CN1099424A - Method for treating blast furnace slag by dilute hydrochloric acid - Google Patents
Method for treating blast furnace slag by dilute hydrochloric acid Download PDFInfo
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- CN1099424A CN1099424A CN94108086A CN94108086A CN1099424A CN 1099424 A CN1099424 A CN 1099424A CN 94108086 A CN94108086 A CN 94108086A CN 94108086 A CN94108086 A CN 94108086A CN 1099424 A CN1099424 A CN 1099424A
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- mother liquor
- hydrochloric acid
- blast furnace
- filtration
- slag
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 239000002893 slag Substances 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 35
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 22
- 238000002386 leaching Methods 0.000 claims abstract description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 17
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims abstract description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 11
- 239000000741 silica gel Substances 0.000 claims abstract description 11
- 239000010440 gypsum Substances 0.000 claims abstract description 7
- 229910052602 gypsum Inorganic materials 0.000 claims abstract description 7
- 229910001629 magnesium chloride Inorganic materials 0.000 claims abstract description 7
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 4
- 235000011167 hydrochloric acid Nutrition 0.000 claims description 25
- 238000001914 filtration Methods 0.000 claims description 24
- 239000012452 mother liquor Substances 0.000 claims description 23
- 238000005406 washing Methods 0.000 claims description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 20
- 239000012065 filter cake Substances 0.000 claims description 18
- 238000001704 evaporation Methods 0.000 claims description 17
- 230000008020 evaporation Effects 0.000 claims description 17
- 239000000706 filtrate Substances 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 16
- 238000006460 hydrolysis reaction Methods 0.000 claims description 15
- 239000000047 product Substances 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000002425 crystallisation Methods 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 11
- 238000009833 condensation Methods 0.000 claims description 11
- 230000005494 condensation Effects 0.000 claims description 11
- 230000008025 crystallization Effects 0.000 claims description 10
- 230000007062 hydrolysis Effects 0.000 claims description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 9
- 239000010936 titanium Substances 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- 235000010215 titanium dioxide Nutrition 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- 238000009835 boiling Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000000284 extract Substances 0.000 claims description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 5
- 239000011575 calcium Substances 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- 239000012141 concentrate Substances 0.000 claims description 5
- 229940072033 potash Drugs 0.000 claims description 5
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 5
- 235000015320 potassium carbonate Nutrition 0.000 claims description 5
- BYGOPQKDHGXNCD-UHFFFAOYSA-N tripotassium;iron(3+);hexacyanide Chemical compound [K+].[K+].[K+].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] BYGOPQKDHGXNCD-UHFFFAOYSA-N 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 4
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 claims description 4
- 229910001424 calcium ion Inorganic materials 0.000 claims description 4
- 239000006210 lotion Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 239000003921 oil Substances 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- 239000008399 tap water Substances 0.000 claims description 3
- 235000020679 tap water Nutrition 0.000 claims description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 2
- 238000003916 acid precipitation Methods 0.000 claims description 2
- 238000005554 pickling Methods 0.000 claims description 2
- 239000003292 glue Substances 0.000 claims 1
- 229960001866 silicon dioxide Drugs 0.000 abstract description 10
- 238000000605 extraction Methods 0.000 abstract description 5
- 229910000805 Pig iron Inorganic materials 0.000 abstract description 2
- 238000003912 environmental pollution Methods 0.000 abstract 1
- 229910052742 iron Inorganic materials 0.000 description 8
- 229910000831 Steel Inorganic materials 0.000 description 7
- 239000010959 steel Substances 0.000 description 7
- 238000011084 recovery Methods 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- 239000000843 powder Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052925 anhydrite Inorganic materials 0.000 description 2
- 230000009194 climbing Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 210000003298 dental enamel Anatomy 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000007885 magnetic separation Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000001117 sulphuric acid Substances 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 241000628997 Flos Species 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 210000000481 breast Anatomy 0.000 description 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
- 230000003588 decontaminative effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- -1 potassium ferricyanide Chemical compound 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- GFNGCDBZVSLSFT-UHFFFAOYSA-N titanium vanadium Chemical compound [Ti].[V] GFNGCDBZVSLSFT-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
Landscapes
- Compounds Of Iron (AREA)
- Processing Of Solid Wastes (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to a method for treating blast furnace slag by dilute hydrochloric acid, which is characterized in that 10-14% hydrochloric acid is used for leaching the blast furnace slag, the leaching with the concentration has high leaching rate, and the leachate is in a solution state, so that the extraction of silica-gel titanium dioxide, crystalline aluminum chloride, magnesium chloride, gypsum and pig iron is facilitated. The method has the advantages of low cost, simple process, low environmental pollution, and high leaching rate and extraction rate of each element.
Description
The present invention relates to a kind of treatment process of slag, a kind of method of more specifically saying so with treating blast furnace slag with diluted chlorhydric acid.
The development research that utilizes to titanium-containing blast furnace slag at present mainly contains two kinds of dry method and wet methods.At " steel climbing high slag extraction TiO
2And Sc
2O
3Research " vitriol oil of having delivered a kind of usefulness about 93% in the literary composition (Chen Qifu etc. (Flos Bombacis Malabarici iron and steel research institute) " steel vanadium titanium " 1991 the 12nd volume the 3rd phases P.30) slag that will be crushed to certain particle size mixes by a certain percentage; 220 ℃ of left and right sides slakings; with about 70 ℃ hot water leaching, add a certain amount of (NH then
4)
2SO
4, be cooled to 5 ℃ of left and right sides crystallizations and reclaim NH
4Al(SO
4)
2, except that TiO is produced in the recovery of the mother liquor hydrolysis behind the aluminium
2, the mother liquor behind the extraction titanium reclaims Sc with the P507 extraction.This method needs to carry out at external heat source and under higher temperature, and insoluble slag is many, produces a large amount of new solid wastes, handles 1 ton of high Shanghai slag and will produce CaSO more than 1 ton
4And silicon-dioxide etc., scandium content in slag is very low, and 33PPM only wants enrichment and reclaims quite difficultly, and cost height, the output value are low.The method of decomposing making chemical products from blast-furnace slags with hydrochloric acid is disclosed in the patent application of CN13036799A.Its method is that shrend titanium-containing blast furnace slag and dilute hydrochloric acid are ground altogether, becomes moisture thin slag, adds 32～40% concentrated hydrochloric acid heating (80～110 ℃) acidolysis 6～20 hours again, filtering SiO
2Hydrochloric acid is removed in back distillation, hydrolysis in 0.2% oxalic acid liquid, metatitanic acid, calcine titanium oxide.With same technological process, be 20～32% if add concentration of hydrochloric acid, then must mix titanium white by what titanium oxide and silicon oxide were formed.In mother liquor, add and forge the rhombspar breast, can separate oxide compounds such as vanadium, iron, aluminium and magnesium, calcium respectively.These method existing problems are also more: (1) used salt acid concentration is very high, need 32～40%, and technical hydrochloric acid only is about 31%.Concentrated hydrochloric acid needs special methods production, and price significantly increases; (2) decompose used acid amount 6～8 times for blast furnace slag weight, handling 1 ton of slag then need be with 6～8 tons of 32～40% hydrochloric acid, and cost improves greatly; (3) reaction needs to carry out under 80～110 ℃ 6～20 hours, and not only energy consumption is big, and corrodibility is bigger under this condition, and equipment and environmental measures are needed higher requirement; (4) level of residue is big after the acidolysis, and its dry weight is estimated as more than 25% of former blast furnace slag weight, and this slag purposes is little, will become the new three wastes; (5) produce the titanium oxide of gained and the mixing titanium white that silicon oxide is formed with this method, owing to be mingled with suitable acidolysis insolubles, its product purity is very poor, and purposes is little, and the output value is also low.
The purpose of this invention is to provide the method that a kind of cost is low, the refuse amount is few, easy and simple to handle with diluted acid processing blast furnace slag.
The present invention implements like this, and the dilute hydrochloric acid of employing 10～14% leaches titanium-containing blast furnace slag under normal temperature condition, and the gained leaching liquid extracts TiO respectively again
2, silica gel, crystal aluminum chloride, gypsum, magnesium chloride etc.This process salt acid recovery is used, and it is few that closed cycle produces the three wastes, and owing to adopt dilute hydrochloric acid, production cost reduces greatly.
Technological process of the present invention is as follows:
(1) blast furnace slag is crushed to 100～75 μ m, selects iron powder with magnetic method;
(2) with the pulverized slag after the deironing with 10～14% hydrochloric acid, filtered in 0.5～1.0 hour by solid-to-liquid ratio 1: 8～10, normal temperature leaching, molten slag is not added in next batch of material and leaches;
(3) will leach filtrate and leave standstill at normal temperatures 48 hours, make the silica gel cohesion in the filtrate, press filtration then, filter cake is with 10～14% salt pickling, and again with the tap water washing, until effluent liquid PH＞6, filter is done again.Take out filter cake, dry being lower than under 100 ℃ of conditions, product silica gel;
(4) mother liquor that will extrude from wet silica gel and washing lotion merge post-heating to boiling, and boiling hydrolysis 2 hours makes TiCL wherein
4Hydrolysis generates the metatitanic acid precipitation, leaves standstill 24 hours after-filtration and collects mother liquor, and filter cake is checked the iron-free ionic reaction through washing to effluent liquid with red prussiate of potash, drying, calcine titanium dioxide;
(5) mother liquid evaporation behind the hydrolysis titanium is concentrated into 1/4～1/6 of original volume, the evaporation steam reclaims through condensation; Add in the concentrated solution with calcium ion wherein and generate CaSO
4The vitriol oil that chemical reaction dosage equates, calcium is with CaSO
4NH
2O precipitation is separated out, after filtration, washing, drying, the product gypsum;
(6) feeding HCl gas is saturated to solution in the mother liquor after deliming, folds white AlCl this moment
3NH
224 hours after-filtration are left standstill in the O crystallization, filter cake with concentrated hydrochloric acid wash decon, dry the crystal aluminum chloride product;
(7) will concentrate except that the mother liquor heating evaporation behind the aluminum chloride, and obtain crystallization magnesium chloride, the vapour condensation of evaporation reclaims, and mother liquor further extracts other element or recycles.
Fig. 1 is a process flow sheet of the present invention.
Blast furnace slag is processed with method of the present invention, its acidleach resolution ratio＞80%, and the rate of recovery of each element in single step process is respectively: SiO2＞70%;TiO
2＞60%;CaO＞70%;Al
2O
3＞60%; MgO＞50%. Each element overall recovery in the cycling production process can reach more than 80%.
Boil when the leaching filtrate of step (2) is heated to, carry out press filtration again, then can get the silicon titanium white, this sampling technology is simpler, more convenient operation. Its technical process is as follows:
(1) blast furnace slag is crushed to 100～75 μ m, selects iron powder with magnetic method;
(2) with the pulverized slag after the deironing with 10～14% hydrochloric acid, filtered in 0.5～1.0 hour by solid-to-liquid ratio 1: 8～10, normal temperature leaching, molten slag is not added in next batch of material and leaches;
(3) (2) gained is leached the filtrate salt adding to boiling 0.2～1.0 hour, make TiCL4Hydrolysis, silicate condensation left standstill 48 hours, and press filtration is filtered, and filter cake is washed with water to filter liquor and checks the non-iron-ion reaction with potassium ferricyanide, and the silicon titanium white is calcined to get in oven dry again.
(4) mother liquid evaporation behind the Hydrolysis of Titanium is concentrated into 1/4～1/6 of original volume, the evaporation steam reclaims through condensation; Add in the concentrate with calcium ion wherein and generate CaSO4The concentrated sulfuric acid that chemical reaction dosage equates, calcium is with CaSO4·nH
2The O Precipitation after filtration, washing, drying, gets the product gypsum;
(5) it is saturated to solution to pass into HCl gas in the mother liquor after deliming, folds white AlCl this moment3·nH
2The O crystallization is left standstill after 24 hours and is filtered, and filter cake washs decontamination, dries to get the crystal aluminum chloride product with concentrated hydrochloric acid;
(6) will concentrate except the mother liquor heating evaporation behind the aluminium chloride, and obtain crystallization magnesium chloride, the steam condensing of evaporation reclaims, and mother liquor further extracts other element or recycles.
In sum as seen, the present invention is owing to adopted watery hydrochloric acid leaching blast furnace slag, and most elements changes solution substep from solution over to ionic condition and separates each essential element of recovery, makes the multiple chemical products of certain grade. Acid consumption of the present invention is low, and about 3 tons of/ton slags adopt the preparation of general industry hydrochloric acid, and normal-temperature reaction does not add heat, and the time is short, reacts about 0.5～1.0 hour, therefore greatly reduces cost, and shortens process cycle.
Present embodiment is selected for use and is climbed the molten steel blast furnace slag of quenching and make raw material.Handle by following technological process:
(1) get and climb steel slag 200 gram, be crushed to 100 μ m, select metallic iron with magnetic separation, metal iron shot powder 5.2 grams;
(2) pulverized slag after selecting iron, 2 liters of the hydrochloric acid with 13.5% stir leaching at normal temperatures, stop after about 0.5 hour stirring, filter, 2 liters of filtrates, filter residue is weighed with a small amount of washing back oven dry and 36 is restrained, and returns acidleach;
(3) (2) filtrate was left standstill 48 hours at normal temperatures, is separated out silica gel, remove silica gel adsorption solution with press filtration, 1.5 liters of filtrates, the silica gel filter cake is with 13.5% salt acid elution, again with the tap water washing, until filtrate PH＞6, the taking-up filter cake dry SiO
237.5 gram;
(4) filtrate and washing lotion are merged totally 3 liters, ebuillition of heated hydrolysis 2 hours makes TiCl
4Hydrolysis is separated out, and aging leaving standstill 24 hours filtered, and the metatitanic acid cake is used deionized water wash again with 13.5% solution drip washing, checks the iron-free ionic reaction until effluent liquid with red prussiate of potash, take out dry calcine TiO
231.5 gram;
Stop heating when (5) mother liquid evaporation behind the hydrolysis titanium being concentrated to about 400 milliliters, evaporated vapor reclaims through condensation, is used to prepare the hydrochloric acid of leaching slag, and concentrated solution adds 65 milliliters 92% industrial sulphuric acid after cooling off, and reaction generates white precipitate CaSO
4NH
2O through filtration, washing, and is dried to such an extent that bassanite 96 restrains at 180 ℃.
(6) feed HCl gas to solution in the mother liquor after deliming and separate out white AlCl
3NH
224 hours after-filtration are left standstill in the O crystallization, and filter cake is removed impurity with 35% concentrated hydrochloric acid washing, and heat drying in enamel tray gets AlCl
3Powder 34 grams;
(7) will remove AlCl
3After mother liquor put into evaporative flask heating and be concentrated into and begin to have small amount of crystalline to occur, pour out the solution crystallisation by cooling, filter, washing dry anhydrous MgCl
225 grams, remaining raffinate can continue condensing crystal or join leaching acid and use.
Embodiment 2.
(1) get and climb molten steel blast furnace slag 200 gram of quenching, be crushed to below the 100 μ m, select metallic iron with magnetic separation, metal iron shot powder 4.9 grams;
(2) pulverized slag after selecting iron, 2 liters of the hydrochloric acid with 13.5% stir leaching after 0.67 hour at normal temperatures, stop to stir and filter, and get 2.1 liters of filtrates, and filter residue restrains with a small amount of washing back oven-dried weight 36, returns acidleach;
(3) with (2) filtrate ebuillition of heated under agitation condition, boiled 15 minutes, filtrate is retrogradation gradually, bleaches into starchiness, stops heating, naturally cooling also left standstill 48 hours, carry out press filtration again, filter cake washs with deionized water, is washed till filtrate and checks the iron-free ionic reaction with red prussiate of potash, the oven dry of taking-up filter cake is calcined to such an extent that silicon titanium white 76 restrains;
(4) liquid that (3) press filtration is got and washing lotion merging heating is concentrated to 400 milliliters, stops heating, and evaporated vapor reclaims through condensation, and concentrated solution adds 65 milliliter 92% industrial sulphuric acid after cooling off, and reaction generates white precipitate CaSO
4NH
2O through filtration washing, and is dried to such an extent that bassanite 101 restrains at 180 ℃;
(5) feed HCl gas to solution in the mother liquor after deliming and separate out white AlCl
3NH
224 hours after-filtration are left standstill in the O crystallization, and filter cake is removed impurity with 35% concentrated hydrochloric acid washing, and heat drying in enamel tray gets AlCl
3Powder 36 grams;
(7) above-mentioned mother liquor is put into evaporative flask heating and is concentrated into and begins to have the equivalent crystal to occur, pour out the solution crystallisation by cooling, filtration washing dry anhydrous MgCl
226.5 joining leaching acid, gram, remaining raffinate use.
It is as shown in table 1 below by experiment yield calculating products obtained therefrom that the present invention handles 1 ton of steel climbing high slag:
Table 1
| Name of product | Silica gel | Titanium dioxide | Crystal aluminum chloride | The magnesium chloride gypsum | The pig iron |
| Quantity (kg) | 145 | 134 | 220 | 97 379 | 25 |
Claims (2)
1, a kind of method with treating blast furnace slag with diluted chlorhydric acid is characterized in that this method technological process is as follows:
(1) blast furnace slag is crushed to 100～75 μ m, selects iron powder with magnetic method;
(2) with the pulverized slag after the deironing with 10～14% hydrochloric acid by solid-to-liquid ratio 1: 8～10, normal temperature down leaching filtered in 0.5～1.0 hour, molten slag is not added to and leaches in next batch of material;
(3) will leach filtrate and leave standstill 48 hours, make the silica gel cohesion in the filtrate, press filtration then, filter cake is with 10～14% salt pickling, and again with the tap water washing, until elutant PH＞6, filter is done again, takes out filter cake, dries being lower than under 100 ℃ of conditions, gets the acid of product glue.
(4) mother liquor and washing lotion that will press filtration goes out from wet silica gel merge post-heating to boiling, and boiling hydrolysis 2 hours makes TICL wherein
4Hydrolysis generates the metatitanic acid precipitation, leaves standstill after-filtration, collects mother liquor, and filter cake is checked the iron-free ionic reaction through washing to effluent liquid with red prussiate of potash, drying, calcine titanium dioxide;
(5) mother liquid evaporation behind the hydrolysis titanium is concentrated into 1/4～1/6 of original volume, the evaporation steam reclaims through condensation; Add in the concentrated solution with calcium ion wherein and generate CaSO
4The vitriol oil that chemical reaction dosage equates, calcium is with CaSO
4NH
2O precipitation is separated out, after filtration, washing, dry product gypsum;
(6) feeding HCl gas is saturated to solution in the mother liquor after deliming, separates out white AlCl this moment
3NH
2After-filtration is left standstill in the O crystallization, filter cake with concentrated hydrochloric acid wash decon, dry the crystal aluminum chloride product;
(7) will concentrate except that the mother liquor heating evaporation of aluminum chloride, crystallisation by cooling extracts magnesium chloride, and the vapour condensation of evaporation reclaims, and mother liquor further extracts other element or recycles.
2, a kind of method with treating blast furnace slag with diluted chlorhydric acid is characterized in that this method technological process is as follows:
(1) blast furnace slag is crushed to 100～75 μ m, selects iron powder with magnetic method;
(2) with the pulverized slag after the deironing with 10～14% hydrochloric acid, filtered in 0.5～1.0 hour by solid-to-liquid ratio 1: 8～10, normal temperature leaching, molten slag is not added in next batch of material and leaches;
(3) with (2) gained leaching filtrate with salt to boiling 0.2～1.0 hour, make TiCL
4Hydrolysis, silicate condensation left standstill 48 hours, press filtration is filtered, filter cake is washed with water to filtrate and checks the iron-free ionic reaction with red prussiate of potash, again oven dry calcine the silicon titanium white.
(4) mother liquid evaporation behind the hydrolysis titanium is concentrated into 1/4～1/6 of original volume, the evaporation steam reclaims through condensation; Add in the concentrated solution with calcium ion wherein and generate CaSO
4The vitriol oil that chemical reaction dosage equates, calcium is with CaSO
4NH
2O precipitation is separated out, after filtration, washing, drying, the product gypsum;
(5) feeding HCl gas is saturated to solution in the mother liquor after deliming, folds white AlCl this moment
3NH
224 hours after-filtration are left standstill in the O crystallization, filter cake with concentrated hydrochloric acid wash decon, dry the crystal aluminum chloride product;
(6) will concentrate except that the mother liquor heating evaporation behind the aluminum chloride, magnesium chloride is extracted in crystallization, and the vapour condensation of evaporation reclaims, and mother liquor further extracts other element or recycles.
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| Application Number | Priority Date | Filing Date | Title |
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| CN94108086A CN1040553C (en) | 1994-08-10 | 1994-08-10 | Method for treating blast furnace slag by dilute hydrochloric acid |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94108086A CN1040553C (en) | 1994-08-10 | 1994-08-10 | Method for treating blast furnace slag by dilute hydrochloric acid |
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| Publication Number | Publication Date |
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| CN1099424A true CN1099424A (en) | 1995-03-01 |
| CN1040553C CN1040553C (en) | 1998-11-04 |
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| CN94108086A Expired - Fee Related CN1040553C (en) | 1994-08-10 | 1994-08-10 | Method for treating blast furnace slag by dilute hydrochloric acid |
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| CN100436334C (en) * | 2007-01-23 | 2008-11-26 | 东北大学 | A preparation method for making high-purity magnetic material nano-iron oxide |
| CN103014332A (en) * | 2013-01-16 | 2013-04-03 | 四川顺应金属材料科技有限公司 | Pretreatment method for extracting molybdenum from molybdenum ore |
| CN103539201A (en) * | 2013-01-23 | 2014-01-29 | 自贡市亚钛化工科技有限公司 | Hydrochloric-acid-method titanium yellow powder production technology |
| WO2014047728A1 (en) * | 2012-09-26 | 2014-04-03 | Orbite Aluminae Inc. | Processes for preparing alumina and magnesium chloride by hc1 leaching of various materials |
| CN104310467A (en) * | 2014-10-15 | 2015-01-28 | 陆世强 | Comprehensive utilization method of high titanium slag |
| CN105671225A (en) * | 2016-01-22 | 2016-06-15 | 山东钢铁股份有限公司 | Method for comprehensively using blast furnace slag and converter slag |
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|---|---|---|---|---|
| JPH07100807B2 (en) * | 1988-02-24 | 1995-11-01 | 川崎製鉄株式会社 | Method for producing molten iron containing low S chromium |
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| CN100436334C (en) * | 2007-01-23 | 2008-11-26 | 东北大学 | A preparation method for making high-purity magnetic material nano-iron oxide |
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| CN103539201A (en) * | 2013-01-23 | 2014-01-29 | 自贡市亚钛化工科技有限公司 | Hydrochloric-acid-method titanium yellow powder production technology |
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| CN104310467B (en) * | 2014-10-15 | 2017-02-01 | 陆世强 | Comprehensive utilization method of high titanium slag |
| CN105671225A (en) * | 2016-01-22 | 2016-06-15 | 山东钢铁股份有限公司 | Method for comprehensively using blast furnace slag and converter slag |
| CN107324352A (en) * | 2017-07-12 | 2017-11-07 | 苏州大学 | A kind of method that blast furnace slag prepares ordered mesoporous silica dioxide |
| CN107354252A (en) * | 2017-07-28 | 2017-11-17 | 华北理工大学 | Titanium-containing blast furnace slag disposal of resources method and rich-titanium material acquisition methods |
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