JP5702453B2 - Process for treating slag for silica and magnesia extraction - Google Patents
Process for treating slag for silica and magnesia extraction Download PDFInfo
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- JP5702453B2 JP5702453B2 JP2013211028A JP2013211028A JP5702453B2 JP 5702453 B2 JP5702453 B2 JP 5702453B2 JP 2013211028 A JP2013211028 A JP 2013211028A JP 2013211028 A JP2013211028 A JP 2013211028A JP 5702453 B2 JP5702453 B2 JP 5702453B2
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- silica
- slag
- magnesia
- hydrochloric acid
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims description 182
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 title claims description 121
- 239000002893 slag Substances 0.000 title claims description 114
- 239000000377 silicon dioxide Substances 0.000 title claims description 89
- 239000000395 magnesium oxide Substances 0.000 title claims description 60
- 238000000034 method Methods 0.000 title claims description 39
- 230000008569 process Effects 0.000 title claims description 20
- 238000000605 extraction Methods 0.000 title claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 130
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- 238000002386 leaching Methods 0.000 claims description 32
- 239000007787 solid Substances 0.000 claims description 32
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 31
- 238000001914 filtration Methods 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 238000000926 separation method Methods 0.000 claims description 28
- 238000010306 acid treatment Methods 0.000 claims description 27
- 239000000706 filtrate Substances 0.000 claims description 27
- 239000002245 particle Substances 0.000 claims description 27
- 239000011777 magnesium Substances 0.000 claims description 26
- 229910052749 magnesium Inorganic materials 0.000 claims description 24
- 239000003513 alkali Substances 0.000 claims description 22
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 21
- 239000012535 impurity Substances 0.000 claims description 19
- 235000019353 potassium silicate Nutrition 0.000 claims description 18
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 18
- 150000002222 fluorine compounds Chemical class 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 16
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 15
- 238000001556 precipitation Methods 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 11
- 239000002002 slurry Substances 0.000 claims description 11
- DHRRIBDTHFBPNG-UHFFFAOYSA-L magnesium dichloride hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-] DHRRIBDTHFBPNG-UHFFFAOYSA-L 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000000746 purification Methods 0.000 claims description 9
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 238000003672 processing method Methods 0.000 claims description 7
- 239000002585 base Substances 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 238000005868 electrolysis reaction Methods 0.000 claims description 5
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 5
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 4
- -1 hexafluorosilicic acid Chemical compound 0.000 claims description 4
- 150000004692 metal hydroxides Chemical class 0.000 claims description 4
- 229910017855 NH 4 F Inorganic materials 0.000 claims description 3
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 238000010517 secondary reaction Methods 0.000 claims description 3
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- 229910000863 Ferronickel Inorganic materials 0.000 description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 17
- 229910004298 SiO 2 Inorganic materials 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 8
- 229910052742 iron Inorganic materials 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- 239000011651 chromium Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 6
- 229910052804 chromium Inorganic materials 0.000 description 6
- 238000000197 pyrolysis Methods 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000001879 gelation Methods 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011343 solid material Substances 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000004137 mechanical activation Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000012445 acidic reagent Substances 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
- 238000004458 analytical method Methods 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Images
Classifications
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- 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
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
- C01B33/186—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof from or via fluosilicic acid or salts thereof by a wet process
-
- 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
- C01F5/00—Compounds of magnesium
- C01F5/02—Magnesia
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B5/00—Treatment of metallurgical slag ; Artificial stone from molten metallurgical slag
- C04B5/06—Ingredients, other than water, added to the molten slag or to the granulating medium or before remelting; Treatment with gases or gas generating compounds, e.g. to obtain porous slag
-
- 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
-
- 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
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Description
本発明はシリカ及びマグネシア抽出のためのスラグの処理方法に係り、さらに詳しくはスラグに含有されたシリカとマグネシウム成分を効率よく抽出して、商業用製品の原料として活用できるスラグの処理方法に関する。 The present invention relates to a method for treating slag for extraction of silica and magnesia, and more particularly to a method for treating slag that can efficiently extract silica and magnesium components contained in slag and can be used as a raw material for commercial products.
ステンレススチールの原料であるフェロニッケルは、一般に原鉱石を還元処理して電気炉で溶融して製造する。原鉱石の主な成分はＳｉＯ２ ３８％、ＭｇＯ２５％であり、有効金属成分はＮｉ ２．３％、Ｆｅ １１％ほど含有している。
フェロニッケルの主な工程としては、原料前処理、乾燥、予備還元、溶融還元（電気炉工程）、精錬、鋳造の過程を経て製品として生産されるが、その中、電気炉工程において副産物であるスラグが発生され、その副産物を通常フェロニッケルスラグ（ｆｅｒｒｏｎｉｃｋｅｌ ｓｌａｇ）と称する。
一般のフェロニッケルスラグの主な成分としてはシリカ（ＳｉＯ２）とマグネシア（ＭｇＯ）が挙げられる。フェロニッケルスラグは日本及びカナダのような先進国ではセメント製造用原料、土木用材料、コンクリート用細骨材、滑走路用骨材などとして多様に再活用されているが、韓国では未だ活用度に乏しい実情である。
フェロニッケルスラグはＭｇの含水ケイ酸塩であって、不純物としてはＡｌ２Ｏ３、ＣａＯ、Ｆｅ２Ｏ３などが存在する。今までフェロニッケルスラグは、主に製鉄製鋼工程の炉壁の保護材及び骨材として使われて来ているが、最近はシリカとマグネシウムを資源として活用するための研究活動が盛んである。
韓国公開特許第１０−２０１０−００８５６２６号、第１０−２０１０−００８５５９９号及び第１０−２０１０−００８５６１８号には、ボールミルによるミリングを通じてスラグの機械的活性化を含むマグネシウム化合物及びシリカ製品の製造過程が公開されている。フェロニッケルスラグの機械的活性化は酸によるスラグ浸出を強化するために結晶シリカを非晶質状態に変形することを目的としている。満足すべき浸出率を達成するために、スラグはできるだけ微細に粉砕して反応面積を増加させるべきである。しかし、この場合スラグ浸出時に発生するシリカのゲル化現象は避けられない問題である。にもかかわらず、前述した出願には、このような問題点が考慮されていない。シリカゲルは反応器内で３次元ネットワーク構造を形成することから浸出率を減少させ、浸出液と固形物の濾過を困難にするか、場合によっては不可能になる。
酸性物質を用いたスラグの処理は多量の酸性試薬を求めることが知られている。対象成分を最大限回収するためには反応媒体の高い酸度を維持すべきなので、化学量論的な量より遥かに大きな比率の試薬が消費される。塩酸を使用する場合、酸の殆どはＭｇＯを溶解性ＭｇＣｌ２に変換するのに使われる。従って、技術の経済性は酸性物質を用いた浸出工程において再使用する塩酸の生成に大きく左右される。
Ferronickel, which is a raw material for stainless steel, is generally produced by reducing raw ore and melting it in an electric furnace. The main components of the raw ore are SiO 2 38% and MgO 25%, and the effective metal components are Ni 2.3% and Fe 11%.
The main process of ferronickel is produced as a product through raw material pretreatment, drying, pre-reduction, smelting reduction (electric furnace process), refining, and casting, but it is a by-product in the electric furnace process. Slag is generated and its by-product is commonly referred to as ferronickel slag.
Main components of general ferronickel slag include silica (SiO 2 ) and magnesia (MgO). Ferro-nickel slag raw materials for cement production in Japan and Canada developed countries, such as, for civil engineering material, concrete for fine aggregate, but since it has a wide range of re-use as etc. gliding road aggregate, still in Korea utilization It is a poor situation.
Ferronickel slag is a hydrous silicate of Mg, and Al 2 O 3 , CaO, Fe 2 O 3 and the like exist as impurities. Until now, ferronickel slag has been used mainly as a protective material and aggregate for furnace walls in the steelmaking process, but recently, research activities are actively conducted to utilize silica and magnesium as resources.
Korean Patent Nos. 10-2010-0085626, 10-2010-0085599 and 10-2010-0085618 describe a process for producing magnesium compounds and silica products including mechanical activation of slag through milling with a ball mill. It has been published. Mechanical activation of ferronickel slag is intended to transform the crystalline silica to enhance slag leaching with an acid in an amorphous state. In order to achieve a satisfactory leaching rate, the slag should be ground as finely as possible to increase the reaction area. However, in this case, the gelation phenomenon of silica that occurs during slag leaching is an unavoidable problem. Nevertheless, such problems are not taken into account in the above-mentioned application. Silica gel forms a three-dimensional network structure in the reactor, thus reducing the leach rate and making it difficult or even impossible to filter the leachate and solids.
It is known that treatment of slag with an acidic substance requires a large amount of acidic reagent. Since a high acidity of the reaction medium should be maintained in order to recover the target component to the maximum extent, a much larger proportion of reagent than the stoichiometric amount is consumed. When hydrochloric acid is used, most of the acid is used to convert MgO to soluble MgCl 2 . Therefore, the economics of the technology depend greatly on the production of hydrochloric acid that is reused in the leaching process using acidic substances.
（特許文献１） １． 韓国公開特許第１０−２０１０−００８５６２６号
（特許文献２） ２． 韓国公開特許第１０−２０１０−００８５５９９号
（特許文献３） ３． 韓国公開特許第１０−２０１０−００８５６１８号
(Patent Document 1) Korean Published Patent No. 10-2010-0085626
(Patent Document 2) Korean Published Patent No. 10-2010-0085599
(Patent Document 3) Korean Published Patent No. 10-2010-0085618
本発明は前述した従来の技術の問題点を解決するために達成されたもので、その目的はスラグの酸による浸出時シリカのゲル化現象を減少させて、浸出及び濾過の容易なスラグの処理方法を提供するところにある。
本発明の他の目的は、シリカおよびマグネシア抽出過程で発生する低濃度の塩酸溶液と塩素ガスを工程に投入して活用することによって、酸性物質の消費量を節減できる経済的なスラグの処理方法を提供するところにある。
The present invention has been achieved in order to solve the above-mentioned problems of the prior art. The object of the present invention is to reduce the gelation phenomenon of silica during leaching with slag acid and to treat slag easily leached and filtered. Is to provide a method.
Another object of the present invention is to provide an economical slag treatment method that can reduce the consumption of acidic substances by using a low-concentration hydrochloric acid solution and chlorine gas generated in the extraction process of silica and magnesia in the process. Is to provide.
前述した目的を達成するための本発明に係るシリカ及びマグネシア抽出のためのスラグの処理方法は、スラグに塩酸溶液を加えて反応させる酸処理工程と、前記酸処理工程において形成されたスラリを濾過して固形物と濾過液を分離する固液分離工程と、前記固形物からシリカを分離するシリカ分離工程と、前記濾過液中の塩化マグネシウムを除いた不純物を除去して塩化マグネシウム溶液を得る精製工程と、前記塩化マグネシウム溶液を濃縮させてから熱分解してマグネシアを分離するマグネシア分離工程と、を含む。
前記酸処理工程は、前記スラグをパウダーに加工した後前記塩酸溶液と反応させ、前記スラグの加工は、ａ）篩を用いて前記スラグを、０．１〜０．９９ｍｍのサイズで構成された第１グループ粒子と、１．０〜７．０ｍｍのサイズよりなる第２グループ粒子とに分類する工程と、ｂ）前記第２グループ粒子を選別して１００〜３００μｍサイズのパウダーに粉砕する工程とを含むことを特徴とする。
前記酸処理工程は、前記スラグと前記塩酸溶液の反応前または反応中にフッ素化合物を加えて反応させることを特徴とする。
前記フッ素化合物は、フッ化アンモニウム（ＮＨ４Ｆ）、フッ化ナトリウム（ＮａＦ）、ヘキサフルオロケイ酸（Ｈ２ＳｉＦ６）の中から選ばれた少なくともいずれか一つであることを特徴とする。
前記酸処理工程は、前記スラグに前記塩酸溶液を加えて１次反応させた後濾過する第１浸出工程と、前記第１浸出工程で分離された残留物を水で洗浄してから前記塩酸溶液を加えて２次反応させる第２浸出工程とを含むことを特徴とする。
前記シリカ分離工程は、ａ）前記固形物にアルカリ溶液を加えて前記固形物に含有されたシリカを溶解させるアルカリ処理工程と、ｂ）前記アルカリ処理工程後濾過して水ガラスを分離する濾過工程と、ｃ）前記水ガラスに酸物質を加えてシリカを沈殿させるシリカ沈殿工程とを含むことを特徴とする。
前記マグネシア分離工程で生成された塩酸溶液を前記シリカ沈殿工程の前記酸物質として用いることを特徴とする。
前記アルカリ処理工程の前記アルカリ溶液は水酸化ナトリウム溶液であることを特徴とする。
前記マグネシア分離工程で生成された塩酸溶液を前記酸処理工程の前記塩酸溶液として用いることを特徴とする。
前記精製工程は、ａ）前記濾過液に塩基を加えて前記不純物を金属水酸化物形態に沈殿させる沈殿工程と、ｂ）前記沈殿工程で形成された沈殿物を濾過して除去する濾過工程とを含むことを特徴とする。
前記マグネシア分離工程で発生する塩化マグネシウム水和物を脱水させた後電気分解してマグネシウムを分離するマグネシウム分離工程とをさらに含むことを特徴とする。
前記電気分解により生成された塩素ガスを原料にして生産した塩酸溶液を前記酸処理工程の塩酸溶液として用いることを特徴とする。
The method for treating slag for silica and magnesia extraction according to the present invention for achieving the above-described object includes an acid treatment step in which a hydrochloric acid solution is added to the slag for reaction, and the slurry formed in the acid treatment step is filtered. The solid-liquid separation step of separating the solid and the filtrate, the silica separation step of separating the silica from the solid, and the purification of removing the impurities except the magnesium chloride in the filtrate to obtain a magnesium chloride solution And a magnesia separation step in which the magnesium chloride solution is concentrated and then pyrolyzed to separate magnesia.
In the acid treatment step, the slag is processed into a powder and then reacted with the hydrochloric acid solution. The processing of the slag is a) the slag is configured with a size of 0.1 to 0.99 mm using a sieve. A step of classifying the first group particles into second group particles having a size of 1.0 to 7.0 mm; and b) a step of selecting the second group particles and pulverizing them into a powder having a size of 100 to 300 μm. It is characterized by including.
The acid treatment step is characterized in that a fluorine compound is added and reacted before or during the reaction of the slag and the hydrochloric acid solution.
The fluorine compound is at least one selected from ammonium fluoride (NH 4 F), sodium fluoride (NaF), and hexafluorosilicic acid (H 2 SiF 6 ).
The acid treatment step includes a first leaching step in which the hydrochloric acid solution is added to the slag to cause a primary reaction, followed by filtration, and the residue separated in the first leaching step is washed with water and then the hydrochloric acid solution. And a second leaching step of performing a secondary reaction.
The silica separation step includes a) an alkali treatment step in which an alkali solution is added to the solid matter to dissolve silica contained in the solid matter, and b) a filtration step in which water glass is separated by filtration after the alkali treatment step. And c) a silica precipitation step of precipitating silica by adding an acid substance to the water glass.
The hydrochloric acid solution produced in the magnesia separation step is used as the acid substance in the silica precipitation step.
The alkali solution in the alkali treatment step is a sodium hydroxide solution.
The hydrochloric acid solution produced in the magnesia separation step is used as the hydrochloric acid solution in the acid treatment step.
The purification step includes a) a precipitation step in which a base is added to the filtrate to precipitate the impurities in the form of a metal hydroxide, and b) a filtration step in which the precipitate formed in the precipitation step is filtered and removed. It is characterized by including.
The method further includes a magnesium separation step of dehydrating magnesium chloride hydrate generated in the magnesia separation step and then electrolyzing and separating magnesium.
A hydrochloric acid solution produced using chlorine gas generated by the electrolysis as a raw material is used as the hydrochloric acid solution in the acid treatment step.
以上説明したように本発明によれば、スラグの酸による浸出時フッ素化合物を用いてシリカのゲル化現象を減少させることができる。従って、浸出及び濾過が容易である。
また、本発明はシリカ及びマグネシア抽出過程で発生する塩酸と塩素ガスを工程に投入して再活用することによって、酸性廃水の発生を減少させ経済的である。
このように本発明はスラグに含有されたシリカとマグネシウム成分を効率よく抽出して 商業用製品の原料として活用できるスラグの処理方法を提供する。
As described above, according to the present invention, the gelation phenomenon of silica can be reduced by using a fluorine compound during leaching of slag with an acid. Therefore, leaching and filtration are easy.
In addition, the present invention is economical by reducing the generation of acidic wastewater by introducing and reusing hydrochloric acid and chlorine gas generated in the silica and magnesia extraction process.
Thus, the present invention provides a method for treating slag that can be efficiently used as a raw material for commercial products by efficiently extracting silica and magnesium components contained in the slag.
以下、添付図面を参照しながら、本発明の好適な実施の形態によるスラグの処理方法について詳細に説明する。
本発明の一実施形態に係るスラグの処理方法を図１にフローチャートで示した。本発明に係るスラグ処理方法は、スラグに塩酸溶液を加えて反応させる酸処理工程と、酸処理工程で形成されたスラリを濾過して固形物と濾過液を分離する固液分離工程と、固形物からシリカを分離するシリカ分離工程と、濾過液中の不純物を除去して塩化マグネシウム溶液を得る精製工程と、塩化マグネシウム溶液からマグネシアを分離するマグネシア分離工程とに大別される。以下、各工程別に具体的に説明する。
１．酸処理工程
まず、スラグに塩酸溶液を加えて反応させる。
本発明の出発物質は、スラグ（ｓｌａｇ）としてフェロニッケルスラグを用いることが好ましい。フェロニッケルスラグはフェロニッケル（ｆｅｒｒｏｎｉｃｋｅｌ）の製造時電気炉の溶融還元過程で発生する。フェロニッケルスラグはシリカの含量が高くて材料として利用するのに有利である。従って、高炉スラグを用いることもできるが、 フェロニッケルスラグは高炉スラグに比べてシリカの含量が約５２〜５５重量％と高く、さらに不純物が少なくて高純度のシリカを回収することができる。
一例として、フェロニッケルスラグの主要成分は下記の表１の通りである。
A slag processing method according to an embodiment of the present invention is shown in a flowchart in FIG. The slag treatment method according to the present invention includes an acid treatment step in which a hydrochloric acid solution is added to the slag for reaction, a solid-liquid separation step in which the slurry formed in the acid treatment step is filtered to separate a solid and a filtrate, and a solid There are roughly divided into a silica separation step for separating silica from a product, a purification step for removing impurities in the filtrate to obtain a magnesium chloride solution, and a magnesia separation step for separating magnesia from the magnesium chloride solution. Hereinafter, it demonstrates concretely according to each process.
1. Acid treatment step First, a hydrochloric acid solution is added to slag to cause a reaction.
The starting material of the present invention preferably uses ferronickel slag as the slag. Ferronickel slag is generated during the smelting reduction process of the electric furnace during the manufacture of ferronickel. Ferronickel slag has a high silica content and is advantageous for use as a material. Therefore, although blast furnace slag can be used, ferronickel slag has a high silica content of about 52 to 55% by weight as compared with blast furnace slag, and can collect high-purity silica with less impurities.
As an example, the main components of ferronickel slag are as shown in Table 1 below.
前記表１に示したように、フェロニッケルスラグはＳｉＯ２ ５７％、ＭｇＯ３２％であり、その他 Ｆｅ、Ａｌ、Ｍｎなどの金属成分が殆どを占める。
酸との反応性を向上させるために、スラグはパウダーに加工するのが好ましい。このため、塊状のスラグを粗く破砕した後、一定サイズの粒子のスラグだけを選別した後、細かく 粉砕する過程を経る。
望ましくは、破砕後スラグを粒子のサイズ別に分類選別して使う。仮に、篩を用いてスラグを、０．１〜０．９９ｍｍサイズで構成された第１グループ粒子と、１．０〜７．０ｍｍサイズで構成された第２グループ粒子とに分類する。スラグのうち第１グループ粒子は１０〜１２重量％であり、第２グループ粒子は約８８〜９０重量％である。
第１グループ粒子は少量の非晶質ガラス状構造を含むが、殆どは結晶構造を有する。そして、第２グループ粒子は少量の結晶構造を含むが、殆どは非晶質ガラス状構造を有する。この構造的な差異に鑑みて、本発明は第１及び第２グループ粒子を分離して処理する技術を提供する。非晶質ガラス状構造を有する第２グループ粒子は、スラグの格別な前処理なしで大気圧雰囲気下で酸溶液に直ちに溶けることができる。また、第２グループ粒子は第１グループ粒子に比べてＭｇ、ＳｉＯ２ 以外の不純物（Ｆｅ、Ａｌ、Ｃｒ、Ｃａ、Ｍｎ、Ｎｉ）の含量が低い。これは、酸処理過程で消費される塩酸溶液の量を節減できる。Ｆｅ、Ａｌ、Ｃｒなどのように高い原子価を有する金属は２価のＭｇに比べて遥かに多量の酸を消費するからである。
選別された第２グループ粒子はボールミルのような粉砕装置を用いて１００〜３００μｍサイズのパウダーに粉砕する。微細なスラグ粒子は酸との高い反応性を提供する。粒子サイズが大きければ反応速度が低くて生産面において非効率的である。一方、第１グループ粒子は研磨後セメント組成物のための充填材などとして活用できる。
第２グループ粒子を粉砕したスラグが用意されると、塩酸溶液を加えてスラグを塩酸と反応させる。例えば、スラグ１００ｇ当たり１５〜３５％濃度の塩酸溶液２００〜５００ｍｌを加えて反応させる。
As shown in Table 1, ferronickel slag is composed of 57% SiO 2 and 32% MgO, and other metal components such as Fe, Al, and Mn account for the majority.
In order to improve the reactivity with the acid, the slag is preferably processed into a powder. For this reason, after the coarse slag is roughly crushed, only the slag of a certain size is selected and then finely pulverized.
Preferably, the slag after crushing is classified and selected according to the size of the particles. Temporarily, a slag is classified into the 1st group particle comprised by 0.1-0.99 mm size, and the 2nd group particle comprised by 1.0-7.0 mm size using a sieve. Of the slag, the first group particles are 10 to 12% by weight, and the second group particles are about 88 to 90% by weight.
The first group particles contain a small amount of amorphous glassy structure, but most have a crystalline structure. The second group particles have a small amount of crystal structure, but most have an amorphous glassy structure. In view of this structural difference, the present invention provides a technique for separating and processing the first and second group particles. The second group particles having an amorphous glassy structure can be immediately dissolved in an acid solution under an atmospheric pressure atmosphere without any special pretreatment of slag. Further, the second group particles have a lower content of impurities (Fe, Al, Cr, Ca, Mn, Ni) other than Mg and SiO 2 compared to the first group particles. This can save the amount of hydrochloric acid solution consumed in the acid treatment process. This is because a metal having a high valence such as Fe, Al, Cr, etc. consumes a much larger amount of acid than divalent Mg.
The selected second group particles are pulverized into a powder having a size of 100 to 300 μm using a pulverizer such as a ball mill. Fine slag particles provides high have reactivity with acid. If the particle size is large, the reaction rate is low and the production is inefficient. On the other hand, the first group particles can be used as a filler for the cement composition after polishing.
When slag pulverized second group particles Ru are prepared, the reaction of the slag with hydrochloric acid by addition of a solution of hydrochloric acid. For example, 200-500 ml of a 15-35% strength hydrochloric acid solution per 100 g of slag is added and reacted.
塩酸とスラグの反応を通じてスラグ中に含有された金属成分が塩酸に溶けて浸出される。浸出された金属成分は塩酸塩の形態で存在する。そして、塩酸に不溶性であるシリカはスラグから分離されて固形物に沈殿される。このように塩酸との反応を通じて浸出された塩酸塩とシリカ、それから未反応スラグ、過剰の塩酸は混在してスラリ（ｓｌｕｒｙ）状に存在する。 Through the reaction between hydrochloric acid and slag, the metal components contained in the slag are dissolved in hydrochloric acid and leached. The leached metal component is present in the form of hydrochloride. Silica that is insoluble in hydrochloric acid is then separated from the slag and precipitated into a solid. Thus, the hydrochloride and silica leached through the reaction with hydrochloric acid, unreacted slag, and excess hydrochloric acid are mixed and exist in a slurry state.
スラグと塩酸の反応式は次の通りである。
スラグ（Ｃａ，Ａｌ，Ｍｇ， ．．．） ＋ ＨＣｌ → ＳｉＯ２↓ ＋ Ｍ（Ｃｌ）ｎ， Ｍ＝Ｃａ， Ａｌ， Ｍｇ．．．
塩酸の反応時間によるスラグ内のマグネシウムとシリカの浸出率を図４に示した。図４から分かるように、反応開始後５分以内に４３％（スラグに含有されたマグネシウム量に対する浸出マグネシウム量の百分率）のマグネシウムと５７％（スラグに含有されたシリカ量に対する浸出シリカ量の百分率）のシリカが浸出される。そして、５分経過後浸出速度が遅くなることが分かるが、これはシリカのゲル化の発生に起因する。このようなシリカゲル化はスラグの反応性を低下させ、濾過を困難にする。このような問題点を、本発明ではフッ素化合物の使用によって克服する。
フッ素化合物はスラグと塩酸の反応前にスラグに加えられたり、スラグと塩酸の反応中に加えられる。フッ素化合物としてフッ化アンモニウム（ＮＨ４Ｆ）、フッ化ナトリウム（ＮａＦ）、ヘキサフルオロケイ酸（Ｈ２ＳｉＦ６）の中から選ばれた少なくともいずれか一つを利用できる。スラグ１００ｇ当たりフッ素化合物の適正量はヘキサフルオロケイ酸の場合は、０．０１〜０．０５ｍｏｌ程であり、フッ化アンモニウムとフッ化ナトリウムは０．０４〜０．１０ｍｏｌほどである。
酸処理工程においてフッ素化合物をスラグに加えることは、スラグの非晶質ガラス状構造をエッチングして、スラグの浸出に有利な効果を奏する。また、フッ素化合物のような強い酸化剤によって鉄、クロム、マンガンなどのような金属成分を容易に酸化させることができる。
シリカの回収率を向上させるため、酸処理工程はスラグと塩酸反応を数回繰返して行える。例えば、スラグに塩酸溶液を加えて１次反応させた後に濾過する第１浸出工程と、前記第１浸出工程において分離された残留物を水で洗浄した後に塩酸溶液を再び加えて２次反応させる第２浸出工程とからなる。
２．固液分離工程
スラグと塩酸の反応により形成されたスラリを濾過液と固形物とに分離する。濾過は圧力濾過器や遠心分離機など多様な固液分離機を用いて行える。
濾過液には塩酸に溶解された金属成分が塩酸塩の形態で存在する。そして、固形物は８０〜９５重量％のシリカ及び残量の不純物、未反応スラグで構成される。
固液分離工程で得られた固形物からシリカを抽出し、濾過液からマグネシアを抽出する。
３．シリカ分離工程
固液分離工程で得られた固形物からシリカを抽出するためのシリカ分離工程は、ａ）固形物にアルカリ溶液を加えて固形物に含有されたシリカを溶解させるアルカリ処理工程と、 ｂ）アルカリ処理工程後に濾過して水ガラスを分離する濾過工程と、ｃ）水ガラスに酸物質を加えてシリカを沈殿させるシリカ沈殿工程とを含む。
アルカリ処理工程は、固形物１００重量部に対して１５０〜３００重量部のアルカリを加えて、８０〜９０℃で３０〜６０分間反応させて行える。アルカリとして濃度１２〜１５％の水酸化ナトリウム溶液を用いることができる。
固形物にアルカリ、例えば、水酸化ナトリウム溶液を添加すれば、固形物に含まれたシリカは次のように反応する。
The reaction formula of slag and hydrochloric acid is as follows.
Slag (Ca, Al, Mg, ...) + HCl → SiO 2 ↓ + M (Cl) n, M = Ca, Al, Mg. . .
The leaching rate of magnesium and silica in the slag according to the reaction time of hydrochloric acid is shown in FIG. As can be seen from FIG. 4, within 5 minutes after the start of the reaction, 43% (percentage of the leached magnesium with respect to the amount of magnesium contained in the slag) magnesium and 57% (percentage of the leached silica with respect to the amount of silica contained in the slag) ) Silica is leached. And it turns out that the leaching speed | rate becomes slow after 5 minutes progress, but this originates in generation | occurrence | production of the gelatinization of a silica. Such silica gelation reduces the reactivity of slag and makes filtration difficult. Such problems are overcome by the use of fluorine compounds in the present invention.
The fluorine compound is added to the slag before the reaction between the slag and hydrochloric acid, or is added during the reaction between the slag and hydrochloric acid. As the fluorine compound, at least one selected from ammonium fluoride (NH 4 F), sodium fluoride (NaF), and hexafluorosilicic acid (H 2 SiF 6 ) can be used. The appropriate amount of the fluorine compound per 100 g of slag is about 0.01 to 0.05 mol in the case of hexafluorosilicic acid, and about 0.04 to 0.10 mol for ammonium fluoride and sodium fluoride.
Adding a fluorine compound to the slag in the acid treatment step etches the amorphous glassy structure of the slag and has an advantageous effect on the slag leaching. In addition, metal components such as iron, chromium and manganese can be easily oxidized by a strong oxidizing agent such as a fluorine compound.
In order to improve the recovery rate of silica, the acid treatment step can be performed by repeating the slag and hydrochloric acid reaction several times. For example, a first leaching step in which a hydrochloric acid solution is added to slag and subjected to a primary reaction and then filtered, and a residue separated in the first leaching step is washed with water, and then a hydrochloric acid solution is added again to cause a secondary reaction. It consists of a 2nd leaching process.
2. Solid-liquid separation process
The slurry formed by the reaction of slag and hydrochloric acid is separated into filtrate and solid. Filtration can be performed using various solid-liquid separators such as pressure filters and centrifuges.
In the filtrate, a metal component dissolved in hydrochloric acid is present in the form of hydrochloride. The solid is composed of 80 to 95% by weight of silica, remaining impurities, and unreacted slag.
Silica is extracted from the solid obtained in the solid-liquid separation step, and magnesia is extracted from the filtrate.
3. Silica separation process
The silica separation step for extracting silica from the solid matter obtained in the solid-liquid separation step includes a) an alkali treatment step in which an alkali solution is added to the solid matter to dissolve the silica contained in the solid matter, and b) an alkali. A filtration step of separating the water glass by filtration after the treatment step; and c) a silica precipitation step of precipitating silica by adding an acid substance to the water glass.
The alkali treatment step can be performed by adding 150 to 300 parts by weight of alkali to 100 parts by weight of the solid and reacting at 80 to 90 ° C. for 30 to 60 minutes. A sodium hydroxide solution having a concentration of 12 to 15% can be used as the alkali.
If an alkali such as a sodium hydroxide solution is added to the solid, the silica contained in the solid reacts as follows.
ＳｉＯ２ ＋ ２ＮａＯＨ → Ｎａ２ＳｉＯ３（ｗａｔｅｒ ｇｌａｓｓ） ＋ Ｈ２Ｏ
固形物とアルカリの反応後の液状の水ガラスと溶解されない固形の残留物を分離するために濾過する。濾過は濾過紙または通常の固液分離機を用いて行える。
濾過過程を通じて得られた水ガラスは、時間が経つにつれて綺麗で安定的な状態になる。水ガラスは比重１．５０〜１．６０ｇ／ｍｌ、ＳｉＯ２／Ｎａ２Ｏモル比率が２．５〜３．３であって、シリカ生産のための良質の材料になる。
SiO 2 + 2NaOH → Na 2 SiO 3 (water glass) + H 2 O
Filtration is performed to separate the liquid water glass after the reaction between the solid and the alkali and the undissolved solid residue. Filtration can be performed using filter paper or a normal solid-liquid separator.
The water glass obtained through the filtration process becomes clean and stable over time. Water glass has a specific gravity of 1.50 to 1.60 g / ml and a SiO 2 / Na 2 O molar ratio of 2.5 to 3.3, which makes it a good material for silica production.
そして、濾過で発生された残留物はシリカの含量が高いことを除けばスラグに似ている。これは、残留物が非溶解スラグで構成されていることを意味する。従って、残留物は出発物質であるスラグとして再活用される。
水ガラスが用意されると、酸物質を加えてシリカを沈殿させて分離する。
シリカを沈殿させるために水ガラスに塩酸溶液を加えてｐＨを８．５程度に調整する。５〜６分後にシリカの沈殿が開始する。シリカを沈殿させた後に濾過してシリカを分離できる。スラグから分離されたシリカは純度９８重量％以上である。実験を通じて分離されたシリカの成分は、一例として、ＳｉＯ２ ９８．７３重量％、ＡｌＯ３ ０．６６重量％、Ｎａ２Ｏ ０．４７重量％、ＣａＯ ０．０４重量％、ＭｇＯ ０．０３重量％、Ｆｅ２Ｏ３ ０．０３重量％である。
このように中間物質である水ガラスは、沈殿シリカ生産のための極めて適切な材料であり、大事なことはシリカ回収率が高いということである。スラグに含有されたシリカのうち約８０％が本発明により分離しており、これはフェロニッケルスラグ１トン当たり４５０ｋｇのシリカ生産量に該当するものである。
And the residue generated by filtration resembles slag except for the high silica content. This means that the residue consists of undissolved slag. Therefore, the residue is reused as the starting slag.
When the water glass is prepared, an acid substance is added to precipitate silica and separate it.
In order to precipitate silica, a hydrochloric acid solution is added to water glass to adjust the pH to about 8.5. Silica precipitation begins after 5-6 minutes. The silica can be separated by precipitating the silica and then filtering. Silica separated from the slag has a purity of 98% by weight or more. For example, the components of silica separated through the experiment include 98.73% by weight of SiO 2 , 0.66% by weight of AlO 3 , 0.47% by weight of Na 2 O, 0.04% by weight of CaO, and 0.03% by weight of MgO. %, Fe 2 O 3 0.03% by weight.
Thus, water glass, which is an intermediate substance, is a very suitable material for producing precipitated silica, and the important thing is that the silica recovery rate is high. About 80% of the silica contained in the slag is separated according to the present invention, which corresponds to a production of 450 kg of silica per ton of ferronickel slag.
４．精製工程
固液分離工程で得られた濾過液からマグネシアを抽出するために精製工程が行われる。
精製工程は、ａ）濾過液に塩基を加えて不純物を金属水酸化物形態に沈殿させる沈殿工程と、ｂ）沈殿工程で形成された沈殿物を濾過して除去する濾過工程とを含む。
4). Purification process
As purification Engineering to extract magnesia filtrate obtained in the solid-liquid separation step.
The purification step includes a) a precipitation step in which a base is added to the filtrate to precipitate impurities into a metal hydroxide form, and b) a filtration step in which the precipitate formed in the precipitation step is filtered and removed.
固液分離工程で得られた濾過液には塩化マグネシウム、塩化アルミニウム、塩化カルシウムなどが存在する。従って、所望の塩化マグネシウムのほか、他の不純物を除去するために塩基を加えて塩化アルミニウム、塩化カルシウムなどを金属水酸化物の形態に沈殿させた後に分離する。塩基として水酸化ナトリウムを用いることができる。また、塩基として過酸化水素と水酸化ナトリウムを用いることもできる。
一例として、濾過液に過酸化水素水を添加してｐＨ３〜４にした後、水酸化ナトリウム溶液を加えてｐＨ６．５〜７．５まで調節して不純物を沈殿させることができる。
沈殿反応が済んだ後に濾過してマグネシウム溶液を得ることができる。マグネシウム溶液と分離された沈殿物は、主に鉄、酸化マグネシウム、アルミニウム及び他の微量不純物で構成されている。従って、適切な処理後製鉄原料として用いられる。
５． マグネシア分離工程
塩化マグネシウム溶液からマグネシアを分離するために濃縮及び熱分解を行う。まず、蒸発によって塩化マグネシウム溶液を濃縮させて塩化マグネシウム水和物 （ＭｇＣｌ２・ｎＨ２Ｏ）を得る。そして、塩化マグネシウム水和物を流動層乾燥機、回転釜、スプレイ乾燥機などのような多様な装置を使って熱分解する。熱分解時の温度は約７００℃である。
熱分解を通じて塩化マグネシウム水和物は、下記のようにマグネシアと塩酸に分解される。
ＭｇＣｌ２・ｎＨ２Ｏ →ＭｇＯ（ｓ） ＋ ２ＨＣｌ ＋ （ｎ−１）Ｈ２Ｏ
熱分解後の濾過を介してマグネシアを分離する。このように得られたマグネシアの回収率はフェロニッケルスラグ１トン当たり約１７０ｋｇに該当する。
Magnesium chloride, aluminum chloride, calcium chloride and the like are present in the filtrate obtained in the solid-liquid separation step. Therefore, in addition to the desired magnesium chloride, a base is added to remove other impurities, and aluminum chloride, calcium chloride and the like are precipitated in the form of metal hydroxide and then separated. Sodium hydroxide can be used as the base. Further, hydrogen peroxide and sodium hydroxide can also be used as the base.
As an example, after adding hydrogen peroxide water to the filtrate to adjust the pH to 3 to 4, a sodium hydroxide solution can be added to adjust the pH to 6.5 to 7.5 to precipitate impurities.
After the precipitation reaction is completed, it can be filtered to obtain a magnesium solution. The precipitate separated from the magnesium solution is mainly composed of iron, magnesium oxide, aluminum and other trace impurities. Therefore, it is used as an appropriate post-treatment ironmaking raw material.
5. Magnesia separation process
Concentration and pyrolysis are performed to separate magnesia from the magnesium chloride solution. First, the magnesium chloride solution is concentrated by evaporation to obtain magnesium chloride hydrate (MgCl 2 · nH 2 O). Then, the magnesium chloride hydrate is pyrolyzed using various devices such as a fluidized bed dryer, a rotary kettle, a spray dryer and the like. The temperature during pyrolysis is about 700 ° C.
Through pyrolysis, magnesium chloride hydrate is decomposed into magnesia and hydrochloric acid as follows.
MgCl 2 .nH 2 O → MgO (s) + 2HCl + (n−1) H 2 O
Magnesia is separated through filtration after pyrolysis. The magnesia recovery rate thus obtained corresponds to about 170 kg per ton of ferronickel slag.
マグネシアと分離された濾過液は濃度８ないし１２％の塩酸溶液である。このような濾過液は酸処理工程における塩酸溶液と、シリカ沈殿工程における酸物質として再活用して製造コストを節減できる。
一方、本発明は他の実施例として図３に示したように、マグネシア分離工程で発生する塩化マグネシウム水和物を用いてマグネシウムを得ることができる。このため、塩化マグネシウム水和物（ＭｇＣｌ２・ｎＨ２Ｏ）を脱水させて得た無水塩化マグネシウムを電気分解してマグネシウムを分離する。電気分解を用いてマグネシウムを分離する技術は公知の技術であることから、具体的な説明を省く。
電気分解により生成されたマグネシウムは各種のマグネシウム製品の原料として用いる。そして、マグネシウムと共に生成された塩素ガスは塩化マグネシウム水和物の脱水過程で触媒として再活用できる。また、塩素ガスを用いて塩酸を生産した後の酸処理工程の塩酸溶液として再活用できる。
一方、図２に本発明の他の実施例によってスラグからシリカを得るための酸処理及びアルカリ処理工程のフローチャートを示した。
図２を参照すれば、第１浸出及び第２浸出過程からなる酸処理工程と、アルカリ処理工程を通じてスラグからシリカを得る。
The filtrate separated from magnesia is a hydrochloric acid solution having a concentration of 8 to 12%. Such a filtrate can be reused as a hydrochloric acid solution in the acid treatment step and an acid substance in the silica precipitation step, thereby reducing manufacturing costs.
On the other hand, as shown in FIG. 3 as another embodiment of the present invention, magnesium can be obtained using magnesium chloride hydrate generated in the magnesia separation step. For this reason, anhydrous magnesium chloride obtained by dehydrating magnesium chloride hydrate (MgCl 2 · nH 2 O) is electrolyzed to separate magnesium. Since the technique for separating magnesium using electrolysis is a known technique, a detailed description thereof will be omitted.
Magnesium produced by electrolysis is used as a raw material for various magnesium products. And the chlorine gas produced | generated with magnesium can be reused as a catalyst in the dehydration process of magnesium chloride hydrate. Further, it can be reused as a hydrochloric acid solution in an acid treatment step after hydrochloric acid is produced using chlorine gas.
On the other hand, FIG. 2 shows a flowchart of acid treatment and alkali treatment steps for obtaining silica from slag according to another embodiment of the present invention.
Referring to FIG. 2, silica is obtained from slag through an acid treatment process including a first leaching process and a second leaching process, and an alkali treatment process.
スラグに塩酸溶液を１次に加えて第１浸出工程を行う。そして、濾過して残留物と濾過液とに分離する。濾過液は前述した実施例において説明したように、精製及び熱分解を通じてマグネシアを得る。そして、残留物は洗浄後塩酸溶液を加えて第２浸出工程を行う。この際、塩酸溶液で熱分解を通じて生成されたマグネシアから分離された濾過液を再活用できる。第２浸出工程後に濾過して濾過液と残留物に分離する。この際の濾過液は塩酸の濃度が低いので、高濃度の商業用塩酸と混合して第１浸出で使用される塩酸溶液として用いる。 A first leaching step is performed by first adding a hydrochloric acid solution to the slag. And it filters and isolate | separates into a residue and a filtrate. The filtrate obtains magnesia through purification and pyrolysis, as described in the previous examples. Then, the residue is washed and added with a hydrochloric acid solution to perform a second leaching step. At this time, the filtrate separated from magnesia produced through pyrolysis with a hydrochloric acid solution can be reused. Filter after the second leaching step to separate the filtrate and residue. At this time, since the concentration of hydrochloric acid is low, the filtrate is mixed with commercial hydrochloric acid having a high concentration and used as a hydrochloric acid solution used in the first leaching.
第２浸出工程後に濾過して分離された残留物に水酸化ナトリウムを加えてアルカリ処理する。そして、濾過して残留物と水ガラスを分離する。この際発生する残留物は第１浸出過程で使われるスラグ材料として活用される。そして、水ガラス中のシリカを沈殿させるための酸物質として熱分解を通じて生成されたマグネシアから分離された濾過液を再活用できる。 Sodium hydroxide is added to the residue separated by filtration after the second leaching step and treated with alkali. Then, the residue and water glass are separated by filtration. The residue generated at this time is used as a slag material used in the first leaching process. And the filtrate isolate | separated from the magnesia produced | generated through thermal decomposition as an acid substance for precipitating the silica in water glass can be reused.
以下、実験例を通じて本発明について説明する。但し、下記の実験例は本発明を具体的に説明するためのものであって、本発明の範囲を下記の実験例に限定するものではない。
＜酸処理実験＞
（１）第１実験例
用意したフェロニッケルスラグを１次に破砕した後、篩を用いてサイズ別に分類した。分類された各粒子の成分を分析して、下記の表２に示した。
<Acid treatment experiment>
(1) First experiment example
The prepared ferronickel slag was first crushed and then classified by size using a sieve. The components of each classified particle were analyzed and shown in Table 2 below.
前記表２に示したように、１．０以上の粒子だけを使う場合、マグネシアとシリカの含量が１．０未満の粒子に比べてさらに高いことが分かる。
サイズ１．０ｍｍ以上の粒子だけを選別した後、２００μｍに粉砕した。粉砕されたスラグ粉末１００ｇを、濃度２０％塩酸溶液３２ｍｌが入っている１０００ｍｌのフラスコに投入した。フラスコには攪拌機、還流コンデンサ、温度計及びヒート装置が具備されているものを用いた。５時間攪拌しつつ９０℃の大気圧下で１次浸出の反応を進めた。
（２）第２及び第３実験例
前記第１実験例と同様の方法で行い、スラグ１００ｇにフッ素化合物としてＨ２ＳｉＦ６ ０．０３ｍｏｌを添加した。フッ素化合物の添加は２種の方法に分けて行った。第２実験例は、塩酸溶液との反応前にフッ素化合物をスラグに添加し、第３実験例は、フッ素化合物をスラグと塩酸溶液の反応中に添加した。
前記第１〜第２実験例を通じて得たスラリのマグネシア及びシリカの浸出率、スラリの 濾過後の濾過液と固形物との特性を、下記の表３に示した。
After selecting only particles having a size of 1.0 mm or more, it was pulverized to 200 μm. 100 g of the pulverized slag powder was put into a 1000 ml flask containing 32 ml of a 20% strength hydrochloric acid solution. A flask equipped with a stirrer, a reflux condenser, a thermometer, and a heat device was used. The reaction of primary leaching proceeded under an atmospheric pressure of 90 ° C. with stirring for 5 hours.
(2) Second and third experimental examples
The same method as in the first experimental example was performed, and 0.03 mol of H 2 SiF 6 was added as a fluorine compound to 100 g of slag. The addition of the fluorine compound was performed in two ways. In the second experimental example, the fluorine compound was added to the slag before the reaction with the hydrochloric acid solution, and in the third experimental example, the fluorine compound was added during the reaction between the slag and the hydrochloric acid solution.
Table 3 below shows the leaching rate of the slurry magnesia and silica obtained through the first and second experimental examples, and the characteristics of the filtrate and the solid after the slurry filtration.
前記表３を参照すると、第１実験例に比べてフッ素化合物を使用した第２及び第３実験例の浸出特性がさらに優れていることが分かった。マグネシアとシリカの浸出率において第２及び第３実験例が第１実験例の結果よりさらに良好であった。特に、フッ素化合物を添加して反応させる場合、濾過機能を大幅に向上させることが確認された。
（３）第４実験例
第３実験例のスラリをろ過して分離した固形物には、ＳｉＯ２ ８３．５９重量％、ＭｇＯ４．２４重量％、ＦｅＯ／Ｆｅ２Ｏ３ ０．８４重量％、Ａｌ２Ｏ３ ３．２３重量％、Ｃｒ２Ｏ３ ０．１５重量％、ＣａＯ ０．４９重量％、Ｃｌ ０．４９重量％及びその他の微量の元素が含まれていた。ここで、シリカのほか、他の成分は不純物と見なされる。アルカリ処理工程を行う前に、不純物はできるだけ最大に除去されるべきであり、特にアルミニウムとマグネシウムは最大限減少されるべきである。
このため、第３実験例のスラリを濾過して分離した固形物１２５ｇに濃度１０％塩酸溶液２１０ｍｌを加えてから持続的に攪拌した。反応温度は８０℃、浸出時間は９０分であった。反応完了後のスラリを濾過して濾過液と固形物とに分離した。
第４実験例を通じて得た固形物は、ＳｉＯ２ ９４．７９重量％、ＭｇＯ ０．９２重量％、ＦｅＯ／Ｆｅ２Ｏ３ ０．５４重量％、Ａｌ２Ｏ３ １．７４重量％、Ｃｒ２Ｏ３ ０．１２重量％、ＣａＯ ０．３６重量％、Ｃｌ０．５０重量％ 及び他の微量の不純物が含まれている。
図５に示した固形物の写真をみると、シリカ粒子（四角形で表示）の間に不純物粒子（円
形で表示）が混入されていることが分かる。
（４）第５実験例
第４実験例を通じて得た固形物１１８ｇに濃度１２．５％ＮａＯＨ溶液２００ｇを加えてから８０℃の温度で４５分間攪拌しつつ反応させた。反応完了後スラリを濾過して固体残留物と水ガラスとを分離した。分離された固体残留物は、最初に５０ｍｌの脱イオン水で、２回目は約３００ｍｌの脱イオン水で、最後は水道水で洗浄した。最初の洗浄後発生した洗浄液はシリカ成分の損失を最小化するために水ガラスに混合した。それから２回目の洗浄後発生した洗浄液は、後述する第６実験例におけるシーディング（ｓｅｅｄｉｎｇ）溶液として用いた。
前記第５実験例を通じて得た水ガラスは、密度１．５８ｇ／ｍｌ、ＳｉＯ２／Ｎａ２０モル比２．８であり、主要成分としてＳｉＯ２ １１．６ｗｔ％、Ｎａ２Ｏ ４．２ｗｔ％であり、不純物として（Ａｌ２Ｏ３ ＋Ｆｅ２Ｏ３）０．０６ｗｔ％、（ＭｇＯ ＋ ＣａＯ） ０．０２ｗｔ％であった。
（５）第６実験例
５ｇのＳｉＯ２／ｌの濃度を有するケイ酸塩溶液を作るために、１１℃の温度下で前記第５実験例を通じて得たシーディング溶液２９０ｍｌを５００ｍｌの水に希釈した後、攪拌機とヒーター、温度計が備えられた１０００ｍｌガラス容器に投入した。そして、１０％塩酸２００ｍｌを３５０ｍｌの水に希釈した後ガラス容器に加えながら攪拌してｐＨ９に調整した。シリカは混濁状態の形態に現れるが、５〜６分後に沈殿が始まり、その後凝集した形態で沈殿した。最後に、濃度１０％のＮａＯＨ溶液を加えてｐＨを７に調整した。
そして、濾過して沈殿したシリカを分離した後、水で洗浄してから１２５℃で乾燥させた。
スラグ１００ｇからの分離された最終シリカの量は４５．０３ｇであった。従って、シリカ製品の収率は４５％に至った。シリカは純度９８．７重量％であった。その他の不純物として、Ａｌ２Ｏ３ ０．６６重量％、Ｎａ２Ｏ ０．４７重量％、ＣａＯ ０．０４重量％、ＭｇＯ ０．０３重量％、Ｆｅ２Ｏ３ ０．０３重量％であることが確認された。
（６）第７実験例
前記第４実験例を通じて得た濾過液に濃度１０％の水酸化ナトリウム溶液を加えてｐＨ５に調整して１次に沈殿させた後濾過してから、再び濃度１０％の水酸化ナトリウム溶液を加えてｐＨに調整した後濾過して、塩化マグネシウム溶液と沈殿物を分離した。
分離された塩化マグネシウム溶液は密度１．１７ｇ／ｍｌであり、リットル当たり金属濃度はマグネシウム４１．９８ｇ、ナトリウム７．９５ｇ、カルシウム０．４２ｇであった。そして、鉄、マンガン、クロム、ニッケル、コバルト、アルミニウムは検出されなかった。
（７）第８実験例
前記第７実験例で得た塩化マグネシウム溶液２４８ｍｌを真空蒸発器で蒸発させて濃縮した後にアルミナるつぼに配置し、１時間８００℃で実験室のマッフル炉で熱分解した後、残渣塩化物を分解するために熱水を混合した。得られた懸濁液を濾過して濾過液と残留物を分離した。残留物を脱イオン水で２回洗浄して２時間１２０℃で実験室乾燥機に乾燥させて、１６．３ｇ量の白色のマグネシアを得た。得られたマグネシアの成分はＭｇＯ ９８．５重量％、Ｎａ２Ｏ ０．３３重量％、Ａｌ２Ｏ３ ０．１２重量％、ＳｉＯ２ ０．３０重量％、Ｆｅ２Ｏ３ ０．１４重量％、Ｃｒ２Ｏ３ ０．０１重量％、Ｃｌ０．４２重量％、ＳＯ３ ０．０７重量％であった。従って、フェロニッケルスラグ１００ｇにおいてマグネシアの生産は１６．３ｇであり、５２．６％のＭｇＯを回収した。
前述した実験結果を通じてフェロニッケルスラグからシリカとマグネシアを効率よく分離できることを確認した。下記の表４に、実験を通じて得られた各物質の成分分析結果をまとめた。表４において第１試料は第１実験例で得た１．０〜７．０ｍｍサイズのフェロニッケルスラグであり、第２試料は第３実験例で得た固形物であり、第３試料は第４実験例で得た固形物であり、第４試料は第５実験例から得た残留物であり、第５試料は第７実験例で得た沈殿物であり、第６試料は第６実験例から得たシリカである。
(3) Fourth Experimental Example The solid material obtained by filtering and separating the slurry of the third experimental example was 83.59 wt% SiO 2, 4.24 wt% MgO, 0.84 wt% FeO / Fe 2 O 3 , Al 2 O 3 3.23 wt%, Cr 2 O 3 0.15 wt%, CaO 0.49 wt%, Cl 0.49 wt% and other trace elements were included. Here, in addition to silica, other components are regarded as impurities. Prior to performing the alkaline treatment step, impurities should be removed as much as possible, especially aluminum and magnesium.
For this reason, 210 ml of a 10% hydrochloric acid solution was added to 125 g of the solid matter separated by filtering the slurry of the third experimental example, and then continuously stirred. The reaction temperature was 80 ° C. and the leaching time was 90 minutes. The slurry after completion of the reaction was filtered to separate into a filtrate and a solid.
The solid obtained through the fourth experimental example was SiO 2 94.79 wt%, MgO 0.92 wt%, FeO / Fe 2 O 3 0.54 wt%, Al 2 O 3 1.74 wt%, Cr 2 O 3 0.12% by weight, CaO 0.36% by weight, Cl 0.50% by weight and other trace impurities.
When the photograph of the solid substance shown in FIG. 5 is seen, it can be seen that impurity particles (displayed in a circle) are mixed between silica particles (displayed in a square).
(4) Fifth Experimental Example After adding 200 g of a 12.5% NaOH solution to 118 g of the solid material obtained through the fourth experimental example, the reaction was conducted at a temperature of 80 ° C. with stirring for 45 minutes. After the reaction was completed, the slurry was filtered to separate the solid residue and water glass. The separated solid residue was washed first with 50 ml deionized water, a second time with about 300 ml deionized water and finally with tap water. The cleaning solution generated after the first cleaning was mixed with water glass to minimize the loss of silica component. Then, the cleaning solution generated after the second cleaning was used as a seeding solution in a sixth experimental example to be described later.
The water glass obtained through the fifth experimental example has a density of 1.58 g / ml and a SiO 2 / Na 2 molar ratio of 2.8, and the main components are SiO 2 11.6 wt% and Na 2 O 4.2 wt%. The impurities were (Al 2 O 3 + Fe 2 O 3 ) 0.06 wt% and (MgO + CaO) 0.02 wt%.
(5) Sixth Experimental Example To make a silicate solution having a concentration of 5 g of SiO 2 / l, 290 ml of the seeding solution obtained through the fifth experimental example was diluted to 500 ml of water at a temperature of 11 ° C. After that, it was put into a 1000 ml glass container equipped with a stirrer, a heater and a thermometer. Then, 200 ml of 10% hydrochloric acid was diluted with 350 ml of water, and then stirred to adjust to
And the silica which precipitated by filtration was isolate | separated, Then, it wash | cleaned with water, Then, it was made to dry at 125 degreeC.
The amount of final silica separated from 100 g of slag was 45.03 g. Accordingly, the yield of silica product reached 45%. Silica had a purity of 98.7% by weight. As other impurities, Al 2 O 3 0.66 wt%, Na 2 O 0.47 wt%, CaO 0.04 wt%, MgO 0.03% wt, Fe 2 O 3 0.03% wt. Was confirmed.
(6) Seventh
The separated magnesium chloride solution had a density of 1.17 g / ml, and the metal concentration per liter was 41.98 g of magnesium, 7.95 g of sodium, and 0.42 g of calcium. And iron, manganese, chromium, nickel, cobalt, and aluminum were not detected.
(7) Eighth Experimental Example 248 ml of the magnesium chloride solution obtained in the seventh experimental example was evaporated and concentrated in a vacuum evaporator, then placed in an alumina crucible and pyrolyzed in a laboratory muffle furnace at 800 ° C. for 1 hour. Later, hot water was mixed to decompose the residual chloride. The resulting suspension was filtered to separate the filtrate and residue. The residue was washed twice with deionized water and dried in a laboratory dryer at 120 ° C. for 2 hours to give 16.3 g of white magnesia. The components of the obtained magnesia were MgO 98.5% by weight, Na 2 O 0.33% by weight, Al 2 O 3 0.12% by weight, SiO 2 0.30% by weight, Fe 2 O 3 0.14% by weight. Cr 2 O 3 0.01 wt%, Cl 0.42 wt%, SO 3 0.07 wt%. Therefore, in 100 g of ferronickel slag, magnesia production was 16.3 g, and 52.6% of MgO was recovered.
Through the above experimental results, it was confirmed that silica and magnesia can be efficiently separated from ferronickel slag. Table 4 below, meta summarizes the component analysis results for each material obtained through experimentation. In Table 4, the first sample is a ferronickel slag having a size of 1.0 to 7.0 mm obtained in the first experimental example, the second sample is a solid material obtained in the third experimental example, and the third sample is the first sample. The solid sample obtained in 4 experimental examples, the fourth sample is the residue obtained from the fifth experimental example, the fifth sample is the precipitate obtained in the seventh experimental example, and the sixth sample is the sixth experiment. Silica obtained from the examples.
以上、添付図面を参照しながら本発明の好適な実施形態について詳細に説明したが、本発明は係る例に限定されない。本発明の属する技術の分野における通常の知識を有する者であれば、特許請求の範囲に記載された技術的思想の範囲内において、各種の変更例または修正例に想到しうることは明らかであり、これらについても当然に本発明の技術的範囲に属するものと了解される。 The preferred embodiments of the present invention have been described in detail above with reference to the accompanying drawings, but the present invention is not limited to such examples. It is obvious that a person having ordinary knowledge in the technical field to which the present invention belongs can come up with various changes or modifications within the scope of the technical idea described in the claims. Of course, it is understood that these also belong to the technical scope of the present invention.
Claims (11)
前記酸処理工程で形成されたスラリを濾過して固形物と濾過液とを分離する固液分離工程と、
前記固形物からシリカを分離するシリカ分離工程と、
前記濾過液中の塩化マグネシウムを除いた不純物を除去して塩化マグネシウム溶液を収得する精製工程と、
前記塩化マグネシウム溶液を濃縮させた後、塩化マグネシウム水和物を得て、前記塩化マグネシウム水和物を熱分解してマグネシアと塩酸を得て、濾過を介してマグネシアを分離するマグネシア分離工程とを含み、
前記精製工程は、ａ）前記濾過液に塩基を加えて前記不純物を金属水酸化物の形態で沈殿させる沈殿工程と、ｂ）前記沈殿工程で形成された沈殿物を濾過して除去する濾過工程とを含むことを特徴とするシリカ及びマグネシア抽出のためのスラグの処理方法。 An acid treatment step in which a hydrochloric acid solution is added to the slag and reacted;
A solid-liquid separation step of filtering the slurry formed in the acid treatment step to separate a solid and a filtrate;
A silica separation step of separating silica from the solid,
A purification step of obtaining a magnesium chloride solution by removing impurities excluding magnesium chloride in the filtrate;
After the magnesium chloride solution is concentrated , magnesium chloride hydrate is obtained, the magnesium chloride hydrate is pyrolyzed to obtain magnesia and hydrochloric acid, and a magnesia separation step of separating magnesia through filtration. seen including,
The purification step includes a) a precipitation step in which a base is added to the filtrate to precipitate the impurities in the form of a metal hydroxide; and b) a filtration step in which the precipitate formed in the precipitation step is removed by filtration. silica and processing method of the slag for magnesia extract characterized by including Mukoto and.
前記スラグの加工は、ａ）篩を用いて前記スラグを、０．１〜０．９９ｍｍサイズで構成された第１グループ粒子と、１．０〜７．０ｍｍサイズで構成された第２グループ粒子とに分類する工程と、ｂ）前記第２グループ粒子を選別して１００〜３００μｍサイズのパウダーに粉砕する工程とを含むことを特徴とする請求項１に記載のシリカ及びマグネシア抽出のためのスラグの処理方法。 In the acid treatment step, the slag is processed into a powder and then reacted with the hydrochloric acid solution.
The processing of the slag includes: a) a first group particle composed of 0.1 to 0.99 mm size and a second group particle composed of 1.0 to 7.0 mm size using a sieve. 2. The slag for silica and magnesia extraction according to claim 1, comprising: a step of classifying the second group particles into a powder having a size of 100 to 300 μm. Processing method.
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| KR101718440B1 (en) * | 2015-10-15 | 2017-03-21 | 박민규 | Method for preparing magnesium compound from Fe-Ni slag |
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| CN111060417B (en) * | 2019-11-25 | 2023-03-21 | 中国石油化工股份有限公司 | Quantitative analysis method for gasified slag mineral phase |
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| CN112322903B (en) * | 2020-10-26 | 2022-07-19 | 西安建筑科技大学 | Method for reducing magnesium oxide in nickel-iron slag and method for preparing mineral wool |
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