TWI494437B - A method of eliminating free calcium oxide and calcium hydroxide contents in furnace slag - Google Patents
A method of eliminating free calcium oxide and calcium hydroxide contents in furnace slag Download PDFInfo
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- TWI494437B TWI494437B TW102121285A TW102121285A TWI494437B TW I494437 B TWI494437 B TW I494437B TW 102121285 A TW102121285 A TW 102121285A TW 102121285 A TW102121285 A TW 102121285A TW I494437 B TWI494437 B TW I494437B
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- steelmaking
- calcium oxide
- calcium hydroxide
- free calcium
- hearth
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- 238000000034 method Methods 0.000 title claims description 28
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 title claims description 22
- 239000000292 calcium oxide Substances 0.000 title claims description 22
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 title claims description 22
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 title claims description 18
- 239000000920 calcium hydroxide Substances 0.000 title claims description 18
- 229910001861 calcium hydroxide Inorganic materials 0.000 title claims description 18
- 239000002893 slag Substances 0.000 title 1
- 239000004575 stone Substances 0.000 claims description 29
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 26
- 238000009628 steelmaking Methods 0.000 claims description 20
- 239000002351 wastewater Substances 0.000 claims description 18
- 239000001569 carbon dioxide Substances 0.000 claims description 13
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000002002 slurry Substances 0.000 claims description 10
- 238000005097 cold rolling Methods 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims 1
- 239000000463 material Substances 0.000 claims 1
- 239000002245 particle Substances 0.000 claims 1
- 229940087373 calcium oxide Drugs 0.000 description 16
- 235000012255 calcium oxide Nutrition 0.000 description 16
- 238000002347 injection Methods 0.000 description 11
- 239000007924 injection Substances 0.000 description 11
- 238000000227 grinding Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000000926 separation method Methods 0.000 description 7
- 230000006641 stabilisation Effects 0.000 description 4
- 238000011105 stabilization Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 238000003915 air pollution Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 238000001238 wet grinding Methods 0.000 description 2
- 241000283899 Gazella Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000010951 particle size reduction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
Classifications
-
- 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
- Y02P10/10—Reduction of greenhouse gas [GHG] emissions
- Y02P10/122—Reduction of greenhouse gas [GHG] emissions by capturing or storing CO2
-
- 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 Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Processing Of Solid Wastes (AREA)
Description
本發明係關於一種煉鋼爐石中游離態氧化鈣與氫氧化鈣之去除方法；特別關於一種利用冷軋廢水與二氧化碳源，去除煉鋼爐石中游離態氧化鈣與氫氧化鈣含量之方法，以達到爐石安定化。The invention relates to a method for removing free calcium oxide and calcium hydroxide in a steelmaking hearth; in particular, a method for removing free calcium oxide and calcium hydroxide in steelmaking heartstone by using cold rolling wastewater and carbon dioxide source, Reach the stability of the hearthstone.
由於煉鋼爐石(例如：高爐石、轉爐石等)具耐磨、耐高溫、及耐腐蝕等優異之物化特性，因此相當適合取代土木工程中所使用之天然砂石，而深具資源再利用效益；然而，以轉爐石為例，其本身含有部分游離態氧化鈣(Free-CaO)與氫氧化鈣(Ca(OH)2 )等不穩定成份，易造成高鹼度及回脹特性等問題，故若需將轉爐石再利用於土木工程中，多半需先經「安定化」處理，亦即將其中所含之游離態氧化鈣與氫氧化鈣成份去除，否則日後再利用時，易產生路基膨脹破裂或造成地基鬆動等嚴重工安問題。Because steelmaking hearthstone (for example, blast furnace stone, converter stone, etc.) has excellent physicochemical properties such as wear resistance, high temperature resistance and corrosion resistance, it is quite suitable to replace the natural sandstone used in civil engineering, and has deep resources. Benefits; however, taking converter stone as an example, it contains some unstable components such as free calcium oxide (Free-CaO) and calcium hydroxide (Ca(OH) 2 ), which may cause problems such as high alkalinity and swelling property. Therefore, if the converter stone is to be reused in civil engineering, most of it needs to be treated with "safety", and the free calcium oxide and calcium hydroxide contained in it will be removed. Otherwise, it will easily cause roadbed expansion when it is reused in the future. Serious work safety problems such as rupture or loose foundation.
查，2010年11月01日公告之中華民國專利第201038741 A1號中披露之「利用濕磨法進行安定化之轉爐石資源化處理方法」，該發明針對未完全安定化之轉爐石進行濕磨成漿體狀，同時進行安定化步驟，所得知該轉爐石漿體可直接拌合應用於混凝土上；另一方面，現已有商業化運轉之煉鋼爐石，例如：室外自然養生法，高壓蒸氣養生法，常壓蒸氣養生法，HK水淬粒化法，悶罐法，滾筒法，及改質法等，皆可去除游離態氧化 鈣與氫氧化鈣之去除方法。The method of "recycling of the converter stone by the wet grinding method" disclosed in the Republic of China Patent No. 201038741 A1, which is disclosed in the Japanese Patent No. 201038741 A1, which is used for wet grinding of the converter stone which is not completely stabilized. In the form of slurry, and at the same time, the stabilization step is carried out, and it is known that the converter stone slurry can be directly mixed and applied to concrete; on the other hand, there are commercialized steelmaking heartstones, such as: outdoor natural health method, High pressure steam curing method, atmospheric pressure steam curing method, HK water quenching granulation method, stuffing tank method, roller method, and upgrading method can all remove free oxidation Calcium and calcium hydroxide removal methods.
然，以室外自然養生法為例，其係將煉鋼爐石堆置於室外， 利用大氣中之水氣、二氧化碳、及雨水產生水化反應，亦可藉由加水以加速其水化反應；由於此法安定化所需時間相當長，且需相當大面積之處理場地，因此若需大量處理較為困難。However, taking the outdoor natural health method as an example, the system places the steelmaking furnace stone outdoors. The use of moisture, carbon dioxide, and rainwater in the atmosphere to produce hydration reactions can also accelerate the hydration reaction by adding water; since the process takes a long time to stabilize, and requires a relatively large area of treatment, It is more difficult to handle a lot.
然，若以常壓蒸氣養生法為例，其將轉爐石放置在儲坑內後 上面蓋帆布，用噴槍加壓噴射蒸氣至坑內，蒸氣壓力約為1 kg/cm2 ，溫度保持100℃以上，促使轉爐石與蒸氣反應；此法僅將游離態氧化鈣轉化成氫氧化物，而氫氧化物仍處於不穩定狀態。However, if the atmospheric pressure steam regimen is taken as an example, the converter stone is placed in the storage pit and the canvas is covered with a spray gun, and the steam is sprayed into the pit with a spray gun, the vapor pressure is about 1 kg/cm 2 , and the temperature is maintained at 100 ° C. Above, the converter stone is caused to react with the vapor; this method only converts the free calcium oxide into a hydroxide, and the hydroxide is still in an unstable state.
據此，可發現過去煉鋼爐石安定化技術，若係傾倒於廠內或 室外，亦造成揚塵現象產生空污問題；且有些所需時間長，有些占地面積大；游離態氧化鈣轉換成氫氧化物仍處於不穩定狀態；同時，有些尚需消耗額外資源(如水、蒸氣等)或操作於高溫高壓之環境下，製造與維修成本較高，且高壓操作恐產生工安之虞。According to this, it can be found that in the past, the steelmaking furnace stability technology was dumped in the factory or Outdoor, it also causes air pollution to cause air pollution problems; some of them take a long time, some have a large area; the free calcium oxide is still unstable in conversion to hydroxide; at the same time, some need to consume additional resources (such as water, steam) Etc.) Or operating in a high temperature and high pressure environment, manufacturing and maintenance costs are high, and high-voltage operation may cause work safety.
因此，本發明目的係在提一種轉爐石安定化處理方法，並結合使用製程廢水與二氧化碳源，藉以減少廢棄物處理成本與資源使用量，降低環境污染與衝擊。Therefore, the object of the present invention is to provide a converter stone stabilization treatment method, and combine the use of process wastewater and carbon dioxide source, thereby reducing waste disposal cost and resource usage, and reducing environmental pollution and impact.
於是，本研究團隊整合廢棄物處理概念與爐石安定化處理，乃研究出一結合製程產生之冷軋廢水與煉鋼爐石處理技術，並以一二氧化碳源進行安定化反應，參閱圖1，其方法依序包含有爐石研磨步驟(11)，廢水注入步驟(12)，攪拌步驟(13)，二氧化碳源注入反應步驟(1 4)，及分離步驟(15)；其中，藉由該爐石研磨步驟(11)可將未完全安定化之該等轉爐石進行研磨，且與該廢水注入步驟(12)形成液固比為5：1到25：1之泥漿，並進行攪拌步驟(13)，而後再依據所得之該轉爐石漿體一併進行二氧化碳源注入反應步驟(14)，以去除轉爐石中游離態氧化鈣與氫氧化鈣成份。最後，藉由該分離步驟(15)進行液固分離，所得之該安定化轉爐石可做後續資源化用途。Therefore, the research team integrated the waste treatment concept and the furnace stone stabilization treatment, and studied a cold rolling wastewater and steelmaking calculus treatment technology combined with the process, and stabilized with a carbon dioxide source, see Figure 1. The method comprises the gazelle grinding step (11), the wastewater injecting step (12), the stirring step (13), and the carbon dioxide source injecting the reaction step (1). 4), and a separation step (15); wherein the furnace stone grinding step (11) can be used to grind the converter stone which is not completely stabilized, and form a liquid-solid ratio with the wastewater injection step (12) 5:1 to 25:1 slurry, and stirring step (13), and then according to the obtained converter stone slurry, a carbon dioxide source injection reaction step (14) is performed to remove free calcium oxide and hydrogen in the converter stone. Calcium oxide component. Finally, the liquid-solid separation is carried out by the separation step (15), and the stabilized converter stone obtained can be used for subsequent resource utilization.
故，本發明方法除能有效去除轉爐石中游離態氧化鈣與氫氧 化鈣成份外，亦能有效降低水資源使用成本，確實能同時達到資源再利用之環境與經濟效益。Therefore, the method of the present invention can effectively remove free calcium oxide and hydrogen oxygen in the converter stone. In addition to calcium, it can also effectively reduce the cost of water use, and indeed achieve the environmental and economic benefits of resource reuse.
11‧‧‧爐石研磨步驟11‧‧‧ Hearthstone grinding step
12‧‧‧廢水注入步驟12‧‧‧ Wastewater injection step
13‧‧‧攪拌步驟13‧‧‧ stirring step
14‧‧‧二氧化碳源注入反應步驟14‧‧‧ Carbon dioxide source injection reaction step
15‧‧‧分離步驟15‧‧‧Separation steps
第1圖係本發明之流程示意圖。Figure 1 is a schematic flow diagram of the present invention.
第2圖係本發明一實施例，就「未處理轉爐石A」，「處理後對照組B」，及「本發明處理後C」之游離態氧化鈣與氫氧化鈣含量分析結果之示意圖。Fig. 2 is a schematic view showing the results of analysis of the contents of free calcium oxide and calcium hydroxide in "untreated converter stone A", "processed control group B", and "process C after treatment of the present invention" according to an embodiment of the present invention.
請參看第1圖所示，本發明煉鋼爐石中游離態氧化鈣與氫氧化鈣之去除方法，係包括有下述步驟：爐石研磨步驟(11)，廢水注入步驟(12)，攪拌步驟(13)，二氧化碳源注入反應步驟(14)，及分離步驟(15)。Referring to Fig. 1, the method for removing free calcium oxide and calcium hydroxide in the steelmaking hearth of the present invention comprises the following steps: a hearth grinding step (11), a wastewater injection step (12), and a stirring step. (13), the carbon dioxide source is injected into the reaction step (14), and the separation step (15).
1.於該爐石研磨步驟(11)：係通過研磨設備，將煉鋼爐石進行粒徑縮小化處理至250 μm以下。1. In the hearth grinding step (11): the steelmaking hearth is subjected to particle size reduction treatment to 250 μm or less by a grinding device.
2.於該廢水注入步驟(12)：係指透過爐石研磨步驟(11)所得之該粉末，再與冷軋廢水進行混和形成泥漿狀，此泥漿調配比例為液固比5：1到25：1間。2. In the wastewater injection step (12): the powder obtained by the whetstone grinding step (11) is mixed with the cold-rolled wastewater to form a slurry, and the slurry is formulated to have a liquid-solid ratio of 5:1 to 25 : 1 room.
3.於該攪拌步驟(13)：將廢水注入步驟(12)所得之泥漿透過攪拌程序，使煉鋼爐石能均勻分散於冷軋廢水中。3. In the stirring step (13): the slurry obtained by injecting the wastewater into the step (12) is passed through a stirring procedure to uniformly disperse the steelmaking whetstone in the cold rolling waste water.
4.於該二氧化碳源注入反應步驟(14)：係指將含有二氧化碳之氣體來源，與攪拌步驟(13)所得之該均勻漿體，均勻分散地接觸進行反應。4. Injecting the carbon dioxide source into the reaction step (14): means that the source of the gas containing carbon dioxide is uniformly contacted with the uniform slurry obtained in the stirring step (13) to carry out the reaction.
5.於該分離步驟(15)：係指將該二氧化碳源注入反應步驟(14)所得之該反應後煉鋼爐石與冷軋廢水漿體進行固液分離，其中，反應後煉鋼爐石中游離態氧化鈣與氫氧化鈣之含量應已去除。5. In the separating step (15), the step of injecting the carbon dioxide source into the reaction step (14), the steelmaking whetstone and the cold-rolled wastewater slurry are subjected to solid-liquid separation, wherein the steel smelting furnace after the reaction The content of free calcium oxide and calcium hydroxide should be removed.
請參閱第2圖，本發明之一較佳實施例，此實施例係將未處理轉爐石A，根據本發明煉鋼爐石中游離態氧化鈣與氫氧化鈣之去除方法進行安定化處理，該所得之轉爐石成份分析即為本發明處理C；可發現未處理前轉爐石A分別含有游離態氧化鈣約5.08%及氫氧化鈣約1.83%，而經過此方法於常溫常壓下處理，可將其游離態氧化鈣及氫氧化鈣含量降至0%。由此可知，結合製程冷軋廢水進行轉爐石安定化，可有效地將轉爐石中不穩定物質完全消除，達到轉爐石性質改良，並利於其後續資源化再利用用途。Referring to FIG. 2, a preferred embodiment of the present invention, the untreated converter stone A is stabilized according to the method for removing free calcium oxide and calcium hydroxide in the steelmaking hearth according to the present invention. The obtained composition analysis of the converter stone is the treatment C of the present invention; it can be found that the unprocessed converter stone A contains about 5.08% of free calcium oxide and about 1.83% of calcium hydroxide, respectively, and is treated under normal temperature and pressure by this method. The free calcium oxide and calcium hydroxide content is reduced to 0%. It can be seen that the stabilization of the converter stone in combination with the process cold rolling wastewater can effectively eliminate the unstable substances in the converter stone, improve the properties of the converter stone, and facilitate its subsequent resource recycling.
另外，本實施例中對照組B係未進行該廢水注入步驟(12)，而改以自來水注入替代冷軋廢水注入；可發現在與本發明處理C之 相同處理條件下，使用自來水進行安定化處理之對照組B，處理後轉爐石尚含有游離態氧化鈣約0.07%及氫氧化鈣約0.84%(第2圖)。In addition, in the present embodiment, the control group B is not subjected to the wastewater injection step (12), and the tap water injection is replaced by the cold rolling wastewater injection; it can be found in the treatment with the present invention C. Under the same treatment conditions, the control group B was treated with tap water. After the treatment, the converter stone still contained about 0.07% of free calcium oxide and about 0.84% of calcium hydroxide (Fig. 2).
11‧‧‧爐石研磨步驟11‧‧‧ Hearthstone grinding step
12‧‧‧廢水注入步驟12‧‧‧ Wastewater injection step
13‧‧‧攪拌步驟13‧‧‧ stirring step
14‧‧‧二氧化碳源注入反應步驟14‧‧‧ Carbon dioxide source injection reaction step
15‧‧‧分離步驟15‧‧‧Separation steps
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|---|---|---|---|---|
| CN1911829A (en) * | 2006-08-21 | 2007-02-14 | 李春放 | Treatment technology for waste water of steel iron acid cleaning |
| CN101460638A (en) * | 2006-06-14 | 2009-06-17 | Ecomaister株式会社 | A method for stabilizing slag and novel materials produced thereby |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| TW201500554A (en) | 2015-01-01 |
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