TW201708114A - Method for manufacturing gypsum and method for manufacturing cement composition capable of effectively using spent sulfuric acid to manufacture gypsum and to produce cement composition using the gypsum - Google Patents
Method for manufacturing gypsum and method for manufacturing cement composition capable of effectively using spent sulfuric acid to manufacture gypsum and to produce cement composition using the gypsum Download PDFInfo
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- TW201708114A TW201708114A TW105119036A TW105119036A TW201708114A TW 201708114 A TW201708114 A TW 201708114A TW 105119036 A TW105119036 A TW 105119036A TW 105119036 A TW105119036 A TW 105119036A TW 201708114 A TW201708114 A TW 201708114A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/46—Sulfates
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- 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
- C04B11/00—Calcium sulfate cements
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- 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
- C04B11/00—Calcium sulfate cements
- C04B11/26—Calcium sulfate cements strating from chemical gypsum; starting from phosphogypsum or from waste, e.g. purification products of smoke
- C04B11/262—Calcium sulfate cements strating from chemical gypsum; starting from phosphogypsum or from waste, e.g. purification products of smoke waste gypsum other than phosphogypsum
- C04B11/264—Gypsum from the desulfurisation of flue gases
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Abstract
Description
本發明關於一種石膏的製造方法及水泥組合物的製造方法。The present invention relates to a method for producing gypsum and a method for producing a cement composition.
利用鈣化合物對各種工業生產的步驟中所產生的廢硫酸進行中和處理，而製造作為其副產物的石膏的方法廣為人知。但是，關於含有許多氟的廢硫酸，若僅進行中和處理，則石膏中的氟含量也變高，因此作為石膏的利用受到限定。因此，從前為了從含有氟的廢硫酸中獲得氟的含量低的石膏，一面將pH維持成2.5±0.3的範圍，一面使鈣化合物與硫酸進行反應，由此從廢硫酸製造石膏（例如參照專利文獻1）。 [先前技術文獻] [專利文獻]A method of producing a gypsum as a by-product thereof by neutralizing waste sulfuric acid generated in various industrial production steps using a calcium compound is widely known. However, in the case of the waste sulfuric acid containing a large amount of fluorine, if only the neutralization treatment is performed, the fluorine content in the gypsum is also increased, so that the use as gypsum is limited. Therefore, in order to obtain a gypsum having a low fluorine content from the waste sulfuric acid containing fluorine, the calcium compound is reacted with sulfuric acid while maintaining the pH in the range of 2.5 ± 0.3, thereby producing gypsum from waste sulfuric acid (for example, refer to the patent). Document 1). [Prior Technical Literature] [Patent Literature]
[專利文獻1]日本專利特開平9-67118號公報[Patent Document 1] Japanese Patent Laid-Open No. Hei 9-67118
[發明所要解決的問題][Problems to be solved by the invention]
但是，在專利文獻1中記載的從廢硫酸製造石膏的方法中，在為了製造石膏而進行處理後的廢硫酸中也殘留有許多成為石膏的原料的SO4 2- ，而期望廢硫酸的進一步的有效利用。因此，本發明的目的在於提供一種與從前相比，可更有效地利用廢硫酸的石膏的製造方法，及使用通過所述石膏的製造方法所製造的石膏來製造水泥組合物的水泥組合物的製造方法。 [解決問題的技術手段]However, in the method of producing gypsum from waste sulfuric acid described in Patent Document 1, SO 4 2- which is a raw material of gypsum remains in the waste sulfuric acid after the treatment for producing gypsum, and further waste sulfuric acid is desired. Effective use. Accordingly, it is an object of the present invention to provide a method for producing gypsum which can utilize waste sulfuric acid more effectively than before, and a cement composition for producing a cement composition using gypsum produced by the method for producing gypsum. Production method. [Technical means to solve the problem]
本發明者等進行努力研究的結果，發現從使氟的含量低的石膏析出並進行分離去除後的廢硫酸中使氟的含量高的石膏析出，而降低廢硫酸中的氟的含量，並使石膏從降低了氟的含量的所述廢硫酸中進一步析出，由此可更有效地利用廢硫酸中的SO4 2- 作為石膏，從而完成了本發明。即，本發明如下所述。 [1] 一種石膏的製造方法，其特徵在於包括：向含有氟的廢硫酸中添加鈣源，一面將廢硫酸的pH維持成2.0以下一面使石膏析出的步驟（A）；將步驟（A）中所析出的石膏從廢硫酸中分離去除的步驟（B）；向在步驟（B）中分離去除了石膏的廢硫酸中添加鈣源，一面將廢硫酸的pH維持成2.5～4.0一面使石膏析出的步驟（C）；將步驟（C）中所析出的石膏從廢硫酸中分離去除的步驟（D）；向在步驟（D）中分離去除了石膏的廢硫酸中添加鈣源，一面將廢硫酸的pH維持成6.0～8.0一面使石膏析出的步驟（E）；以及將步驟（E）中所析出的石膏從廢硫酸中分離去除的步驟（F）。 [2] 根據所述[1]中記載的石膏的製造方法，其特徵在於：步驟（A）是向含有氟的廢硫酸中添加鈣源，一面將廢硫酸的pH維持成1.5以下一面使石膏析出。 [3] 根據所述[1]或[2]中記載的石膏的製造方法，其特徵在於：步驟（C）是向分離去除了石膏的廢硫酸中添加鈣源，一面將廢硫酸的pH維持成2.5～3.0一面使石膏析出。 [4] 根據所述[1]至[3]中任一項記載的石膏的製造方法，其特徵在於：步驟（A）中所使用的鈣源為碳酸鈣。 [5] 根據所述[1]至[4]中任一項記載的石膏的製造方法，其特徵在於：步驟（C）中所使用的鈣源為氫氧化鈣。 [6] 根據所述[1]至[5]中任一項記載的石膏的製造方法，其特徵在於：步驟（E）中所使用的鈣源為氫氧化鈣。 [7] 一種水泥組合物的製造方法，其特徵在於：使用根據所述[1]至[6]中任一項記載的石膏的製造方法中的步驟（B）中所分離去除的石膏、及步驟（F）中所分離去除的石膏的至少一種石膏來製造水泥組合物。 [發明的效果]As a result of intensive studies, the present inventors have found that gypsum having a high fluorine content is precipitated from waste sulfuric acid which has been precipitated and removed by removing gypsum having a low fluorine content, thereby reducing the content of fluorine in the waste sulfuric acid. The gypsum is further precipitated from the spent sulfuric acid having a reduced fluorine content, whereby SO 4 2- in the spent sulfuric acid can be more effectively utilized as gypsum, thereby completing the present invention. That is, the present invention is as follows. [1] A method for producing gypsum, comprising: a step (A) of adding gypsum to a waste sulfuric acid containing fluorine, maintaining a pH of the spent sulfuric acid to 2.0 or less; and (A) Step (B) of separating the gypsum precipitated from the waste sulfuric acid; adding a calcium source to the waste sulfuric acid in which the gypsum is separated and removed in the step (B), maintaining the pH of the waste sulfuric acid to 2.5 to 4.0 while making the gypsum a step (C) of separating; a step (D) of separating and removing the gypsum precipitated in the step (C) from the waste sulfuric acid; and adding a calcium source to the waste sulfuric acid in which the gypsum is separated and removed in the step (D), The step (E) of precipitating gypsum with the pH of the spent sulfuric acid being maintained at 6.0 to 8.0; and the step (F) of separating and removing the gypsum precipitated in the step (E) from the spent sulfuric acid. [2] The method for producing gypsum according to [1], wherein the step (A) is a step of adding a calcium source to the waste sulfuric acid containing fluorine, and maintaining the pH of the waste sulfuric acid to 1.5 or less. Precipitate. [3] The method for producing gypsum according to [1] or [2], wherein the step (C) is to add a calcium source to the waste sulfuric acid from which the gypsum is separated and removed, and maintain the pH of the waste sulfuric acid while maintaining The gypsum is precipitated on the side of 2.5 to 3.0. [4] The method for producing gypsum according to any one of [1] to [3] wherein the calcium source used in the step (A) is calcium carbonate. [5] The method for producing gypsum according to any one of [1] to [4] wherein the calcium source used in the step (C) is calcium hydroxide. [6] The method for producing gypsum according to any one of [1] to [5] wherein the calcium source used in the step (E) is calcium hydroxide. [7] A method for producing a cement composition, which is characterized by using the gypsum separated in the step (B) in the method for producing gypsum according to any one of the above [1] to [6], and At least one gypsum of the gypsum removed in the step (F) is used to produce a cement composition. [Effects of the Invention]
根據本發明，可提供一種與從前相比，可更有效地利用廢硫酸的石膏的製造方法，及使用通過所述石膏的製造方法所製造的石膏來製造水泥組合物的水泥組合物的製造方法。According to the present invention, it is possible to provide a method for producing gypsum which can utilize waste sulfuric acid more effectively than before, and a method for producing a cement composition using the gypsum produced by the method for producing gypsum to produce a cement composition .
[石膏的製造方法] 以下，對本發明的石膏的製造方法進行說明。本發明的石膏的製造方法包括：向含有氟的廢硫酸中添加鈣源，一面將廢硫酸的pH維持成2.0以下一面使石膏析出的步驟（A）；將步驟（A）中所析出的石膏從廢硫酸中分離去除的步驟（B）；向在步驟（B）中分離去除了石膏的廢硫酸中添加鈣源，一面將廢硫酸的pH維持成2.5～4.0一面使石膏析出的步驟（C）；將步驟（C）中所析出的石膏從廢硫酸中分離去除的步驟（D）；向在步驟（D）中分離去除了石膏的廢硫酸中添加鈣源，一面將廢硫酸的pH維持成6.0～8.0一面使石膏析出的步驟（E）；以及將步驟（E）中所析出的石膏從廢硫酸中分離去除的步驟（F）。[Method for Producing Gypsum] Hereinafter, a method for producing gypsum according to the present invention will be described. The method for producing gypsum according to the present invention includes a step (A) of adding gypsum to a waste sulfuric acid containing fluorine, maintaining the pH of the spent sulfuric acid to 2.0 or less, and depositing the gypsum deposited in the step (A). Step (B) of separating and removing from waste sulfuric acid; adding a calcium source to waste sulfuric acid in which gypsum is separated and removed in the step (B), and maintaining the pH of the spent sulfuric acid to 2.5 to 4.0 to precipitate gypsum (C) a step (D) of separating and removing the gypsum precipitated in the step (C) from the spent sulfuric acid; adding a calcium source to the waste sulfuric acid in which the gypsum is separated and removed in the step (D), while maintaining the pH of the spent sulfuric acid Step (E) of precipitating gypsum on a side of 6.0 to 8.0; and step (F) of separating and removing gypsum precipitated in the step (E) from waste sulfuric acid.
步驟（A） 在步驟（A）中，向含有氟的廢硫酸中添加鈣源，一面將廢硫酸的pH維持成2.0以下一面使石膏析出。Step (A) In the step (A), a calcium source is added to the waste sulfuric acid containing fluorine, and the gypsum is precipitated while maintaining the pH of the spent sulfuric acid to 2.0 or less.
（廢硫酸） 步驟（A）中所使用的廢硫酸只要是含有氟者，則並無特別限定。含有氟的廢硫酸例如是回收將硫化精礦作為原料的非鐵金屬精煉爐的排氣中的SO2 所製造的廢硫酸。所述排氣含有氟，因此廢硫酸也含有氟。(Waste sulfuric acid) The waste sulfuric acid used in the step (A) is not particularly limited as long as it contains fluorine. The waste sulfuric acid containing fluorine is, for example, waste sulfuric acid produced by SO 2 in the exhaust gas of a non-ferrous metal refining furnace in which a sulfide concentrate is used as a raw material. The exhaust gas contains fluorine, so the spent sulfuric acid also contains fluorine.
（鈣源） 步驟（A）中所使用的鈣源是含有鈣的化合物及將這些化合物作為主成分的各種材料，只要是石膏以外者，則並無特別限定。鈣源例如可列舉：氧化鈣、氫氧化鈣、碳酸鈣及磷酸鈣等。另外，也可以將貝殼或未加工的混凝土污泥（concrete sludge）等鈣的含量大的廢棄物用作鈣源。這些鈣源可單獨使用一種、或將兩種以上組合使用。這些鈣源之中，優選的鈣源為碳酸鈣。再者，可將粉末狀態的鈣源添加至廢硫酸中，也可以將漿料狀態的鈣源添加至廢硫酸中。(Calcium source) The calcium source used in the step (A) is a compound containing calcium and various materials containing these compounds as a main component, and is not particularly limited as long as it is other than gypsum. Examples of the calcium source include calcium oxide, calcium hydroxide, calcium carbonate, and calcium phosphate. Further, waste having a large content of calcium such as shells or unprocessed concrete sludge may be used as the calcium source. These calcium sources may be used alone or in combination of two or more. Among these calcium sources, a preferred source of calcium is calcium carbonate. Further, a calcium source in a powder state may be added to the waste sulfuric acid, or a calcium source in a slurry state may be added to the waste sulfuric acid.
（鈣源的添加量） 鈣源的添加量是以將添加有鈣源的廢硫酸的pH維持成2.0以下，優選維持成1.5以下的方式進行控制。(Amount of Addition of Calcium Source) The amount of the calcium source to be added is controlled such that the pH of the spent sulfuric acid to which the calcium source is added is maintained at 2.0 or less, preferably at 1.5 or less.
（石膏） 步驟（A）中所析出的石膏為二水石膏。廢硫酸中的氟不會析出，而殘留在廢硫酸中，因此步驟（A）中所析出的石膏中的氟的含量小。(Gypsum) The gypsum precipitated in the step (A) is dihydrate gypsum. The fluorine in the spent sulfuric acid does not precipitate but remains in the spent sulfuric acid, so the content of fluorine in the gypsum precipitated in the step (A) is small.
（廢硫酸的pH） 在步驟（A）中，將向廢硫酸中添加鈣源來使石膏析出時的廢硫酸的pH維持成2.0以下，優選維持成1.5以下。若廢硫酸的pH大於2.0，則與石膏一同析出的氟化鈣的析出量變大，石膏中的氟的含量變大。另外，只要石膏析出，則向廢硫酸中添加鈣源來使石膏析出時的廢硫酸的pH的下限值並無特別限定。例如，廢硫酸的pH的下限值為1.0。(pH of waste sulfuric acid) In the step (A), a calcium source is added to the waste sulfuric acid to maintain the pH of the spent sulfuric acid at the time of gypsum deposition to 2.0 or less, preferably to 1.5 or less. When the pH of the spent sulfuric acid is more than 2.0, the amount of precipitation of calcium fluoride precipitated together with the gypsum becomes large, and the content of fluorine in the gypsum becomes large. In addition, as long as the gypsum is deposited, the lower limit of the pH of the waste sulfuric acid when the calcium source is added to the waste sulfuric acid to precipitate the gypsum is not particularly limited. For example, the lower limit of the pH of the spent sulfuric acid is 1.0.
（水） 在步驟（A）中，為了調整添加有鈣源的廢硫酸的粘度等，也可以向廢硫酸中添加水。可用于本發明的石膏的製造方法的水例如可列舉：離子交換水、純水、蒸餾水及自來水等。這些水可單獨使用一種、或將兩種以上組合使用。再者，在步驟（A）以外的步驟中也可以向廢硫酸中添加水。(Water) In the step (A), water may be added to the waste sulfuric acid in order to adjust the viscosity or the like of the waste sulfuric acid to which the calcium source is added. Examples of the water which can be used in the method for producing gypsum of the present invention include ion-exchanged water, pure water, distilled water, tap water, and the like. These waters may be used alone or in combination of two or more. Further, water may be added to the waste sulfuric acid in a step other than the step (A).
步驟（B） 在步驟（B）中，將步驟（A）中所析出的石膏從廢硫酸中分離去除。Step (B) In the step (B), the gypsum precipitated in the step (A) is separated from the spent sulfuric acid.
（分離去除） 可通過使石膏沉澱來將石膏從廢硫酸中分離去除，也可以通過對含有石膏的廢硫酸進行過濾來將石膏從廢硫酸中分離去除。另外，也可以採用使用液體分流器、傾析器、離心分離機、壓濾機等固液分離裝置的分離方法來將石膏從廢硫酸中分離去除。這些分離去除方法可單獨實施，也可以將兩種以上組合來實施。(Separation and Removal) Gypsum can be separated from waste sulfuric acid by precipitating gypsum, and gypsum can also be separated from waste sulfuric acid by filtering waste sulfuric acid containing gypsum. Alternatively, the gypsum may be separated from the spent sulfuric acid by a separation method using a solid-liquid separation device such as a liquid flow divider, a decanter, a centrifugal separator, or a filter press. These separation and removal methods may be carried out singly or in combination of two or more.
步驟（C） 在步驟（C）中，向在步驟（B）中分離去除了石膏的廢硫酸中添加鈣源，一面將廢硫酸的pH維持成2.5～4.0一面使石膏析出。Step (C) In the step (C), a calcium source is added to the waste sulfuric acid in which the gypsum is separated and removed in the step (B), and the gypsum is precipitated while maintaining the pH of the spent sulfuric acid at 2.5 to 4.0.
（廢硫酸） 步驟（C）中所使用的廢硫酸為在步驟（B）中分離去除了石膏的廢硫酸。(Waste sulfuric acid) The waste sulfuric acid used in the step (C) is waste sulfuric acid in which the gypsum is separated and removed in the step (B).
（鈣源） 步驟（C）中所使用的鈣源是含有鈣的化合物及將這些化合物作為主成分的各種材料，只要是石膏以外者，則並無特別限定。鈣源例如可列舉：氧化鈣、氫氧化鈣、碳酸鈣及磷酸鈣等。另外，也可以將貝殼或未加工的混凝土污泥等鈣的含量大的廢棄物用作鈣源。這些鈣源可單獨使用一種、或將兩種以上組合使用。這些鈣源之中，優選的鈣源為氫氧化鈣。再者，可將粉末狀態的鈣源添加至廢硫酸中，也可以將漿料狀態的鈣源添加至廢硫酸中。(Calcium Source) The calcium source used in the step (C) is a compound containing calcium and various materials containing these compounds as a main component, and is not particularly limited as long as it is other than gypsum. Examples of the calcium source include calcium oxide, calcium hydroxide, calcium carbonate, and calcium phosphate. Further, waste having a large content of calcium such as shells or unprocessed concrete sludge may be used as a calcium source. These calcium sources may be used alone or in combination of two or more. Among these calcium sources, a preferred source of calcium is calcium hydroxide. Further, a calcium source in a powder state may be added to the waste sulfuric acid, or a calcium source in a slurry state may be added to the waste sulfuric acid.
（鈣源的添加量） 鈣源的添加量是以將添加有鈣源的廢硫酸的pH維持成2.5～4.0，優選維持成2.5～3.0的方式進行控制。(Amount of Addition of Calcium Source) The amount of the calcium source to be added is controlled such that the pH of the spent sulfuric acid to which the calcium source is added is maintained at 2.5 to 4.0, preferably at 2.5 to 3.0.
（石膏） 步驟（C）中所析出的石膏為二水石膏。廢硫酸中的氟的大部分作為氟化鈣而與石膏一同析出，因此步驟（C）中所析出的石膏中的氟的含量變大，並且廢硫酸中的氟的含量變小。(Gypsum) The gypsum precipitated in the step (C) is dihydrate gypsum. Most of the fluorine in the spent sulfuric acid is precipitated together with the gypsum as calcium fluoride. Therefore, the content of fluorine in the gypsum precipitated in the step (C) becomes large, and the content of fluorine in the spent sulfuric acid becomes small.
步驟（C）中所析出的石膏也可以廢棄。但是，在水泥組合物中存在含有氟作為必需的微量成分者。因此，也可以將步驟（C）中所析出的石膏用作此種水泥組合物的原料。The gypsum precipitated in the step (C) can also be discarded. However, those containing fluorine as an essential trace component are present in the cement composition. Therefore, the gypsum precipitated in the step (C) can also be used as a raw material of such a cement composition.
（廢硫酸的pH） 在步驟（C）中，將向廢硫酸中添加鈣源來使石膏析出時的廢硫酸的pH維持成2.5～4.0，優選維持成2.5～3.0。若廢硫酸的pH小於2.5，則存在無法使廢硫酸中的大部分氟作為氟化鈣而與石膏一同析出的情況。在此情況下，將步驟（C）中所析出的石膏分離去除後的廢硫酸中的氟的含量變大。另外，若廢硫酸的pH大於4.0，則可在步驟（E）中回收的石膏的量變少。(pH of waste sulfuric acid) In the step (C), a calcium source is added to the waste sulfuric acid to maintain the pH of the spent sulfuric acid at the time of gypsum deposition to 2.5 to 4.0, preferably 2.5 to 3.0. If the pH of the spent sulfuric acid is less than 2.5, most of the fluorine in the spent sulfuric acid cannot be precipitated together with the gypsum as calcium fluoride. In this case, the content of fluorine in the waste sulfuric acid after the gypsum separated in the step (C) is separated and removed is increased. Further, if the pH of the spent sulfuric acid is more than 4.0, the amount of gypsum recovered in the step (E) becomes small.
步驟（D） 在步驟（D）中，將步驟（C）中所析出的石膏從廢硫酸中分離去除。Step (D) In the step (D), the gypsum precipitated in the step (C) is separated and removed from the spent sulfuric acid.
（分離去除） 步驟（D）中的分離去除的說明與步驟（B）中的分離去除的說明相同，因此省略步驟（D）中的分離去除的說明。再者，步驟（D）中的分離去除的方法可與步驟（B）中的分離去除的方法相同，也可以不同。另外，為了使分離變得更快，也可以添加高分子凝聚劑。(Separation and Removal) The description of the separation and removal in the step (D) is the same as the description of the separation and removal in the step (B), and therefore the description of the separation and removal in the step (D) is omitted. Further, the method of separation and removal in the step (D) may be the same as or different from the method of separation and removal in the step (B). Further, in order to make the separation faster, a polymer flocculating agent may be added.
步驟（E） 在步驟（E）中，向在步驟（D）中分離去除了石膏的廢硫酸中添加鈣源，一面將廢硫酸的pH維持成6.0～8.0一面使石膏析出。由此，可使在所述步驟（A）中未作為石膏析出的SO4 2- 從廢硫酸中進一步析出，而可更有效地利用廢硫酸。Step (E) In the step (E), a calcium source is added to the waste sulfuric acid in which the gypsum is separated and removed in the step (D), and the gypsum is precipitated while maintaining the pH of the spent sulfuric acid at 6.0 to 8.0. Thereby, SO 4 2- which is not precipitated as gypsum in the step (A) can be further precipitated from the waste sulfuric acid, and waste sulfuric acid can be utilized more effectively.
（廢硫酸） 步驟（E）中所使用的廢硫酸為在步驟（D）中分離去除了石膏的廢硫酸。(Waste sulfuric acid) The waste sulfuric acid used in the step (E) is waste sulfuric acid in which the gypsum is separated and removed in the step (D).
（鈣源） 步驟（E）中所使用的鈣源是含有鈣的化合物及將這些化合物作為主成分的各種材料，只要是石膏以外者，則並無特別限定。鈣源例如可列舉：氧化鈣、氫氧化鈣、碳酸鈣及磷酸鈣等。另外，也可以將貝殼或未加工的混凝土污泥等鈣的含量大的廢棄物用作鈣源。這些鈣源可單獨使用一種、或將兩種以上組合使用。這些鈣源之中，優選的鈣源為氫氧化鈣。再者，可將粉末狀態的鈣源添加至廢硫酸中，也可以將漿料狀態的鈣源添加至廢硫酸中。(Calcium Source) The calcium source used in the step (E) is a compound containing calcium and various materials containing these compounds as a main component, and is not particularly limited as long as it is other than gypsum. Examples of the calcium source include calcium oxide, calcium hydroxide, calcium carbonate, and calcium phosphate. Further, waste having a large content of calcium such as shells or unprocessed concrete sludge may be used as a calcium source. These calcium sources may be used alone or in combination of two or more. Among these calcium sources, a preferred source of calcium is calcium hydroxide. Further, a calcium source in a powder state may be added to the waste sulfuric acid, or a calcium source in a slurry state may be added to the waste sulfuric acid.
（鈣源的添加量） 鈣源的添加量是以將添加有鈣源的廢硫酸的pH維持成6.0～8.0，優選維持成6.5～7.5的方式進行控制。(Addition amount of calcium source) The calcium source is added in such a manner that the pH of the spent sulfuric acid to which the calcium source is added is maintained at 6.0 to 8.0, preferably at 6.5 to 7.5.
（石膏） 步驟（E）中所析出的石膏為二水石膏。如上所述，在步驟（C）中，廢硫酸中的氟的大部分作為氟化鈣而與石膏一同析出。因此，步驟（E）中所析出的石膏中的氟的含量變小。(Gypsum) The gypsum precipitated in the step (E) is dihydrate gypsum. As described above, in the step (C), most of the fluorine in the spent sulfuric acid is precipitated together with the gypsum as calcium fluoride. Therefore, the content of fluorine in the gypsum precipitated in the step (E) becomes small.
（廢硫酸的pH） 在步驟（E）中，將向廢硫酸中添加鈣源時的廢硫酸的pH維持成6.0～8.0，優選維持成6.5～7.5。若添加有鈣源的廢硫酸的pH小於6.0，則存在殘留在廢硫酸中的SO4 2- 的含量變大的情況，若添加有鈣源的廢硫酸的pH大於8.0，則存在未與廢硫酸反應而殘留的鈣源的含量變大的情況。(pH of waste sulfuric acid) In the step (E), the pH of the spent sulfuric acid when the calcium source is added to the spent sulfuric acid is maintained at 6.0 to 8.0, preferably at 6.5 to 7.5. When the pH of the waste sulfuric acid to which the calcium source is added is less than 6.0, the content of SO 4 2- remaining in the waste sulfuric acid may increase. If the pH of the spent sulfuric acid to which the calcium source is added is more than 8.0, there is no waste. The content of the calcium source remaining by the sulfuric acid reaction becomes large.
步驟（F） 在步驟（F）中，將步驟（E）中所析出的石膏從廢硫酸中分離去除。Step (F) In the step (F), the gypsum precipitated in the step (E) is separated and removed from the spent sulfuric acid.
（分離去除） 步驟（F）中的分離去除的說明與步驟（B）中的分離去除的說明相同，因此省略步驟（F）中的分離去除的說明。再者，步驟（F）中的分離去除的方法可與步驟（B）中的分離去除的方法相同，也可以不同。另外，為了使分離變得更快，也可以添加高分子凝聚劑。(Separation and Removal) The description of the separation and removal in the step (F) is the same as the description of the separation and removal in the step (B), and therefore the description of the separation and removal in the step (F) is omitted. Further, the method of separation and removal in the step (F) may be the same as or different from the method of separation and removal in the step (B). Further, in order to make the separation faster, a polymer flocculating agent may be added.
在步驟（F）中分離去除了石膏的廢硫酸也可以直接作為廢液進行處理。另外，也可以將在步驟（F）中分離去除了石膏的廢硫酸再次用於從廢硫酸製造石膏。例如，也可以將在步驟（F）中分離去除了石膏的廢硫酸用作製作鈣源的漿料時的介質、或用以調節添加鈣源後的廢硫酸的粘度的介質。The waste sulfuric acid from which the gypsum is separated and removed in the step (F) can also be directly treated as a waste liquid. Alternatively, the spent sulfuric acid from which gypsum is separated and removed in the step (F) can be reused for producing gypsum from waste sulfuric acid. For example, a waste sulfuric acid in which gypsum is separated and removed in the step (F) may be used as a medium for preparing a slurry of a calcium source, or a medium for adjusting the viscosity of waste sulfuric acid after adding a calcium source.
[水泥組合物的製造方法] 本發明的水泥組合物的製造方法使用本發明的石膏的製造方法中的步驟（B）中所分離去除的石膏、及步驟（F）中所分離去除的石膏的至少一種石膏來製造水泥組合物。例如，也可以向水泥溶渣（cement clinker）中添加本發明的石膏的製造方法的步驟（B）中所分離去除的石膏與少量混合成分來製造水泥組合物。另外，也可以向將本發明的石膏的製造方法的步驟（B）中所分離去除的石膏用作溶渣原料之一所製造的水泥溶渣中，添加本發明的石膏的製造方法的步驟（B）中所分離去除的石膏或其他石膏與少量混合成分來製造水泥組合物。進而，也可以使用本發明的石膏的製造方法中的步驟（F）中所分離去除的石膏來代替步驟（B）中所分離去除的石膏、或將本發明的石膏的製造方法中的步驟（F）中所分離去除的石膏與步驟（B）中所分離去除的石膏一同使用。由此，可有效利用通過本發明的石膏的製造方法所製造的石膏作為水泥組合物的原料。 [實施例][Manufacturing Method of Cement Composition] The method for producing a cement composition of the present invention uses the gypsum separated and removed in the step (B) in the method for producing gypsum of the present invention, and the gypsum separated and removed in the step (F). At least one gypsum is used to make a cementitious composition. For example, it is also possible to add a gypsum separated in the step (B) of the method for producing gypsum of the present invention to a cement clinker with a small amount of a mixed component to produce a cement composition. Further, the step of producing the gypsum of the present invention may be added to the cement slag produced by using the gypsum separated in the step (B) of the method for producing gypsum of the present invention as a slag raw material ( The gypsum or other gypsum separated in B) is mixed with a small amount of the components to produce a cement composition. Further, instead of the gypsum separated in the step (B) or the step in the method for producing the gypsum of the present invention, the gypsum separated in the step (F) in the method for producing gypsum of the present invention may be used. The gypsum separated in F) is used together with the gypsum removed in step (B). Thereby, gypsum produced by the method for producing gypsum of the present invention can be effectively utilized as a raw material of the cement composition. [Examples]
繼而，通過實施例來更詳細地說明本發明，但本發明並不受這些實施例任何限定。The invention will be described in more detail by way of examples, but the invention is not limited by these examples.
[測定及評價] 如以下般測定及評價通過實施例的石膏的製造方法所製造的石膏及伴隨所述製造所產生的廢硫酸。 （1）廢硫酸的pH 使用pH計（堀場製作所（股份）製造，商品名：pH計 D-51）、pH電極（堀場製作所（股份）製造，商品名：Sleeve ToupH電極 9681-10D），測定添加有鈣源的廢硫酸的pH。 （2）析出物的鑒定 使用X射線繞射裝置，進行向廢硫酸中添加鈣源後從廢硫酸中析出的析出物的鑒定。 （3）析出物中的氟的含量 使用燃燒式離子色譜裝置，測定向廢硫酸中添加鈣源後從廢硫酸中析出的析出物中的氟含量。 （4）廢硫酸中的氟的含量 使用流動注射分析裝置，測定對廢硫酸進行過濾所獲得的廢硫酸中的氟含量。 （5）廢硫酸中的SO4 2- 的含量 使用離子色譜裝置，測定對廢硫酸進行過濾所獲得的廢硫酸中的SO4 2- 的含量。[Measurement and Evaluation] The gypsum produced by the method for producing gypsum of the examples and the waste sulfuric acid produced by the production were measured and evaluated as follows. (1) The pH of the waste sulfuric acid was measured using a pH meter (manufactured by Horiba, Ltd., trade name: pH meter D-51), pH electrode (manufactured by Horiba, Ltd., trade name: Sleeve ToupH electrode 9681-10D). The pH of the spent sulfuric acid with a calcium source is added. (2) Identification of precipitates The X-ray diffraction apparatus was used to identify precipitates which were precipitated from waste sulfuric acid after adding a calcium source to waste sulfuric acid. (3) Content of fluorine in the precipitate The content of fluorine in the precipitate which was precipitated from the waste sulfuric acid after adding a calcium source to the waste sulfuric acid was measured using a combustion type ion chromatography apparatus. (4) Content of fluorine in waste sulfuric acid The fluorine content in the waste sulfuric acid obtained by filtering waste sulfuric acid was measured using a flow injection analysis apparatus. (5) 4 2- content of the waste sulfuric acid SO ion chromatography apparatus measuring the content of the waste sulfuric acid in 42- spent sulfuric acid obtained by SO filtration.
[實施例的石膏的製造方法] （實施例1） （第1階段） 向廢硫酸中添加碳酸鈣來使廢硫酸的pH變成2.0。然後，對廢硫酸進行過濾而獲得廢硫酸的析出物及經過濾的廢硫酸。[Method for Producing Gypsum of the Example] (Example 1) (First Stage) Calcium carbonate was added to waste sulfuric acid to adjust the pH of the spent sulfuric acid to 2.0. Then, the spent sulfuric acid is filtered to obtain precipitates of spent sulfuric acid and filtered waste sulfuric acid.
（第2階段） 向在第1階段中得到過濾的廢硫酸中添加氫氧化鈣來使廢硫酸的pH變成3.0。然後，對廢硫酸進行過濾而獲得廢硫酸的析出物及經過濾的廢硫酸。(Second stage) Calcium hydroxide was added to the spent sulfuric acid filtered in the first stage to adjust the pH of the spent sulfuric acid to 3.0. Then, the spent sulfuric acid is filtered to obtain precipitates of spent sulfuric acid and filtered waste sulfuric acid.
（第3階段） 向在第2階段中得到過濾的廢硫酸中添加氫氧化鈣來使廢硫酸的pH變成6.5。然後，對廢硫酸進行過濾而獲得廢硫酸的析出物及經過濾的廢硫酸。(Phase 3) Calcium hydroxide was added to the spent sulfuric acid filtered in the second stage to adjust the pH of the spent sulfuric acid to 6.5. Then, the spent sulfuric acid is filtered to obtain precipitates of spent sulfuric acid and filtered waste sulfuric acid.
[測定結果及評價結果] 將實施例1的石膏的製造方法中所獲得的析出物及廢硫酸的評價結果示於表1中。[Measurement Results and Evaluation Results] The evaluation results of the precipitates and waste sulfuric acid obtained in the method for producing gypsum of Example 1 are shown in Table 1.
[表1] 表1 實施例1的石膏的製造方法
根據實施例1的評價結果，可知不僅在第1階段中可獲得氟的含量低的石膏，在第3階段中也可以獲得氟的含量低的石膏。由此，可知與僅實施第1階段來利用廢硫酸的情況相比，實施例1的石膏的製造方法可更有效地利用廢硫酸中的SO4 2- 。According to the evaluation results of Example 1, it is understood that gypsum having a low fluorine content can be obtained not only in the first stage but also in the third stage. From this, it is understood that the method for producing gypsum of Example 1 can more effectively utilize SO 4 2- in waste sulfuric acid than in the case where only the first stage is used to utilize waste sulfuric acid.
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