CN109231249A - A kind of high efficiency extraction blast furnace slag active constituent and carbonate fixed CO2The method for producing calcium carbonate - Google Patents
A kind of high efficiency extraction blast furnace slag active constituent and carbonate fixed CO2The method for producing calcium carbonate Download PDFInfo
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- CN109231249A CN109231249A CN201811114216.5A CN201811114216A CN109231249A CN 109231249 A CN109231249 A CN 109231249A CN 201811114216 A CN201811114216 A CN 201811114216A CN 109231249 A CN109231249 A CN 109231249A
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- blast furnace
- furnace slag
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- filter residue
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- 239000002893 slag Substances 0.000 title claims abstract description 78
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 26
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 title claims abstract description 14
- 239000000470 constituent Substances 0.000 title claims abstract description 14
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 13
- 238000000605 extraction Methods 0.000 title claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- 239000011575 calcium Substances 0.000 claims abstract description 78
- 239000000706 filtrate Substances 0.000 claims abstract description 61
- 238000000034 method Methods 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 16
- 238000004090 dissolution Methods 0.000 claims abstract description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 51
- 239000000047 product Substances 0.000 claims description 39
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 36
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 32
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 32
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 31
- 239000007788 liquid Substances 0.000 claims description 30
- 239000007787 solid Substances 0.000 claims description 30
- 229910021529 ammonia Inorganic materials 0.000 claims description 25
- 238000000926 separation method Methods 0.000 claims description 25
- 239000007789 gas Substances 0.000 claims description 24
- 239000013049 sediment Substances 0.000 claims description 22
- 239000011777 magnesium Substances 0.000 claims description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 20
- 239000011259 mixed solution Substances 0.000 claims description 19
- 229910052925 anhydrite Inorganic materials 0.000 claims description 18
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- 150000002500 ions Chemical class 0.000 claims description 14
- 238000001228 spectrum Methods 0.000 claims description 14
- 238000004876 x-ray fluorescence Methods 0.000 claims description 14
- 239000000377 silicon dioxide Substances 0.000 claims description 13
- 238000011084 recovery Methods 0.000 claims description 12
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 11
- 229910052681 coesite Inorganic materials 0.000 claims description 11
- 229910052906 cristobalite Inorganic materials 0.000 claims description 11
- 230000001376 precipitating effect Effects 0.000 claims description 11
- 229910052682 stishovite Inorganic materials 0.000 claims description 11
- 229910052905 tridymite Inorganic materials 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 10
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 claims description 10
- 229910002588 FeOOH Inorganic materials 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 9
- 230000006837 decompression Effects 0.000 claims description 9
- 238000001704 evaporation Methods 0.000 claims description 9
- 230000008020 evaporation Effects 0.000 claims description 9
- 239000012530 fluid Substances 0.000 claims description 9
- 239000000391 magnesium silicate Substances 0.000 claims description 9
- 229910052919 magnesium silicate Inorganic materials 0.000 claims description 9
- 235000019792 magnesium silicate Nutrition 0.000 claims description 9
- 238000010792 warming Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 claims description 5
- 238000005259 measurement Methods 0.000 claims description 5
- 238000004364 calculation method Methods 0.000 claims description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 3
- 239000003245 coal Substances 0.000 claims description 3
- 239000003546 flue gas Substances 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 239000002918 waste heat Substances 0.000 claims description 3
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 2
- 230000020477 pH reduction Effects 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 9
- 229910052749 magnesium Inorganic materials 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 238000004064 recycling Methods 0.000 abstract description 3
- FYHXNYLLNIKZMR-UHFFFAOYSA-N calcium;carbonic acid Chemical compound [Ca].OC(O)=O FYHXNYLLNIKZMR-UHFFFAOYSA-N 0.000 abstract description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 25
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 24
- 238000004458 analytical method Methods 0.000 description 14
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 12
- 229910000831 Steel Inorganic materials 0.000 description 6
- 229910001424 calcium ion Inorganic materials 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 239000012495 reaction gas Substances 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 5
- 238000000441 X-ray spectroscopy Methods 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 4
- 238000003723 Smelting Methods 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 229910000805 Pig iron Inorganic materials 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910021392 nanocarbon Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009919 sequestration Effects 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- HLLSOEKIMZEGFV-UHFFFAOYSA-N 4-(dibutylsulfamoyl)benzoic acid Chemical compound CCCCN(CCCC)S(=O)(=O)C1=CC=C(C(O)=O)C=C1 HLLSOEKIMZEGFV-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000009770 conventional sintering Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002686 phosphate fertilizer Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000003516 soil conditioner Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 210000000952 spleen Anatomy 0.000 description 1
- 210000002784 stomach Anatomy 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/24—Sulfates of ammonium
- C01C1/242—Preparation from ammonia and sulfuric acid or sulfur trioxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/06—Ferric oxide [Fe2O3]
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
A kind of high efficiency extraction blast furnace slag active constituent and carbonate fixed CO2The method for producing calcium carbonate is first to extract mineralising active constituent Ca, Mg in blast furnace slag, then CO2Carbonation reaction occurs under certain temperature, pressure with the filtrate after dissolution blast furnace slag, generates carbonic acid calcium substance, while reaching fixed CO2With the purpose for recycling active constituent in blast furnace slag.The present invention has the advantages that simple process, low energy consumption, pollution-free, high financial profit.
Description
Technical field
The present invention relates to a kind of high efficiency extraction blast furnace slag active constituent and carbonate fixed CO2Produce the side of calcium carbonate
Method belongs to carbon dioxide discharge-reduction and industrial solid castoff application technology as the second resource field.
Background technique
The by-product being discharged from blast furnace when blast furnace slag is manUfaCtUre of pig iron, when furnace temperature reaches 1400 ~ 1600 DEG C, in ore
Gangue, the ash content in coke, cosolvent and other not can enter the impurity in the pig iron formed based on silicate and aluminate,
Float on the slag above iron.China is based on the heavy industry such as steel, metallurgy, the energy (electric power, petroleum, coal, natural gas etc.), often
0.3 ~ 1 ton of blast furnace slag can be discharged by refining 1 ton of iron, China's annual discharge blast furnace slag ten thousand tons about more than 2000 at present, accumulation volume of cargo in storage nearly 1
Hundred million tons.The bulk deposition of blast furnace slag not only occupies a large amount of soils, also seriously polluted ecological environment, while also resulting in resource
Significant wastage, therefore the comprehensive utilization of resources of blast furnace slag is imperative.
Currently, being focused primarily upon for utilizing for blast furnace slag: being on the one hand used for construction industry, produce cement, concrete, slag
Brick etc.;On the other hand for agricultural, production siliceous fertilizer, phosphate fertilizer and soil conditioner etc..But for construction industry and agriculture treating capacity
Small, added value of product is low, less economical.Up to the present, the high value of blast furnace slag can be thoroughly solved still without a kind of industry
Resource utilization.
Due to the difference of the grade of ore and smelting process, the chemical component of blast furnace slag is very complicated.The primary chemical of blast furnace slag
Ingredient (%) includes CaO 30 ~ 40, SiO2 30~40、Al2O3In addition to this 10 ~ 20 and MgO 5 ~ 10 is further comprised a small amount of
MnO、FeO、K2O、Na2O and some sulfide.It is CO since the sum of Ca and Mg content accounts for 50 ~ 60% in blast furnace slag2Mineralising
Desirable feedstock.Fixed CO is carbonated by blast furnace slag2Emission reduction and utilization technology realize blast furnace slag resource utilization, significantly
Limestone yield is reduced, destruction of the mineral exploration and exploitation to ecological environment is farthest reduced, reduces CO to a certain extent2
Discharge amount, to Resources for construction economizing type and friendly environment society etc. play significant role.
But blast furnace slag is the solid solution formed under high temperature, stable structure, therefore the fixed CO of blast furnace slag carbonating at present2
There are many obstacles for process.Alicja(Alicja U B, Eugeniusz M, Roman N. CO2 mineral
sequestration with the use of ground granulated blast furnace slag[J].
Gospodarka Surowcami Mineralnymi, 2017,33 (1): 111-124.) using blast furnace slag after grinding, directly
It is passed through 100% CO2, reacted in the case where pressure is 3bar for 24 hours, XRD characterization carried out to substance after reaction, no calcium carbonate generates.This
Show blast furnace slag directly and CO2Gas reaction, in gas-solid system, the transmitting in gas portion in the porous material is limited, causing
Reaction is learned to mismatch with mass transfer.Therefore, before carbonation reaction, blast furnace slag need to be by pretreatment, or grinding, or uses leachate
Ca, Mg etc. are leached, process energy consumption is high, and economy is bad.Mun(Mun M, Cho H. Mineral Carbonation for
Carbon Sequestration with Industrial Waste[J]. Energy Procedia, 2013, 37:
6999-7005.) using the mixed solution of 0.1M HCl and 0.1% EDTA as extractant, solution then is adjusted with NaOH solution
PH is then passed through CO with 1.5mL/min2Gas 1h, obtaining calcium carbonate product purity can be to 81.91%.But acid solution is used to soak
Out, on the one hand, acid solution is big to equipment extent of corrosion, increases production cost;On the other hand, solution post-processing is more difficult, difficult
To remove solvent, secondary pollution is caused, industrial production can not be applied to.
Summary of the invention
To solve the above-mentioned problems, the purpose of the present invention is to provide one kind, low energy consumption, pollution-free, handles simple a kind of
High efficiency extraction blast furnace slag active constituent and the fixed CO of carbonating2The method for producing calcium carbonate.
Technical principle of the invention is: first extracting mineralising active constituent Ca, Mg in blast furnace slag, then CO2With it is molten
Carbonation reaction occurs under certain temperature, pressure for the filtrate after solution blast furnace slag, generates carbonic acid calcium substance, while reaching fixed
CO2With the purpose for recycling active constituent in blast furnace slag.
A kind of high efficiency extraction blast furnace slag active constituent of the present invention and the fixed CO of carbonating2The method for producing calcium carbonate, packet
Include following steps:
(1) it after blast furnace slag being first ground to 37 ~ 300 μm, is added and reacts after mixing with ammonium sulfate 1:1 ~ 1:5 in mass ratio
Kettle is warming up to 250 ~ 500 DEG C with 2 ~ 6 DEG C/min, reacts 0.5 ~ 3.0h, and stirring rate is 300 ~ 500r/min, is cooled to room temperature
All solids product is taken out afterwards, and collects gaseous product;
(2) all solids product is taken to be dissolved in deionized water, holding liquid-solid ratio is 250:1 ~ 750:1, in 40 ~ 80 DEG C, stirring speed
Rate is that 1 ~ 3h is leached under 250 ~ 500r/min, and dissolution fluid vacuum decompression filters, and first-time filtrate is containing Fe2(SO4)3、MgSO4、CaSO4
Mixed solution, filter residue main component is SiO2And unreacted calcium, magnesium silicate;
(3) into first-time filtrate add mass fraction be 5 ~ 15% ammonia spirit, adjust pH value removed to 8 ~ 10 Fe impurity from
Son is separated by solid-liquid separation, and secondary filtrate is containing MgSO4、CaSO4Mixed solution, secondary filter residue is FeOOH precipitating, available through calcining
Fe2O3;
(4) continue to add the ammonia spirit that mass fraction is 5 ~ 15% into secondary filtrate, adjust pH value to 10 ~ 12 to remove Mg
Foreign ion is separated by solid-liquid separation, and filtrate is containing CaSO three times4Solution, three times filter residue be Mg (OH)2Precipitating;
(5) continue into filtrate three times add mass fraction be 5 ~ 15% ammonia spirit, adjust pH value to 12.4 ~ 13 make Ca from
Son precipitating, is separated by solid-liquid separation, and four times filtrate is sulfuric acid solution, is passed through the gaseous product being collected into step (1), it is molten to obtain ammonium sulfate
Liquid, evaporation and concentration obtain ammonia sulfate crystal, and circulation is used for step (1), and four filter residues are Ca (OH)2Precipitating, to be used for subsequent carbon
Acidification reaction;
(6) four filter residues are dissolved in deionized water and form the solution that Ca concentration is 0.12 ~ 0.28mol/L, with 10 ~ 50mL/
(min·gsample) be passed through containing CO2The gas that mass fraction is 10% ~ 50% reacts 0.5 ~ 2.0h at 30 ~ 50 DEG C, 0.1 ~ 5Mpa
After sediment is obtained by filtration, dry 12 at 80 ~ 105 DEG C ~ for 24 hours.
Step (6) as described above contains CO2Gas is the boiler that waste heat flue gas can be that any combustion carbon boiler emission comes out
Waste heat flue gas, comprising: the tail gas of coal furnace, oil burner or gas furnace discharge.
Ca content in the filter residue obtained using X-ray fluorescence spectra analysis (XRF) method determination step (2), to count
Calculate Ca recovery rate.
Ca content in the sediment obtained using X-ray fluorescence spectra analysis (XRF) method determination step (6) calculates carbonic acid
Change conversion ratio.
Ca recovery rate calculation formula:
m1: blast furnace slag quality (g);
w1: Ca mass fraction (%) in blast furnace slag;
m2: the filter residue quality (g) that step (2) obtains;
w2: Ca mass fraction (%) in the filter residue that step (2) obtains;
Ca carbonate treatment rate calculation formula:
m1: blast furnace slag quality (g);
w1: Ca mass fraction (%) in blast furnace slag;
m2: the filter residue quality (g) that step (2) obtains;
w2: Ca mass fraction (%) in the filter residue that step (2) obtains;
m3: the sediment quality (g) that step (6) obtains;
w3: Ca mass fraction (%) in the sediment that step (6) obtains;
Advantage of the invention is that making full use of CO2Feature is carbonated, mineralising emission reduction is carried out;Carbonic acid is produced by raw material of blast furnace slag
Calcium can be used for steel smelting procedure, avoid exhaustive exploitation mine;Silica can be obtained, can be used for producing Nano carbon white;This
Invention, which plays, subtracts carbon, circular economy and the triple effects of chemicals for producing high added value.
The present invention has the advantages that
(1) substance that whole process generates all has high added value, such as: silica is mainly contained in a filter residue, can be used
In production Nano carbon white;Secondary filter residue is FeOOH precipitating, and Fe can be obtained through calcining2O3;Filter residue is Mg (OH) three times2Precipitating,
MgO can be made through calcining;The sediment that step (6) obtains is calcium carbonate, can be used as the raw material of steel smelting procedure.
(2) process realizes recycling for matter and energy.Firstly, the reaction heat that carbonation reaction releases can
It is reacted for extracting, reduces the energy consumption of the process;Secondly, four filtrates are sulfuric acid solution, it is passed through and extracts the gas that reaction obtains
Body product (mainly contains NH3、SO2Deng), ammonium sulfate is obtained, evaporation and concentration obtains ammonia sulfate crystal, is circularly used for extracting
Reaction.Generally speaking, which reduces the net input of matter and energy, reduces costs, improves process economics.
(3) reaction unit using can churned mechanically reaction kettle, blast furnace slag and sulfuric acid that can be entirely different by physical property
Ammonium is uniformly mixed, and solves solid mass transfer and limit, better than high-temperature roasting furnace used by conventional sintering method (under same reaction conditions,
Ca recovery rate is respectively 95.29%, 39.25%).
(4) process realizes blast furnace slag resource utilization and CO2The dual purpose of emission reduction, while making in carbonation
It is different CO2The gas of volume fraction (10 ~ 50%) avoids and carries out CO using physical solvent, chemical solvent and film2Separation
Process further reduces cost, expands the application field of the technical process.
Detailed description of the invention
Fig. 1 is flow chart of the present invention.
Specific embodiment
Blast furnace slag used in the present invention comes from Shanxi Province's middle-jiao yang, function of the spleen and stomach Iron And Steel Co., Ltd, is measured by XRF and ICP-AES high
Ca, Mg content of clinker are respectively 58.05%, 7.59%.
The chemical composition of blast furnace slag by mass percentage, as shown in table 1.
The ingredient of 1 blast furnace slag of table
Ingredient | Ca | Mg | Si | Al | Fe |
Content/% | 58.05 | 7.59 | 17.81 | 11.02 | 2.72 |
Concentrated ammonia liquor used in the present invention: mass fraction 25%, analysis level are bought in Xilong Chemical Co., Ltd.By dense ammonia
Water prepares the ammonia spirit that mass fraction is 5%, 10%, 15%.
Ammonium sulfate is analysis level, is bought in Tianjin Kermel Chemical Reagent Co., Ltd..
CO2Gas: purity 99.9% is bought in Taiyuan Iron and Steel Co. group gas companies.
N2Gas: purity 99.9% is bought in Taiyuan Iron and Steel Co. group gas companies.
Embodiment 1
(1) blast furnace slag is dried to 1h at 105 DEG C first, is then ground to 37 ~ 53 μm.Then 5g blast furnace slag (m is weighed1=5g,
w1=58.05%) reaction kettle and 5g ammonium sulfate (blast furnace slag and ammonium sulfate mass ratio be 1:1), is added after mixing, with 2 DEG C/
Min is warming up to 250 DEG C, reacts 0.5h, stirring rate 300r/min, and all solids product (total matter is taken out after being cooled to room temperature
Amount is 8.38g), and collect gaseous product;
(2) all solids product (gross mass 8.38g) is taken to be dissolved in 2095mL deionized water (liquid-solid ratio 250:1), at 40 DEG C
Lower leaching 1h, stirring rate 250r/min.Dissolution fluid vacuum decompression filters, and first-time filtrate is containing Fe2(SO4)3、MgSO4、
CaSO4Mixed solution, filter residue main component is SiO2And unreacted calcium, magnesium silicate (m2=3.90g), using X
Fluorescent x ray spectroscopy x (XRF) method measures Ca content (w in a filter residue2=44.93%), to calculate Ca recovery rate and be
39.68%;
(3) 5% ammonia spirit is added into first-time filtrate, is adjusted pH value and is removed Fe foreign ion to 8, is separated by solid-liquid separation, secondary filter
Liquid is containing MgSO4、CaSO4Mixed solution, secondary filter residue be FeOOH precipitating, through calcining Fe can be obtained2O3;
(4) continue to add 5% ammonia spirit into secondary filtrate, adjust pH value and remove Mg foreign ion to 10, be separated by solid-liquid separation,
Filtrate is containing CaSO three times4Solution, three times filter residue be Mg (OH)2Precipitating;
(5) continue to add 5% ammonia spirit into filtrate three times, adjusting pH value to 12.4 makes Ca ion precipitation, is separated by solid-liquid separation, four
Secondary filtrate is sulfuric acid solution, is passed through the gaseous product being collected into step (1), obtains ammonium sulfate, and evaporation and concentration obtains sulphur
Sour ammonium crystal is used for step (1), and four filter residues are Ca (OH)2Precipitating, to be used for subsequent carbonation reaction;
(6) four filter residues are dissolved in 250mL deionized water, the solution that Ca concentration is 0.12mol/L are formed, with 10mL/
(min·gsample) it is passed through CO2Gas, with 90mL/ (mingsample) it is passed through N2Gas (keeps 10%CO2+90%N2For reaction gas
Atmosphere), sediment (m is obtained by filtration after reacting 0.5h under 30 DEG C, atmospheric pressure (0.1MPa)3=1.44g), it is dry at 80 DEG C
12h.Using Ca content (w in X-ray fluorescence spectra analysis (XRF) method measurement sediment3=70.81%) carbonate treatment, is calculated
Rate is 88.53%.
Embodiment 2
(1) blast furnace slag is dried to 1h at 105 DEG C first, is then ground to 53 ~ 75 μm.Then 5g blast furnace slag (m is weighed1=5g,
w1=58.05%) reaction kettle and 10g ammonium sulfate (blast furnace slag and ammonium sulfate mass ratio be 1:2), is added after mixing, with 4 DEG C/
Min is warming up to 300 DEG C, reacts 1.0h, stirring rate 400r/min, and all solids product (total matter is taken out after being cooled to room temperature
Amount is 12.09g), and collect gaseous product;
(2) all solids product (gross mass 12.09g) is taken to be dissolved in 6045mL deionized water (holding liquid-solid ratio is 500:1),
2h, stirring rate 350r/min are leached at 60 DEG C.Dissolution fluid vacuum decompression filters, and first-time filtrate is containing Fe2(SO4)3、
MgSO4、CaSO4Etc. the mixed solution of various sulfate, a filter residue main component is SiO2And unreacted calcium, magnesium silicic acid
Salt (m2=3.14g), Ca content (w in a filter residue is measured using X-ray fluorescence spectra analysis (XRF) method2=30.25%), thus
Calculating Ca recovery rate is 67.24%;
(3) 10% ammonia spirit is added into first-time filtrate, is adjusted pH value and is removed Fe foreign ion to 9, is separated by solid-liquid separation, it is secondary
Filtrate is containing MgSO4、CaSO4Mixed solution, secondary filter residue be FeOOH precipitating, through calcining Fe can be obtained2O3;
(4) continue to add 10% ammonia spirit into secondary filtrate, adjust pH value and remove Mg foreign ion to 11, be separated by solid-liquid separation,
Filtrate is containing CaSO three times4Solution, three times filter residue be Mg (OH)2Precipitating;
(5) continue to add 10% ammonia spirit into filtrate three times, adjusting pH value to 12.7 makes Ca ion precipitation, is separated by solid-liquid separation, four
Secondary filtrate is sulfuric acid solution, is passed through the gaseous product being collected into step (1), obtains ammonium sulfate, and evaporation and concentration obtains sulphur
Sour ammonium crystal is used for step (1), and four filter residues are Ca (OH)2Precipitating, to be used for subsequent carbonation reaction;
(6) four filter residues are dissolved in 250mL deionized water, the solution that Ca concentration is 0.20mol/L are formed, with 20mL/
(min·gsample) it is passed through CO2Gas, with 80mL/ (mingsample) it is passed through N2Gas (keeps 20%CO2+80%N2For reaction gas
Atmosphere), sediment (m is obtained by filtration after reacting 1.0h at 40 DEG C, 1.0Mpa3=2.44g), the dry 18h at 90 DEG C.It is penetrated using X
Line spectrofluorimetry (XRF) method measures Ca content (w in sediment3=75.25%), calculating carbonate treatment rate is 94.08%.
Embodiment 3
(1) blast furnace slag is dried to 1h at 105 DEG C first, is then ground to 75 ~ 106 μm.Then 5g blast furnace slag (m is weighed1=5g,
w1=58.05%) reaction kettle and 15g ammonium sulfate (blast furnace slag and ammonium sulfate mass ratio be 1:3), is added after mixing, with 6 DEG C/
Min is warming up to 350 DEG C, reacts 1.5h, stirring rate 500r/min, and all solids product (total matter is taken out after being cooled to room temperature
Amount is 16.49g), and collect gaseous product;
(2) all solids product (gross mass 16.49g) is taken to be dissolved in 12.37L deionized water (holding liquid-solid ratio is 750:1),
3h, stirring rate 450r/min are leached at 80 DEG C.Dissolution fluid vacuum decompression filters, and first-time filtrate is containing Fe2(SO4)3、
MgSO4、CaSO4Mixed solution, filter residue main component is SiO2And unreacted calcium, magnesium silicate (m2=3.63g),
Ca content (w in filter residue is measured using X-ray fluorescence spectra analysis (XRF) method2=8.45%), to calculate Ca recovery rate and be
89.44%;
(3) 15% ammonia spirit is added into first-time filtrate, is adjusted pH value and is removed Fe foreign ion to 10, is separated by solid-liquid separation, it is secondary
Filtrate is containing MgSO4、CaSO4Mixed solution, secondary filter residue be FeOOH precipitating, through calcining Fe can be obtained2O3;
(4) continue to add 15% ammonia spirit into secondary filtrate, adjust pH value and remove Mg foreign ion to 12, be separated by solid-liquid separation,
Filtrate is containing CaSO three times4Solution, three times filter residue be Mg (OH)2Precipitating;
(5) continue to add 15% ammonia spirit into filtrate three times, adjusting pH value to 13 makes Ca ion precipitation, is separated by solid-liquid separation, four times
Filtrate is sulfuric acid solution, is passed through the gaseous product being collected into step (1), obtains ammonium sulfate, and evaporation and concentration obtains sulfuric acid
Ammonium crystal is used for step (1), and four filter residues are Ca (OH)2Precipitating, to be used for subsequent carbonation reaction;
(6) four filter residues are dissolved in 250mL deionized water, the solution that Ca concentration is 0.26mol/L are formed, with 30mL/
(min·gsample) it is passed through CO2Gas, with 70mL/ (mingsample) it is passed through N2Gas (keeps 30%CO2+70%N2For reaction gas
Atmosphere), sediment (m is obtained by filtration after reacting 2.0h at 50 DEG C, 2.0Mpa3=3.10g), it is dried for 24 hours at 105 DEG C.Using X
Fluorescent x ray spectroscopy x (XRF) method measures Ca content (w in sediment3=78.55%), calculating carbonate treatment rate is
93.80%。
Embodiment 4
(1) blast furnace slag is dried to 1h at 105 DEG C first, is then ground to 106 ~ 150 μm.Then 5g blast furnace slag (m is weighed1=
5g, w1=58.05%) reaction kettle and 17g ammonium sulfate (blast furnace slag and ammonium sulfate mass ratio be 1:3.4), is added after mixing, with
4 DEG C/min is warming up to 450 DEG C, reacts 2.5h, stirring rate 300r/min, and all solids product is taken out after being cooled to room temperature
(gross mass 17.86g), and collect gaseous product;
(2) all solids product (gross mass 17.86g) is taken to be dissolved in 4465mL deionized water (holding liquid-solid ratio is 250:1),
2h, stirring rate 500r/min are leached at 60 DEG C.Dissolution fluid vacuum decompression filters, and first-time filtrate is containing Fe2(SO4)3、
MgSO4、CaSO4Mixed solution, filter residue main component is SiO2And unreacted calcium, magnesium silicate (m2=4.11g),
Ca content (w in filter residue is measured using X-ray fluorescence spectra analysis (XRF) method2=5.13%), to calculate Ca recovery rate and be
92.74%;
(3) 10% ammonia spirit is added into first-time filtrate, is adjusted pH value and is removed Fe foreign ion to 9, is separated by solid-liquid separation, it is secondary
Filtrate is containing MgSO4、CaSO4Mixed solution, secondary filter residue be FeOOH precipitating, through calcining Fe can be obtained2O3;
(4) continue to add 10% ammonia spirit into secondary filtrate, adjust pH value and remove Mg foreign ion to 10, be separated by solid-liquid separation,
Filtrate is containing CaSO three times4Solution, three times filter residue be Mg (OH)2Precipitating;
(5) continue to add 10% ammonia spirit into filtrate three times, adjusting pH value to 13 makes Ca ion precipitation, is separated by solid-liquid separation, four times
Filtrate is sulfuric acid solution, is passed through the gaseous product being collected into step (1), obtains ammonium sulfate, and evaporation and concentration obtains sulfuric acid
Ammonium crystal is used for step (1), and four filter residues are Ca (OH)2Precipitating, to be used for subsequent carbonation reaction;
(6) four filter residues are dissolved in 250mL deionized water, the solution that Ca concentration is 0.27mol/L are formed, with 40mL/
(min·gsample) it is passed through CO2Gas, with 60mL/ (mingsample) it is passed through N2Gas (keeps 40%CO2+60%N2For reaction gas
Atmosphere), sediment (m is obtained by filtration after reacting 1.0h at 50 DEG C, 3.0Mpa3=3.05 g), the dry 12h at 90 DEG C.Using X
Fluorescent x ray spectroscopy x (XRF) method measures Ca content (w in sediment3=82.25%), calculating carbonate treatment rate is
93.20%。
Embodiment 5
(1) blast furnace slag is dried to 1h at 105 DEG C first, is then ground to 150 ~ 212 μm.Then 5g blast furnace slag (m is weighed1=
5g, w1=58.05%) and 20g ammonium sulfate (blast furnace slag and ammonium sulfate mass ratio be 1:4), reaction kettle is added, after mixing with 2
DEG C/min is warming up to 400 DEG C, 2.0h, stirring rate 500r/min are reacted, it is (total that all solids product is taken out after being cooled to room temperature
Quality is 20.64g), and collect gaseous product;
(2) all solids product (gross mass 20.64g) is taken to be dissolved in 15.48L deionized water (holding liquid-solid ratio is 750:1),
3h, stirring rate 300r/min are leached at 40 DEG C.Dissolution fluid vacuum decompression filters, and first-time filtrate is containing Fe2(SO4)3、
MgSO4、CaSO4Mixed solution, filter residue main component is SiO2And unreacted calcium, magnesium silicate (m2=4.44g),
Ca content (w in filter residue is measured using X-ray fluorescence spectra analysis (XRF) method2=3.08%), to calculate Ca recovery rate and be
95.29%;
(3) 5% ammonia spirit is added into first-time filtrate, is adjusted pH value and is removed Fe foreign ion to 8, is separated by solid-liquid separation, secondary filter
Liquid is containing MgSO4、CaSO4Mixed solution, secondary filter residue be FeOOH precipitating, through calcining Fe can be obtained2O3;
(4) continue to add 5% ammonia spirit into secondary filtrate, adjust pH value and remove Mg foreign ion to 11, be separated by solid-liquid separation,
Filtrate is containing CaSO three times4Solution, three times filter residue be Mg (OH)2Precipitating;
(5) continue to add 5% ammonia spirit into filtrate three times, adjusting pH value to 12.4 makes Ca ion precipitation, is separated by solid-liquid separation, four
Secondary filtrate is sulfuric acid solution, is passed through the gaseous product being collected into step (1), obtains ammonium sulfate, and evaporation and concentration obtains sulphur
Sour ammonium crystal is used for step (1), and four filter residues are Ca (OH)2Precipitating, to be used for subsequent carbonation reaction;
(6) four filter residues are dissolved in 250mL deionized water, the solution that Ca concentration is 0.28mol/L are formed, with 50mL/
(min·gsample) it is passed through CO2Gas, with 50mL/ (mingsample) it is passed through N2Gas (keeps 50%CO2+50%N2For reaction gas
Atmosphere), sediment (m is obtained by filtration after reacting 2.0h at 40 DEG C, 5.0Mpa3=3.08g), it is dried for 24 hours at 105 DEG C.Using X
Fluorescent x ray spectroscopy x (XRF) method measures Ca content (w in sediment3=88.40%), calculating carbonate treatment rate is
98.44%。
Embodiment 6
(1) blast furnace slag is dried to 1h at 105 DEG C first, is then ground to 212 ~ 300 μm.Then 5g blast furnace slag (m is weighed1=
5g, w1=58.05%) and 25g ammonium sulfate (blast furnace slag and ammonium sulfate mass ratio be 1:5), reaction kettle is added, after mixing with 6
DEG C/min is warming up to 500 DEG C, 3.0h, stirring rate 400r/min are reacted, it is (total that all solids product is taken out after being cooled to room temperature
Quality is 24.05g), and collect gaseous product;
(2) all solids product (gross mass 24.05g) is taken to be dissolved in 12.03L deionized water (holding liquid-solid ratio is 500:1),
1h, stirring rate 400r/min are leached at 80 DEG C.Dissolution fluid vacuum decompression filters, and first-time filtrate is containing Fe2(SO4)3、
MgSO4、CaSO4Mixed solution, filter residue main component is SiO2And unreacted calcium, magnesium silicate (m2=4.81g),
Ca content (w in filter residue is measured using X-ray fluorescence spectra analysis (XRF) method2=2.14%), to calculate Ca recovery rate and be
96.45%;
(3) 15% ammonia spirit is added into first-time filtrate, is adjusted pH value and is removed Fe foreign ion to 10, is separated by solid-liquid separation, it is secondary
Filtrate is containing MgSO4、CaSO4Mixed solution, secondary filter residue be FeOOH precipitating, through calcining Fe can be obtained2O3;
(4) continue to add 15% ammonia spirit into secondary filtrate, adjust pH value and remove Mg foreign ion to 11, be separated by solid-liquid separation,
Filtrate is containing CaSO three times4Solution, three times filter residue be Mg (OH)2Precipitating;
(5) continue to add 15% ammonia spirit into filtrate three times, adjusting pH value to 12.7 makes Ca ion precipitation, is separated by solid-liquid separation, four
Secondary filtrate is sulfuric acid solution, is passed through the gaseous product being collected into step (1), obtains ammonium sulfate, and evaporation and concentration obtains sulphur
Sour ammonium crystal is used for step (1), and four filter residues are Ca (OH)2Precipitating, to be used for subsequent carbonation reaction;
(6) four filter residues are dissolved in 250mL deionized water, the solution that Ca concentration is 0.28mol/L are formed, with 50mL/
(min·gsample) it is passed through CO2Gas, with 50mL/ (mingsample) it is passed through N2Gas (keeps 50%CO2+50%N2For reaction gas
Atmosphere), sediment (m is obtained by filtration after reacting 1.5h at 30 DEG C, 4.0Mpa3=3.10 g), dries for 24 hours at 85 DEG C.Using X
Fluorescent x ray spectroscopy x (XRF) method measures Ca content (w in product3=89.00%), calculating carbonate treatment rate is 98.55%.
Comparative example 1
(1) blast furnace slag is dried to 1h at 105 DEG C first, is then ground to 37 ~ 75 μm.Then 5g blast furnace slag (m is weighed1=5g,
w1=58.05%) it and 20g ammonium sulfate (blast furnace slag and ammonium sulfate mass ratio be 1:4), is uniformly mixed and is placed in Muffle furnace, with 5
DEG C/min is warming up to 400 DEG C, reacts 2.0h in the case where no mechanical stirring, all solids product is taken out after being cooled to room temperature
(gross mass 18.62g), and collect gaseous product;
(2) all solids product (gross mass 18.62g) is taken to be dissolved in 13.97L deionized water (holding liquid-solid ratio is 750:1),
3h, stirring rate 300r/min are leached at 40 DEG C.Dissolution fluid vacuum decompression filters, and first-time filtrate is containing Fe2(SO4)3、
MgSO4、CaSO4Mixed solution, filter residue main component is SiO2And unreacted calcium, magnesium silicate (m2=3.72g),
Ca content (w in filter residue is measured using X-ray fluorescence spectra analysis (XRF) method2=47.40%), to calculate Ca recovery rate
It is 39.25%;
(3) with 100mL/ (mingsample) CO is passed through into first-time filtrate2Gas, after reacting 2.0h at 40 DEG C, 5.0Mpa
Sediment (m is obtained by filtration3=1.50g), it is dried for 24 hours at 105 DEG C.It is heavy using X-ray fluorescence spectra analysis (XRF) method measurement
Ca content (w in starch3=68.20%), calculating carbonate treatment rate is 89.80%.
Comparative example 2
(1) blast furnace slag is dried to 1h at 105 DEG C first, is then ground to 37 ~ 75 μm.Weigh 330g ammonium sulfate (blast furnace slag with
Ammonium sulfate mass ratio is 1:66), the ammonium sulfate that 1250mL concentration is 2mol/L is prepared, 5g blast furnace slag (m is added1=5g, w1=
58.05%), solid-to-liquid ratio 4g/L reacts 2.0h at 70 DEG C, and being kept stirring rate is 500r/min, after reaction solid-liquid point
From first-time filtrate is containing Fe2(SO4)3、MgSO4、CaSO4Mixed solution, filter residue main component is SiO2And unreacted
Calcium, magnesium silicate (m2=4.17g), Ca content (w in a filter residue is measured using X-ray fluorescence spectra analysis (XRF) method2=
25.60%), so that calculating Ca recovery rate is 36.78%;
(2) with 100mL/ (mingsample) CO is passed through into first-time filtrate2Gas, after reacting 2.0h at 40 DEG C, 5.0Mpa
Sediment (m is obtained by filtration3=1.33g), it is dried for 24 hours at 105 DEG C.It is heavy using X-ray fluorescence spectra analysis (XRF) method measurement
Ca content (w in starch3=68.55%), calculating carbonate treatment rate is 85.40%.
Subordinate list 1
Note: BFS (blast furnace slag): blast furnace slag
AS (ammonium sulfate): ammonium sulfate.
Claims (4)
1. a kind of high efficiency extraction blast furnace slag active constituent and the fixed CO of carbonating2The method for producing calcium carbonate, it is characterised in that packet
Include following steps:
(1) it after blast furnace slag being first ground to 37 ~ 300 μm, is added and reacts after mixing with ammonium sulfate 1:1 ~ 1:5 in mass ratio
Kettle is warming up to 250 ~ 500 DEG C with 2 ~ 6 DEG C/min, reacts 0.5 ~ 3.0h, and stirring rate is 300 ~ 500r/min, is cooled to room temperature
All solids product is taken out afterwards, and collects gaseous product;
(2) all solids product is taken to be dissolved in deionized water, holding liquid-solid ratio is 250:1 ~ 750:1, in 40 ~ 80 DEG C, stirring speed
Rate is that 1 ~ 3h is leached under 250 ~ 500r/min, and dissolution fluid vacuum decompression filters, and first-time filtrate is containing Fe2(SO4)3、MgSO4、CaSO4
Mixed solution, filter residue main component is SiO2And unreacted calcium, magnesium silicate;
(3) into first-time filtrate add mass fraction be 5 ~ 15% ammonia spirit, adjust pH value removed to 8 ~ 10 Fe impurity from
Son is separated by solid-liquid separation, and secondary filtrate is containing MgSO4、CaSO4Mixed solution, secondary filter residue is FeOOH precipitating, available through calcining
Fe2O3;
(4) continue to add the ammonia spirit that mass fraction is 5 ~ 15% into secondary filtrate, adjust pH value to 10 ~ 12 to remove Mg
Foreign ion is separated by solid-liquid separation, and filtrate is containing CaSO three times4Solution, three times filter residue be Mg (OH)2Precipitating;
(5) continue into filtrate three times add mass fraction be 5 ~ 15% ammonia spirit, adjust pH value to 12.4 ~ 13 make Ca from
Son precipitating, is separated by solid-liquid separation, and four times filtrate is sulfuric acid solution, is passed through the gaseous product being collected into step (1), it is molten to obtain ammonium sulfate
Liquid, evaporation and concentration obtain ammonia sulfate crystal, and circulation is used for step (1), and four filter residues are Ca (OH)2Precipitating, to be used for subsequent carbon
Acidification reaction;
(6) four filter residues are dissolved in deionized water and form the solution that Ca concentration is 0.12 ~ 0.28mol/L, with 10 ~ 50mL/
(min·gsample) be passed through containing CO2The gas that mass fraction is 10% ~ 50% reacts 0.5 ~ 2.0h at 30 ~ 50 DEG C, 0.1 ~ 5Mpa
After sediment is obtained by filtration, dry 12 at 80 ~ 105 DEG C ~ for 24 hours.
2. a kind of high efficiency extraction blast furnace slag active constituent as described in claim 1 and the fixed CO of carbonating2Produce calcium carbonate
Method, it is characterised in that the step (6) contains CO2Gas is that waste heat flue gas is what coal furnace, oil burner or gas furnace discharged
Tail gas.
3. a kind of high efficiency extraction blast furnace slag active constituent as described in claim 1 and the fixed CO of carbonating2Produce calcium carbonate
Method, it is characterised in that the measurement of Ca content uses X-ray fluorescence spectra analytic approach in the filter residue that step (2) obtains;
Ca recovery rate calculation formula:
m1: blast furnace slag quality (g);
w1: Ca mass fraction (%) in blast furnace slag;
m2: the filter residue quality (g) that step (2) obtains;
w2: Ca mass fraction (%) in the filter residue that step (2) obtains.
4. a kind of high efficiency extraction blast furnace slag active constituent as described in claim 1 and the fixed CO of carbonating2Produce calcium carbonate
Method, it is characterised in that the measurement of Ca content uses X-ray fluorescence spectra analytic approach in the sediment that step (6) obtains;
Ca carbonate treatment rate calculation formula:
m1: blast furnace slag quality (g);
w1: Ca mass fraction (%) in blast furnace slag;
m2: the filter residue quality (g) that step (2) obtains;
w2: Ca mass fraction (%) in the filter residue that step (2) obtains;
m3: the sediment quality (g) that step (6) obtains;
w3: Ca mass fraction (%) in the sediment that step (6) obtains.
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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CN114149019A (en) * | 2021-11-23 | 2022-03-08 | 江西广源化工有限责任公司 | Preparation method of high-purity heavy calcium carbonate |
CN115354099A (en) * | 2022-09-15 | 2022-11-18 | 重庆中吉达环保科技有限公司 | Method for separating carbon dioxide in blast furnace gas from metallurgical slag |
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 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN102794093A (en) * | 2012-08-14 | 2012-11-28 | 中国华能集团清洁能源技术研究院有限公司 | Integrated technology for capturing and mineralizing carbon dioxide |
CN106430264A (en) * | 2016-07-19 | 2017-02-22 | 四川大学 | Method for mineralizing CO2 with blast iron slag and co-producing alumina |
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2018
- 2018-09-25 CN CN201811114216.5A patent/CN109231249A/en active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN102794093A (en) * | 2012-08-14 | 2012-11-28 | 中国华能集团清洁能源技术研究院有限公司 | Integrated technology for capturing and mineralizing carbon dioxide |
CN106430264A (en) * | 2016-07-19 | 2017-02-22 | 四川大学 | Method for mineralizing CO2 with blast iron slag and co-producing alumina |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114149019A (en) * | 2021-11-23 | 2022-03-08 | 江西广源化工有限责任公司 | Preparation method of high-purity heavy calcium carbonate |
CN114149019B (en) * | 2021-11-23 | 2024-02-06 | 江西广源化工有限责任公司 | Preparation method of high-purity heavy calcium carbonate |
CN115354099A (en) * | 2022-09-15 | 2022-11-18 | 重庆中吉达环保科技有限公司 | Method for separating carbon dioxide in blast furnace gas from metallurgical slag |
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 |
CN115582105B (en) * | 2022-09-30 | 2024-02-02 | 攀钢集团攀枝花钢铁研究院有限公司 | Modification preparation of CO from titanium-containing blast furnace slag 2 Method for coupling mineralization of trapping material |
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Application publication date: 20190118 |