TWI856221B - Method for processing waste sulfuric acid and basic oxygen furnace slag - Google Patents
Method for processing waste sulfuric acid and basic oxygen furnace slag Download PDFInfo
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims abstract description 132
- 239000002699 waste material Substances 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 26
- 239000002893 slag Substances 0.000 title abstract description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title abstract description 9
- 239000001301 oxygen Substances 0.000 title abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 title abstract description 9
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims abstract description 142
- 239000013078 crystal Substances 0.000 claims abstract description 41
- 239000007788 liquid Substances 0.000 claims abstract description 35
- 239000012265 solid product Substances 0.000 claims abstract description 28
- 239000000292 calcium oxide Substances 0.000 claims abstract description 19
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 19
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000926 separation method Methods 0.000 claims abstract description 16
- 239000007787 solid Substances 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 238000004933 hydrothermal crystal growth Methods 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 239000004575 stone Substances 0.000 claims description 32
- 239000012263 liquid product Substances 0.000 claims description 27
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 24
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 20
- 229910000358 iron sulfate Inorganic materials 0.000 claims description 18
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 11
- 238000000746 purification Methods 0.000 claims description 8
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 6
- 239000000920 calcium hydroxide Substances 0.000 claims description 6
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- 239000011575 calcium Substances 0.000 abstract description 18
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 17
- 229910052791 calcium Inorganic materials 0.000 abstract description 17
- 239000000047 product Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 30
- 238000004458 analytical method Methods 0.000 description 15
- 239000006227 byproduct Substances 0.000 description 15
- 239000011248 coating agent Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 239000000945 filler Substances 0.000 description 8
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 239000003973 paint Substances 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 4
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 4
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 101001121408 Homo sapiens L-amino-acid oxidase Proteins 0.000 description 2
- 102100026388 L-amino-acid oxidase Human genes 0.000 description 2
- 235000019738 Limestone Nutrition 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000010426 asphalt Substances 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000008394 flocculating agent Substances 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 239000006028 limestone Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 150000005837 radical ions Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 208000005156 Dehydration Diseases 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 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
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 description 1
- 229960002218 sodium chlorite Drugs 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
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- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
Description
本揭露是有關於一種硫酸廢液與含鈣副產物的處理方法，且特別是有關於一種硫酸廢液與轉爐石渣的處理方法。 The present disclosure relates to a method for treating waste sulfuric acid liquor and calcium-containing byproducts, and in particular to a method for treating waste sulfuric acid liquor and converter slag.
硫酸是工業上一種重要的化學品，其用途相當廣泛，如製造肥料、非鹼性清潔劑、護膚品、以及油漆添加劑與炸藥等。近年來，硫酸也被運用於晶圓製造業。舉例而言，硫酸可被運用於晶圓清洗。由於晶圓製造業的蓬勃發展，硫酸廢液的產量變得相當可觀，硫酸廢液的處理方法也成為相關領域的重要課題之一。 Sulfuric acid is an important chemical in industry, and its uses are quite wide, such as making fertilizers, non-alkaline cleaners, skin care products, paint additives and explosives. In recent years, sulfuric acid has also been used in the wafer manufacturing industry. For example, sulfuric acid can be used for wafer cleaning. Due to the booming wafer manufacturing industry, the output of sulfuric acid waste liquid has become considerable, and the treatment method of sulfuric acid waste liquid has also become one of the important topics in related fields.
另一方面，含鈣副產物例如是利用轉爐冶煉法煉鋼所排出的轉爐石(basic oxygen furnace slag)。轉爐石的主要成分為氧化鈣與氧化鐵，且可包括其他例如是矽、鎂、鋁、錳等元素的氧化物。轉爐石經加工後可作為水泥、塗料、瀝青、油漆等的填料。然而，作為填料的轉爐石具有易吸水膨脹而造成破損、粉化等問題，且機械性質與耐高溫性也有待改善。 On the other hand, calcium-containing byproducts include basic oxygen furnace slag, which is discharged from steel smelting using the converter smelting method. The main components of basic oxygen furnace slag are calcium oxide and iron oxide, and may include oxides of other elements such as silicon, magnesium, aluminum, and manganese. After processing, basic oxygen furnace slag can be used as a filler for cement, paint, asphalt, and paint. However, basic oxygen furnace slag as a filler has the problem of easy water absorption and expansion, resulting in damage and pulverization, and its mechanical properties and high temperature resistance also need to be improved.
本揭露提供一種硫酸廢液與含鈣副產物的處理方法，其能夠一併處理硫酸廢液與含鈣副產物，並能夠產出具有強化機械性質與良好高溫特性的含鈣填料。 The present disclosure provides a method for treating waste sulfuric acid solution and calcium-containing byproducts, which can simultaneously treat waste sulfuric acid solution and calcium-containing byproducts and produce calcium-containing fillers with enhanced mechanical properties and good high-temperature properties.
根據本揭露的一些實施例，硫酸廢液與含鈣副產物的處理方法包括：進行混合步驟，以混合硫酸廢液與含鈣副產物，其中所述硫酸廢液包括硫酸，所述含鈣副產物包括氧化鈣，且所述硫酸與所述氧化鈣在所述混合步驟期間反應生成硫酸鈣固體；對所述硫酸廢液與所述含鈣副產物的混合液進行固液分離步驟，以分離出包括所述硫酸鈣固體的第一固態產物；以及進行水熱法長晶步驟，而藉由水熱法使所述硫酸鈣固體進行長晶，以形成硫酸鈣晶鬚。 According to some embodiments of the present disclosure, the method for treating waste sulfuric acid solution and calcium-containing byproducts includes: performing a mixing step to mix waste sulfuric acid solution and calcium-containing byproducts, wherein the waste sulfuric acid solution includes sulfuric acid, the calcium-containing byproducts include calcium oxide, and the sulfuric acid and the calcium oxide react during the mixing step to generate solid calcium sulfate; performing a solid-liquid separation step on the mixed solution of the waste sulfuric acid solution and the calcium-containing byproducts to separate a first solid product including the solid calcium sulfate; and performing a hydrothermal crystal growth step to grow the solid calcium sulfate by hydrothermal method to form calcium sulfate whiskers.
在一些實施例中，所述硫酸廢液更包括過氧化氫。 In some embodiments, the sulfuric acid waste liquid further includes hydrogen peroxide.
在一些實施例中，所述氧化鈣在所述混合步驟期間與所述過氧化氫反應生成氫氧化鈣，且所述氫氧化鈣在所述混合步驟期間與所述硫酸反應生成所述硫酸鈣固體。 In some embodiments, the calcium oxide reacts with the hydrogen peroxide during the mixing step to form calcium hydroxide, and the calcium hydroxide reacts with the sulfuric acid during the mixing step to form the calcium sulfate solid.
在一些實施例中，所述含鈣副產物更包括氧化鐵。 In some embodiments, the calcium-containing byproduct further comprises iron oxide.
在一些實施例中，所述氧化鐵在所述混合步驟期間與所述硫酸反應生成硫酸鐵溶液。 In some embodiments, the iron oxide reacts with the sulfuric acid during the mixing step to form an iron sulfate solution.
在一些實施例中，所述固液分離步驟更分離出包括所述硫酸鐵溶液的第一液態產物。 In some embodiments, the solid-liquid separation step further separates a first liquid product including the ferric sulfate solution.
在一些實施例中，在所述固液分離步驟之後且在所述水 熱法長晶步驟之前，更包括：進行水洗純化步驟，以對所述第一固態產物進行水洗。 In some embodiments, after the solid-liquid separation step and before the hydrothermal crystal growth step, it further includes: performing a water washing purification step to wash the first solid product with water.
在一些實施例中，在所述水洗純化步驟之後且在所述水熱法長晶步驟之前，更包括：進行額外固液分離步驟，以將所述水洗純化步驟得到的混合液分離出包括所述硫酸鈣固體的第二固態產物以及包括水的第二液態產物。 In some embodiments, after the water washing and purification step and before the hydrothermal crystal growth step, it further includes: performing an additional solid-liquid separation step to separate the mixed liquid obtained in the water washing and purification step into a second solid product including the calcium sulfate solid and a second liquid product including water.
在一些實施例中，所述第二液態產物更包括硫酸鐵溶液。 In some embodiments, the second liquid product further comprises a ferric sulfate solution.
在一些實施例中，更包括：對所述第一液態產物與所述第二液態產物的混合液進行提濃步驟，以至少部分地去除包括所述第一液態產物與所述第二液態產物的所述混合液中的水。 In some embodiments, the method further includes: performing a concentration step on the mixture of the first liquid product and the second liquid product to at least partially remove water from the mixture of the first liquid product and the second liquid product.
基於上述，本揭露的硫酸廢液與轉爐石的處理流程能夠一併處理硫酸廢液與轉爐石。不但如此，更可將硫酸廢液與轉爐石轉變為具有高經濟價值的塗層填料以及工業廢水的絮凝劑。特別來說，此塗層填料包括硫酸鈣晶鬚。相較於含有氧化鈣的轉爐石，硫酸鈣晶鬚不易與水汽反應，故不易產生吸水膨脹而造成破損、粉化等問題。因此，可延長塗層的使用壽命。再者，基於硫酸鈣晶鬚錯綜排列而形成網狀結構，可大幅加強塗層的機械強度。除此之外，相較於顆粒狀的硫酸鈣晶體，硫酸鈣晶鬚的一維形狀使得其比表面積(specific surface area)大幅降低。因此，相較於顆粒狀的硫酸鈣晶體，硫酸鈣晶鬚可具有更高的熔點。據此，硫酸鈣晶鬚可具有較佳的熱穩定性以及防火性。 Based on the above, the treatment process of sulfuric acid waste liquid and converter stone disclosed in the present invention can treat sulfuric acid waste liquid and converter stone at the same time. In addition, sulfuric acid waste liquid and converter stone can be transformed into coating fillers with high economic value and flocculants for industrial wastewater. In particular, this coating filler includes calcium sulfate crystal whiskers. Compared with converter stone containing calcium oxide, calcium sulfate crystal whiskers are not easy to react with water vapor, so they are not easy to produce water absorption and expansion to cause damage, powdering and other problems. Therefore, the service life of the coating can be extended. Furthermore, based on the criss-cross arrangement of calcium sulfate crystal whiskers to form a network structure, the mechanical strength of the coating can be greatly enhanced. In addition, the one-dimensional shape of calcium sulfate whiskers significantly reduces their specific surface area compared to granular calcium sulfate crystals. Therefore, calcium sulfate whiskers can have a higher melting point than granular calcium sulfate crystals. Accordingly, calcium sulfate whiskers can have better thermal stability and fire resistance.
AQ:液態產物 AQ: Liquid product
SL:固態產物 SL: Solid product
S100、S102、S104、S106、S108、S110、S112、S114、S116、S118:步驟 S100, S102, S104, S106, S108, S110, S112, S114, S116, S118: Steps
WH:硫酸鈣晶鬚 WH: Calcium sulfate crystal whiskers
圖1是依照本揭露一些實施例的硫酸廢液與含鈣副產物的處理方法的流程圖。 FIG1 is a flow chart of a method for treating waste sulfuric acid solution and calcium-containing byproducts according to some embodiments of the present disclosure.
圖2示出硫酸鈣晶鬚的掃描式電子顯微鏡影像。 Figure 2 shows a scanning electron microscope image of calcium sulfate crystal whiskers.
圖1是依照本揭露一些實施例的硫酸廢液與含鈣副產物的處理方法的流程圖。以下將以轉爐石作為含鈣副產物的範例來說明上述處理方法的各個步驟。 FIG1 is a flow chart of a method for treating waste sulfuric acid solution and calcium-containing byproducts according to some embodiments of the present disclosure. The following will use converter stone as an example of calcium-containing byproducts to illustrate the various steps of the above treatment method.
請參照圖1，進行步驟S100，以提供轉爐石。轉爐石為生產鋼鐵之鐵礦原料所含有的黏土雜質與石灰石助熔劑在高溫熔爐中反應所產生的熔渣。具體而言，一般煉鋼製程所產出的爐石可包括高爐石(blast furnace slag)與轉爐石(basic oxygen furnace slag)。由高爐產生的鐵水運送至轉爐，以進行轉爐吹煉。藉由轉爐吹煉形成鋼液時，須加入石灰石等助熔劑，以去除鐵水中的雜質。此過程中的熱熔渣經冷卻後形成轉爐石。轉爐石的主要成分為氧化鈣與氧化鐵，且可包括其他例如是矽、鎂、鋁、錳等元素的氧化物。在一些實施例中，可先將塊狀的轉爐石敲碎至顆粒狀，之後進行粗篩與研磨，而得到轉爐石粉。在其他實施例中，也可使用顆粒狀的轉爐石進行後續處理步驟。 Please refer to FIG. 1 and perform step S100 to provide converter slag. Converter slag is slag produced by the reaction of clay impurities contained in the iron ore raw material for producing steel and limestone flux in a high-temperature melting furnace. Specifically, the slag produced by the general steelmaking process may include blast furnace slag and basic oxygen furnace slag. The molten iron produced by the blast furnace is transported to the converter for converter blowing. When the molten steel is formed by converter blowing, flux such as limestone must be added to remove impurities in the molten iron. The hot slag in this process is cooled to form converter slag. The main components of converter stone are calcium oxide and iron oxide, and may include oxides of other elements such as silicon, magnesium, aluminum, manganese, etc. In some embodiments, the block converter stone may be first broken into granules, and then coarsely screened and ground to obtain converter stone powder. In other embodiments, the granular converter stone may also be used for subsequent processing steps.
進行步驟S102，以提供硫酸廢液。在一些實施例中，硫 酸廢液為晶圓製造過程中所產生的硫酸廢液。在晶圓製造過程中，硫酸可被運用於晶圓清洗。在此些實施例中，硫酸廢液含有硫酸以及過氧化氫，且可能包括微量的其他金屬與酸根離子。舉例而言，硫酸廢液中的硫酸佔約50wt%；過氧化氫佔約4wt%；其他金屬與酸根離子約佔0.1wt%。 Step S102 is performed to provide sulfuric acid waste liquid. In some embodiments, the sulfuric acid waste liquid is sulfuric acid waste liquid generated in the wafer manufacturing process. In the wafer manufacturing process, sulfuric acid can be used for wafer cleaning. In these embodiments, the sulfuric acid waste liquid contains sulfuric acid and hydrogen peroxide, and may include trace amounts of other metals and acid radical ions. For example, sulfuric acid in the sulfuric acid waste liquid accounts for about 50wt%; hydrogen peroxide accounts for about 4wt%; and other metals and acid radical ions account for about 0.1wt%.
隨後，進行步驟S104，以混合轉爐石與硫酸廢液。在一些實施例中，可在常溫常壓下於攪拌器中進行攪拌。如式(1)所示，硫酸廢液中的硫酸會與轉爐石中的氧化鈣反應，而生成硫酸鈣與水。硫酸鈣在常溫常壓下幾乎不溶於水。舉例而言，在攝氏20度、1大氣壓下，硫酸鈣在水中的溶解度約為0.24g/100mL。 Then, step S104 is performed to mix the converter stone and the waste sulfuric acid solution. In some embodiments, the mixing can be performed in a stirrer at room temperature and pressure. As shown in formula (1), the sulfuric acid in the waste sulfuric acid solution reacts with the calcium oxide in the converter stone to generate calcium sulfate and water. Calcium sulfate is almost insoluble in water at room temperature and pressure. For example, at 20 degrees Celsius and 1 atmosphere, the solubility of calcium sulfate in water is about 0.24g/100mL.
CaO(s)+H2SO4(aq)→CaSO4(s)+H2O(l) (1) CaO (s) +H 2 SO 4(aq) →CaSO 4(s) +H 2 O (l) (1)
如式(2)所示，在硫酸廢液中含有過氧化氫的實施例中，硫酸廢液中的過氧化氫可能會與轉爐石中的氧化鈣反應而生成固態的氫氧化鈣。如式(3)所示，氫氧化鈣可與硫酸反應生成硫酸鈣與水。在此些實施例中，基於過氧化氫作為強氧化劑的作用，可顯著地加速由氧化鈣轉變為硫酸鈣的反應速度。 As shown in formula (2), in the embodiment where the sulfuric acid waste liquid contains hydrogen peroxide, the hydrogen peroxide in the sulfuric acid waste liquid may react with the calcium oxide in the converter stone to generate solid calcium hydroxide. As shown in formula (3), calcium hydroxide may react with sulfuric acid to generate calcium sulfate and water. In these embodiments, based on the role of hydrogen peroxide as a strong oxidant, the reaction rate of calcium oxide to calcium sulfate can be significantly accelerated.
2CaO(s)+2H2O2(aq)→2Ca(OH)2(s)+O2(g) (2) 2CaO (s) +2H 2 O 2(aq) →2Ca(OH) 2(s) +O 2(g) (2)
Ca(OH)2(s)+H2SO4(aq)→CaSO4(s)+2H2O(l) (3) Ca(OH) 2(s) +H 2 SO 4(aq) →CaSO 4(s) +2H 2 O (l) (3)
另一方面，如式(4)所示，硫酸廢液中的硫酸會與轉爐石中的氧化鐵反應，而生成硫酸鐵與水。在常溫常壓下，硫酸鐵可溶於水，故以水溶液的型態作為反應生成物。 On the other hand, as shown in formula (4), sulfuric acid in the sulfuric acid waste liquid reacts with iron oxide in the converter stone to generate iron sulfate and water. At room temperature and pressure, iron sulfate is soluble in water, so the reaction product is in the form of an aqueous solution.
Fe2O3(s)+3H2SO4(aq)→Fe2(SO4)3(aq)+3H2O(l) (4) Fe 2 O 3(s) +3H 2 SO 4(aq) →Fe 2 (SO 4 ) 3(aq) +3H 2 O (l) (4)
在硫酸廢液中含有過氧化氫的實施例中，硫酸廢液中的過氧化氫會加速與轉爐石中的氧化鐵之反應，而生成溶於水的硫酸鐵。在此些實施例中，基於過氧化氫作為強氧化劑的作用，可顯著地加速由氧化鐵轉變為硫酸鐵的反應速度。 In the embodiments where the waste sulfuric acid solution contains hydrogen peroxide, the hydrogen peroxide in the waste sulfuric acid solution will accelerate the reaction with the iron oxide in the converter stone to generate water-soluble iron sulfate. In these embodiments, based on the role of hydrogen peroxide as a strong oxidant, the reaction rate of converting iron oxide into iron sulfate can be significantly accelerated.
進行步驟S106，以對混合液進行固液分離。前一步驟所形成的包括硫酸鈣固體與硫酸鐵溶液的混合液可在此步驟中進行固液分離。在一些實施例中，藉由離心分離法、板框過濾法或其類似者對上述的混合液進行固液分離。所分離出的固態產物SL可包括硫酸鈣，而所分離出的液態產物AQ可包括硫酸鐵溶液。在一些實施例中，分離出的固態產物SL更可包括轉爐石中未與硫酸反應的固態雜質，例如是包括矽、鋁、鎂、錳或其氧化物。 Step S106 is performed to perform solid-liquid separation on the mixed solution. The mixed solution including solid calcium sulfate and ferric sulfate solution formed in the previous step can be subjected to solid-liquid separation in this step. In some embodiments, the mixed solution is subjected to solid-liquid separation by centrifugal separation, plate and frame filtration or the like. The separated solid product SL may include calcium sulfate, and the separated liquid product AQ may include ferric sulfate solution. In some embodiments, the separated solid product SL may further include solid impurities in the converter stone that have not reacted with sulfuric acid, such as silicon, aluminum, magnesium, manganese or their oxides.
進行步驟S108，以對於前一步驟所分離出的固態產物SL進行水洗純化。如上所述，前一步驟(亦即步驟S106)所分離出的固態產物SL主要包括硫酸鈣。然而，此些固態產物SL更可能附著有一些硫酸鐵溶液。在當前步驟(亦即步驟S108)中，以水洗製程將可能附著於這些固態產物SL上的硫酸鐵溶液洗除。如此一來，可純化此些主要包括硫酸鈣的固態產物SL。 Step S108 is performed to purify the solid product SL separated in the previous step by water washing. As described above, the solid product SL separated in the previous step (i.e., step S106) mainly includes calcium sulfate. However, these solid products SL are more likely to be attached with some iron sulfate solution. In the current step (i.e., step S108), the iron sulfate solution that may be attached to these solid products SL is washed away by a water washing process. In this way, these solid products SL mainly including calcium sulfate can be purified.
進行步驟S110，以再次進行固液分離。前一步驟(亦即步驟S108)將水與固態產物SL混合，以使可能附著於固態產物SL上的硫酸鐵溶液溶於水中。在當前步驟中(亦即步驟S110)，將可能含有硫酸鐵的水溶液與前述的固態產物SL分離，以得到液態產物AQ與固態產物SL。需注意的是，此步驟(亦即步驟S110) 分離出的液態產物AQ的硫酸鐵濃度可能低於步驟S106所分離出的液態產物AQ的硫酸鐵濃度。然而，以簡潔起見，兩步驟所得的液態產物均標示為液態產物AQ。在一些實施例中，藉由離心分離法、板框過濾法或其類似者進行固液分離處理。 Step S110 is performed to perform solid-liquid separation again. In the previous step (i.e., step S108), water is mixed with the solid product SL so that the iron sulfate solution that may be attached to the solid product SL is dissolved in water. In the current step (i.e., step S110), the aqueous solution that may contain iron sulfate is separated from the aforementioned solid product SL to obtain a liquid product AQ and a solid product SL. It should be noted that the iron sulfate concentration of the liquid product AQ separated in this step (i.e., step S110) may be lower than the iron sulfate concentration of the liquid product AQ separated in step S106. However, for the sake of simplicity, the liquid products obtained in both steps are labeled as liquid product AQ. In some embodiments, the solid-liquid separation process is performed by centrifugation, plate and frame filtration, or the like.
選擇性地進行步驟S112，以對於經水洗純化的固態產物SL進行材料分析。材料分析可包括成分分析以及結晶相分析。在一些實施例中，成分分析的方法包括X光螢光(X-ray fluorescence，XRF)分析以及感應耦合電漿質譜儀(inductively coupled plasma optical emission spectrometry，ICP-OES)分析。藉由進行成分分析，可確認附著於這些固態產物SL上的包含硫酸鐵的溶液是否低於預設標準。若是，則可對這些固態產物SL進行後續步驟。若否，則可再次進行步驟S108的水洗純化處理以及步驟S110的固液分離處理。另一方面，結晶相分析可例如是X光繞射(X-ray diffraction，XRD)分析。藉由進行此結晶相分析，可取得上述固態產物SL進行後續的長晶處理之前的起始結晶狀態。 Step S112 is selectively performed to perform material analysis on the solid product SL that has been purified by water washing. The material analysis may include component analysis and crystal phase analysis. In some embodiments, the component analysis method includes X-ray fluorescence (XRF) analysis and inductively coupled plasma optical emission spectrometry (ICP-OES) analysis. By performing component analysis, it can be confirmed whether the solution containing iron sulfate attached to these solid products SL is lower than the preset standard. If so, subsequent steps can be performed on these solid products SL. If not, the water washing purification treatment of step S108 and the solid-liquid separation treatment of step S110 can be performed again. On the other hand, the crystal phase analysis can be, for example, X-ray diffraction (XRD) analysis. By performing this crystal phase analysis, the initial crystal state of the solid product SL before the subsequent crystal growth process can be obtained.
進行步驟S114，以使經水洗純化的固態產物SL進行長晶。具體而言，固態產物SL中原本可能是顆粒狀或塊狀的硫酸鈣可在當前步驟中成長為硫酸鈣晶鬚WH。在一些實施例中，以水熱法進行硫酸鈣的長晶處理。在此些實施例中，上述的固態產物SL經加水後輸入至蒸汽反應釜中，以使固態產物SL中的硫酸鈣在高溫高壓環境下進行長晶。舉例而言，長晶條件可控制在約攝氏90度至約攝氏130度的範圍中，而長晶的壓力可控制在約0.1MPa 至約0.3MPa的範圍中。在高溫高壓環境下，可迫使硫酸鈣溶於水，且結晶析出為晶體。除此之外，可將助長劑與催化劑加入蒸汽反應釜中。助長劑在水中可溶解出離子，且因此會基於同離子效應而提高硫酸鈣在水中的溶解度。再者，此些離子可能會附著於硫酸鈣晶核周圍，進而增大晶核在特定方向上的表面能，而使硫酸鈣晶體能夠單向生長而形成晶鬚。舉例而言，助長劑可包括硫酸鈉溶液與氧化鈣溶液，且更可包括氯化鎂溶液、氯化銨溶液、硫酸銅溶液或硫酸錳溶液。另一方面，催化劑可促進硫酸根離子與鈣離子在硫酸鈣晶核上結晶。舉例而言，催化劑可包括亞氯酸鈉溶液或過錳酸鉀溶液。再者，蒸汽反應釜更可連通於加酸管路。加酸管路經配置以將酸性溶液加入至蒸汽反應釜中，以調整蒸汽反應釜中的pH值。在一些實施例中，蒸汽反應釜中的pH值經控制在約3至4的範圍中。在形成硫酸鈣晶鬚WH之後，可進行脫水處理，而將硫酸鈣晶鬚WH分離出來。 Step S114 is performed to grow the solid product SL after washing and purification. Specifically, the calcium sulfate in the solid product SL, which may be originally in the form of granules or blocks, can grow into calcium sulfate whiskers WH in the current step. In some embodiments, the calcium sulfate growth treatment is performed by a hydrothermal method. In these embodiments, the solid product SL is added with water and then input into a steam reactor so that the calcium sulfate in the solid product SL grows in a high temperature and high pressure environment. For example, the crystal growth conditions can be controlled in the range of about 90 degrees Celsius to about 130 degrees Celsius, and the crystal growth pressure can be controlled in the range of about 0.1MPa to about 0.3MPa. In a high temperature and high pressure environment, calcium sulfate can be forced to dissolve in water and crystallize into crystals. In addition, a promoter and a catalyst can be added to the steam reactor. The promoter can dissolve ions in water, and thus increase the solubility of calcium sulfate in water based on the same ion effect. Furthermore, these ions may attach to the surrounding of the calcium sulfate crystal nucleus, thereby increasing the surface energy of the crystal nucleus in a specific direction, so that the calcium sulfate crystal can grow unidirectionally to form crystal whiskers. For example, the promoter may include a sodium sulfate solution and a calcium oxide solution, and may further include a magnesium chloride solution, an ammonium chloride solution, a copper sulfate solution or a manganese sulfate solution. On the other hand, the catalyst can promote the crystallization of sulfate ions and calcium ions on the calcium sulfate crystal nucleus. For example, the catalyst may include a sodium chlorite solution or a potassium permanganate solution. Furthermore, the steam reactor may be connected to an acid adding pipeline. The acid adding pipeline is configured to add an acidic solution to the steam reactor to adjust the pH value in the steam reactor. In some embodiments, the pH value in the steam reactor is controlled in the range of about 3 to 4. After the calcium sulfate crystal whiskers WH are formed, a dehydration treatment may be performed to separate the calcium sulfate crystal whiskers WH.
圖2示出硫酸鈣晶鬚WH的掃描式電子顯微鏡影像。 Figure 2 shows a scanning electron microscope image of calcium sulfate crystal whiskers WH.
請參照圖2，硫酸鈣晶體大致上朝單一方向生長，而形成硫酸鈣晶鬚WH。此外，多條沿不同方向生長的硫酸鈣晶鬚WH可錯綜堆疊而形成網狀結構。在一些實施例中，硫酸鈣晶鬚WH的直徑約1μm至2μm，長度可達到約100mm。相似於轉爐石的應用，硫酸鈣晶鬚WH也可應用於水泥、塗料、瀝青、油漆等的填料。相較於含有氧化鈣的轉爐石，硫酸鈣不易與水汽反應，故不易產生吸水膨脹而造成破損、粉化等問題。因此，可延長塗層 的使用壽命。再者，基於硫酸鈣晶鬚WH錯綜排列而形成網狀結構，可大幅加強塗層的機械強度。除此之外，相較於顆粒狀的硫酸鈣晶體，硫酸鈣晶鬚WH的一維形狀使得其比表面積(specific surface area)大幅降低。因此，相較於顆粒狀的硫酸鈣晶體，硫酸鈣晶鬚WH可具有更高的熔點。據此，硫酸鈣晶鬚可具有較佳的熱穩定性以及防火性。舉例而言，顆粒狀的硫酸鈣晶體的熔點約為攝氏1200度，而硫酸鈣晶鬚WH的熔點可達約攝氏1450度。此外，作為測試，硫酸鈣晶鬚WH在攝氏1800度下兩小時僅失重0.75%。 Please refer to Figure 2. Calcium sulfate crystals generally grow in a single direction to form calcium sulfate whiskers WH. In addition, multiple calcium sulfate whiskers WH growing in different directions can be stacked to form a network structure. In some embodiments, the diameter of the calcium sulfate whiskers WH is about 1μm to 2μm, and the length can reach about 100mm. Similar to the application of converter stone, calcium sulfate whiskers WH can also be used as fillers for cement, paint, asphalt, paint, etc. Compared with converter stone containing calcium oxide, calcium sulfate is not easy to react with water vapor, so it is not easy to produce water absorption and expansion to cause damage, powdering, etc. Therefore, the service life of the coating can be extended. Furthermore, the mechanical strength of the coating can be greatly enhanced based on the crisscross arrangement of the calcium sulfate crystal whiskers WH to form a network structure. In addition, compared with the granular calcium sulfate crystals, the one-dimensional shape of the calcium sulfate crystal whiskers WH greatly reduces its specific surface area. Therefore, compared with the granular calcium sulfate crystals, the calcium sulfate crystal whiskers WH can have a higher melting point. Accordingly, the calcium sulfate crystal whiskers can have better thermal stability and fire resistance. For example, the melting point of the granular calcium sulfate crystals is about 1200 degrees Celsius, while the melting point of the calcium sulfate crystal whiskers WH can reach about 1450 degrees Celsius. In addition, as a test, calcium sulfate whisker WH lost only 0.75% of its weight in two hours at 1800 degrees Celsius.
另一方面，進行步驟S116，以對於步驟S106與步驟S110的固液分離處理所得到的液態產物AQ進行提濃處理。在當前步驟(亦即步驟S116)中，去除液態產物AQ中的水，以提高硫酸鐵的濃度。在一些實施例中，藉由蒸發器或多效蒸發管來進行提濃處理(亦即除水處理)。經提濃的液態產物AQ具有相對高濃度的硫酸鐵溶液，且可作為處理工業鹼性廢水的絮凝劑。 On the other hand, step S116 is performed to concentrate the liquid product AQ obtained by the solid-liquid separation treatment of step S106 and step S110. In the current step (i.e., step S116), water in the liquid product AQ is removed to increase the concentration of iron sulfate. In some embodiments, the concentration treatment (i.e., water removal treatment) is performed by an evaporator or a multi-effect evaporation tube. The concentrated liquid product AQ has a relatively high concentration of iron sulfate solution and can be used as a flocculant for treating industrial alkaline wastewater.
在一些實施例中，在進行步驟S116之前，可選擇性地進行步驟S118，以對即將進行提濃處理的液態產物AQ進行檢測。在一些實施例中，檢測可包括pH值檢測與成分分析。pH值檢測可能是為了確認液態產物AQ是否符合絮凝劑的需求。另外，成分分析可用於檢測液態產物AQ中的硫酸鐵的濃度。在一些實施例中，成分分析的方法包括感應耦合電漿質譜儀(inductively coupled plasma optical emission spectrometry，ICP-OES)分析。 In some embodiments, before performing step S116, step S118 may be optionally performed to detect the liquid product AQ to be concentrated. In some embodiments, the detection may include pH detection and component analysis. pH detection may be to confirm whether the liquid product AQ meets the requirements of the flocculant. In addition, component analysis can be used to detect the concentration of iron sulfate in the liquid product AQ. In some embodiments, the method of component analysis includes inductively coupled plasma optical emission spectrometry (ICP-OES) analysis.
至此，已完成根據一些實施例的硫酸廢液與轉爐石的處理流程，其能夠一併處理硫酸廢液與轉爐石。不但如此，更可將硫酸廢液與轉爐石轉變為具有高經濟價值的塗層填料以及工業廢水的絮凝劑。特別來說，此塗層填料包括硫酸鈣晶鬚。相較於含有氧化鈣的轉爐石，硫酸鈣晶鬚不易與水汽反應，故不易產生吸水膨脹而造成破損、粉化等問題。因此，可延長塗層的使用壽命。再者，基於硫酸鈣晶鬚錯綜排列而形成網狀結構，可大幅加強塗層的機械強度。除此之外，相較於顆粒狀的硫酸鈣晶體，硫酸鈣晶鬚的一維形狀使得其比表面積(specific surface area)大幅降低。因此，相較於顆粒狀的硫酸鈣晶體，硫酸鈣晶鬚可具有更高的熔點。據此，硫酸鈣晶鬚可具有較佳的熱穩定性以及防火性。 At this point, the treatment process of sulfuric acid waste liquid and converter stone according to some embodiments has been completed, which can treat sulfuric acid waste liquid and converter stone at the same time. In addition, sulfuric acid waste liquid and converter stone can be transformed into coating fillers with high economic value and flocculants for industrial wastewater. In particular, this coating filler includes calcium sulfate crystal whiskers. Compared with converter stone containing calcium oxide, calcium sulfate crystal whiskers are not easy to react with water vapor, so it is not easy to produce water absorption and expansion to cause damage, powdering and other problems. Therefore, the service life of the coating can be extended. Furthermore, based on the mesh structure formed by the staggered arrangement of calcium sulfate crystal whiskers, the mechanical strength of the coating can be greatly enhanced. In addition, the one-dimensional shape of calcium sulfate whiskers significantly reduces their specific surface area compared to granular calcium sulfate crystals. Therefore, calcium sulfate whiskers can have a higher melting point than granular calcium sulfate crystals. Accordingly, calcium sulfate whiskers can have better thermal stability and fire resistance.
在其他含鈣副產物並非為轉爐石的實施例中，含鈣副產物可能包括氧化鈣而並未包括氧化鐵。在此些實施例中，可省略與氧化鐵有關的步驟(例如是包括步驟S116與步驟S118)，或者對應於含鈣副產物的原料而將上述步驟更改為其他步驟。 In other embodiments where the calcium-containing byproduct is not blast furnace stone, the calcium-containing byproduct may include calcium oxide but not iron oxide. In these embodiments, the steps related to iron oxide (such as including step S116 and step S118) can be omitted, or the above steps can be changed to other steps corresponding to the raw materials of the calcium-containing byproduct.
AQ:液態產物 AQ: Liquid product
SL:固態產物 SL: Solid product
S100、S102、S104、S106、S108、S110、S112、S114、S116、S118:步驟 S100, S102, S104, S106, S108, S110, S112, S114, S116, S118: Steps
WH:硫酸鈣晶鬚 WH: Calcium sulfate crystal whiskers
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| TW201835337A (en) * | 2017-03-15 | 2018-10-01 | 日玉盛複合材料股份有限公司 | Method for treatment and regenerate hearthstone |
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