carbonate is not satisfied.
This is because the adsorption time cannot be too long, which can lead to saturation of adsorption of the molecular sieve adsorbent and CO 2 No longer adsorbed on the adsorbent and discharged along with the adsorption tail gas, resulting in CO 2 The trapping amount is reduced; adsorption temperature vs. CO 2 The adsorption effect is great, the higher the temperature is, the CO 2 The lower the adsorption amount, the CO 2 The lower the trapping amount.
Comparative example 6
The only difference from example 1 is that the pressure of vacuum desorption was 100kPa.
Comparative example 6 CO produced 2 The volume concentration of the product gas is 60.1%, and the prepared molecular sieve adsorbent is used for CO in the pressure swing adsorption process 2 The adsorption quantity is 54.3mg/g, CO 2 The trapping amount is 324.5kg/h, the yield of calcium carbonate prepared by mineralizing leaching solution is 736.8kg/h, caCO 3 The purity of (2) is 85.9%, and the standard of industrial calcium carbonate is not satisfied.
Comparative example 7
The difference from example 1 is only that the equalizing time is 5s.
Comparative example 7 CO 2 The volume concentration of the product gas is 80.1%, and the prepared molecular sieve adsorbent is used for CO in the pressure swing adsorption process 2 The adsorption quantity is 95.2mg/g, CO 2 The trapping amount is 378.3kg/h, the yield of calcium carbonate prepared by mineralizing leaching solution is 859.1kg/h, caCO 3 The purity of (2) is 87.6%, and the standard of industrial calcium carbonate is not satisfied.
This is because too short a pressure equalization time affects CO 2 Product gas purity, too long can affect CO 2 Collection amount.
The foregoing is merely a preferred embodiment of the present application, but the scope of the present application is not limited thereto, and any changes or substitutions easily conceivable by those skilled in the art within the technical scope of the present application should be covered in the scope of the present application. Therefore, the protection scope of the present application shall be subject to the protection scope of the claims.
Claims (10)
1. A method for high-value utilization and synergistic carbon fixation of blast furnace slag is characterized in that the blast furnace slag is used as raw material to prepare calcium carbonate and molecular sieve adsorbent, and the obtained molecular sieve adsorbent is used for CO in blast furnace gas 2 Is trapped by pressure swing adsorption of trapped CO 2 And the method is used for preparing calcium carbonate by mineralizing blast furnace slag.
2. The method for high-value utilization and synergistic carbon fixation of blast furnace slag according to claim 1, which is characterized by comprising the following steps:
grinding blast furnace slag, and leaching with acid to obtain leaching solution and leaching slag;
adjusting the silicon-aluminum ratio of the leaching slag, performing hydrothermal treatment, washing and drying to obtain a molecular sieve adsorbent;
the blast furnace gas is pretreated, then pressure swing adsorption is carried out, and CO is carried out 2 Adsorption trapping, wherein the adsorbent used in the pressure swing adsorption process is a molecular sieve adsorbent prepared from leaching residues;
removing impurities from the leaching solution to obtain calcium hydroxide, and adsorbing and capturing CO with the calcium hydroxide 2 Mineralizing reaction to obtain calcium carbonate.
3. The method for high-value utilization and synergistic carbon fixation of blast furnace slag according to claim 2, wherein the temperatures required for the hydrothermal treatment, drying and mineralization reactions are provided by the waste heat of blast furnace gas.
4. The method for high-value utilization and synergistic carbon fixation of blast furnace slag according to claim 2, wherein the acid leaching temperature is 20-90 ℃ and the time is 1-6h.
5. The method for high-value utilization and synergistic carbon fixation of blast furnace slag according to claim 2, wherein the concentration of the acid solution used for acid leaching is 1-6mol/L.
6. The method for high-value utilization and synergistic carbon fixation of blast furnace slag according to claim 2, wherein the hydrothermal temperature of the hydrothermal treatment is 50-200 ℃ and the hydrothermal time is 1-20h.
7. The method for high-value utilization and synergistic carbon fixation of blast furnace slag according to claim 2, wherein the pretreated blast furnace gas is compressed to 150-500kPa.
8. The method for high-value utilization and synergistic carbon fixation of blast furnace slag according to claim 2, wherein the pressure swing adsorption process comprises pressure boost adsorption, inter-tower pressure equalization and vacuum desorption;
the adsorption time of the pressurized adsorption is 1-10min, and the adsorption temperature is 10-80 ℃;
the time for equalizing pressure among towers is 10-30s;
the pressure of the vacuum desorption is 10-50kPa, and the time is 1-10min.
9. The method for high-value utilization and synergistic carbon fixation of blast furnace slag according to claim 2, wherein the leaching solution impurity removal process is divided into two sections, and the pH values are respectively adjusted to 3-5 and 10-12.
10. The method for high-value utilization and synergistic carbon fixation of blast furnace slag according to claim 2, wherein the mass ratio of water to calcium hydroxide in mineralization reaction is 10-20, the time is 1-10h, and the temperature is 30-60 ℃.
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| KR102505258B1 (en) * | 2021-12-16 | 2023-02-28 | 정충의 | Construction material manufacturing method by capturing carbon dioxide using calcium carbonate generated from steelmaking slag |
| CN115364618A (en) * | 2022-08-16 | 2022-11-22 | 西南化工研究设计院有限公司 | Flue gas separation and comprehensive utilization method |
| CN115582105A (en) * | 2022-09-30 | 2023-01-10 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for preparing CO by modifying titanium-containing blast furnace slag 2 Method for coupling mineralization of capture material |
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