TWI694057B - Method for manufacturing gypsum and method for manufacturing cement composition - Google Patents
Method for manufacturing gypsum and method for manufacturing cement composition Download PDFInfo
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- TWI694057B TWI694057B TW105108182A TW105108182A TWI694057B TW I694057 B TWI694057 B TW I694057B TW 105108182 A TW105108182 A TW 105108182A TW 105108182 A TW105108182 A TW 105108182A TW I694057 B TWI694057 B TW I694057B
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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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
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- Y02W30/91—Use of waste materials as fillers for mortars or concrete
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Abstract
本發明提供一種可直接使用含有重金屬的廢硫酸來製造重金屬的含量低的石膏的石膏的製造方法、及使用通過該石膏的製造方法所製造的石膏的水泥組成物的製造方法。本發明的石膏的製造方法包括向含有重金屬的廢硫酸中添加鈣源來使石膏析出的步驟（A），且在步驟（A）中，使向廢硫酸中添加鈣源來使石膏析出時的廢硫酸的pH變成3.0以下。本發明的水泥組成物的製造方法包括通過本發明的石膏的製造方法來製造石膏的步驟、以及使用製造石膏的步驟中所製造的石膏來製造水泥組成物的步驟。The present invention provides a method for producing gypsum that can directly use waste sulfuric acid containing heavy metals to produce gypsum with a low heavy metal content, and a method for producing a cement composition using gypsum produced by the method for producing gypsum. The method for producing gypsum of the present invention includes the step (A) of adding a calcium source to waste sulfuric acid containing heavy metals to precipitate gypsum, and in step (A), adding a calcium source to the waste sulfuric acid to precipitate gypsum The pH of waste sulfuric acid becomes 3.0 or less. The method for producing a cement composition of the present invention includes a step of producing gypsum by the method of producing gypsum of the present invention, and a step of producing a cement composition using the gypsum produced in the step of producing gypsum.
Description
本發明涉及一種有效利用含有重金屬的廢硫酸來製造石膏的石膏的製造方法、及使用通過該石膏的製造方法所製造的石膏來製造水泥組成物的水泥組成物的製造方法。The present invention relates to a method for producing gypsum that effectively uses waste sulfuric acid containing heavy metals to produce gypsum, and a method for producing a cement composition that uses gypsum produced by the method for producing gypsum to produce a cement composition.
利用鈣化合物對各種工業生產的步驟中所產生的硫酸進行中和處理，而製造作為其副產物的石膏的方法廣為人知。但是，關於含有許多重金屬的廢硫酸，石膏中的重金屬的含量也變高，因此作為石膏的利用受到限定。因此，已提出有由含有重金屬的廢硫酸製造重金屬的含量低的石膏的各種方法。例如，當使用含有鐵成分作為重金屬的廢硫酸來製造鐵成分的含量低的石膏時，事先實施削減鐵成分的處理後使用廢硫酸、或僅在鐵不會析出的低pH區域的反應中製造石膏。作為從含有鐵成分的廢硫酸中減少鐵成分，由此對含有鐵成分的廢硫酸進行處理的方法，例如專利文獻1中所記載的廢硫酸的處理方法及專利文獻2中所記載的廢硫酸的處理方法作為現有技術而為人所知。根據專利文獻1中所記載的廢硫酸的處理方法，對含有鐵成分的廢硫酸進行冷卻，使硫酸亞鐵析出並分離去除，而降低廢硫酸中的鐵成分濃度。另外，根據專利文獻2中所記載的廢硫酸的處理方法，將濃硫酸混入至廢硫酸中，由此使該廢硫酸的硫酸濃度變得非常高，而使鐵成分的溶解度下降，並使硫酸鐵結晶從溶解有鐵成分的廢硫酸中析出，且將該硫酸鐵結晶去除，由此削減溶解在廢硫酸中的鐵成分。 [現有技術文獻] [專利文獻]The calcium compound is used to neutralize sulfuric acid generated in various industrial production steps, and a method of producing gypsum as a by-product thereof is widely known. However, regarding the waste sulfuric acid containing many heavy metals, the content of heavy metals in gypsum also becomes high, so the use as gypsum is limited. Therefore, various methods for producing gypsum with a low heavy metal content from waste sulfuric acid containing heavy metals have been proposed. For example, when waste sulfuric acid containing iron components as heavy metals is used to produce gypsum with a low iron content, waste sulfuric acid is used after the treatment for reducing iron components is performed in advance, or only in a reaction in a low pH region where iron does not precipitate plaster. Examples of methods for treating waste sulfuric acid containing iron components by reducing iron components from waste sulfuric acid containing iron components include, for example, the treatment method for waste sulfuric acid described in Patent Document 1 and the waste sulfuric acid described in Patent Document 2 The processing method is known as the prior art. According to the method for treating waste sulfuric acid described in Patent Document 1, the waste sulfuric acid containing iron components is cooled to precipitate and separate and remove ferrous sulfate, thereby reducing the concentration of iron components in the waste sulfuric acid. In addition, according to the method of treating waste sulfuric acid described in Patent Document 2, by mixing concentrated sulfuric acid into waste sulfuric acid, the sulfuric acid concentration of the waste sulfuric acid becomes very high, so that the solubility of the iron component is reduced, and the sulfuric acid Iron crystals are precipitated from the waste sulfuric acid in which iron components are dissolved, and the iron sulfate crystals are removed, thereby reducing iron components dissolved in the waste sulfuric acid. [Prior Art Literature] [Patent Literature]
[專利文獻1]日本專利特開2004-256334號公報 [專利文獻2]日本專利特開2002-284509號公報[Patent Document 1] Japanese Patent Laid-Open No. 2004-256334 [Patent Document 2] Japanese Patent Laid-Open No. 2002-284509
[發明所要解決的問題][Problems to be solved by the invention]
但是，當使用通過廢硫酸的處理方法削減了鐵成分的廢硫酸製造石膏時，存在石膏的製造變得繁雜這一問題。另外，也有可能產生難以將鐵成分含量降低至足以製造石膏的水平為止的情況。另一方面，當僅在鐵不會析出的低pH區域的反應中製造石膏時，可製造石膏的量變少，無法充分地利用硫酸。因此，本發明的目的在於提供一種不限於含有鐵成分的廢硫酸，可直接使用含有重金屬的廢硫酸來製造重金屬的含量低的石膏的石膏的製造方法，及使用通過該石膏的製造方法所製造的石膏來製造水泥組成物的水泥組成物的製造方法。 [解決問題的技術手段]However, there is a problem that the production of gypsum becomes complicated when using waste sulfuric acid in which iron components have been reduced by the treatment method of waste sulfuric acid. In addition, it may be difficult to reduce the iron component content to a level sufficient to produce gypsum. On the other hand, when gypsum is produced only in a reaction in a low pH region where iron does not precipitate, the amount of gypsum that can be produced becomes small, and sulfuric acid cannot be fully utilized. Therefore, an object of the present invention is to provide a method for producing gypsum that can directly use waste sulfuric acid containing heavy metals to produce gypsum having a low heavy metal content, and to use the method for producing gypsum by using the method for producing gypsum. A method of manufacturing a cement composition using gypsum to manufacture a cement composition. [Technical means to solve the problem]
本發明者等進行努力研究的結果，發現通過調整向含有重金屬的廢硫酸中直接添加鈣源來使石膏析出時的廢硫酸的pH，可降低所析出的石膏中的重金屬的含量，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：包括向含有重金屬的廢硫酸中添加鈣源來使石膏析出的步驟（A），且在步驟（A）中，使向廢硫酸中添加鈣源來使石膏析出時的廢硫酸的pH變成3.0以下。 [2] 根據所述[1]中記載的石膏的製造方法，其特徵在於：還包括將步驟（A）中所析出的石膏從廢硫酸中分離去除的步驟（B），以及向分離去除了石膏的廢硫酸中添加選自由氫氧化鈉、氫氧化鉀及氫氧化鎂所組成的群組中的至少一種來使重金屬的氫氧化物析出的步驟（C），且在步驟（C）中，使向廢硫酸中添加選自由氫氧化鈉、氫氧化鉀及氫氧化鎂所組成的群組中的至少一種來使氫氧化物析出時的廢硫酸的pH變成3.5以上、10.0以下。 [3] 根據所述[2]中記載的石膏的製造方法，其特徵在於：還包括將步驟（C）中所析出的氫氧化物從廢硫酸中分離去除的步驟（D）、以及向分離去除了氫氧化物的廢硫酸中添加鈣源來使石膏析出的步驟（E）。 [4] 一種水泥組成物的製造方法，其特徵在於：包括通過根據所述[1]至[3]中任一項記載的石膏的製造方法來製造石膏的步驟、以及使用製造石膏的步驟中所製造的石膏來製造水泥組成物的步驟。 （發明的效果）As a result of intensive research, the inventors have found that by adjusting the pH of the waste sulfuric acid when gypsum is precipitated by directly adding a calcium source to the waste sulfuric acid containing heavy metals, the content of heavy metals in the precipitated gypsum can be reduced, thereby completing this invention. That is, the present invention is as follows. [1] A method for producing gypsum, characterized in that it includes a step (A) of adding a calcium source to waste sulfuric acid containing heavy metals to precipitate gypsum, and in step (A), adding a calcium source to the waste sulfuric acid In order to make the pH of the waste sulfuric acid at the time of gypsum precipitation below 3.0. [2] The method for producing gypsum according to the above [1], further comprising the step (B) of separating and removing the gypsum precipitated in step (A) from the waste sulfuric acid, and Step (C) of adding at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, and magnesium hydroxide to the waste sulfuric acid of gypsum to precipitate hydroxides of heavy metals, and in step (C), At least one selected from the group consisting of sodium hydroxide, potassium hydroxide, and magnesium hydroxide is added to the waste sulfuric acid to make the pH of the waste sulfuric acid at the time of precipitation of the hydroxide 3.5 or more and 10.0 or less. [3] The method for producing gypsum according to the above [2], further comprising the step (D) of separating and removing the hydroxide precipitated in the step (C) from the waste sulfuric acid, and the separation Step (E) of adding calcium source to the waste sulfuric acid from which the hydroxide has been removed to precipitate gypsum. [4] A method for producing a cement composition, comprising the steps of producing gypsum by the method of producing gypsum according to any one of the above [1] to [3], and using the step of producing gypsum The step of making gypsum to make cement composition. (Effect of invention)
根據本發明，可提供一種能夠直接使用含有重金屬的廢硫酸來製造重金屬的含量低的石膏的石膏的製造方法、及使用通過該石膏的製造方法所製造的石膏來製造水泥組成物的水泥組成物的製造方法。According to the present invention, it is possible to provide a method for producing gypsum that can directly use waste sulfuric acid containing heavy metals to produce gypsum with a low heavy metal content, and a cement composition that uses gypsum produced by the method for producing gypsum to produce a cement composition Manufacturing method.
[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重金屬的廢硫酸中添加鈣源來使石膏析出的步驟（A）。[Method for producing gypsum] Hereinafter, the method for producing gypsum of the present invention will be described. The method for producing gypsum of the present invention includes the step (A) of adding a calcium source to waste sulfuric acid containing heavy metals to precipitate gypsum.
步驟（A） 在步驟（A）中，向含有重金屬的廢硫酸中添加鈣源來使石膏析出。Step (A) In step (A), a calcium source is added to the waste sulfuric acid containing heavy metals to precipitate gypsum.
（重金屬） 本發明的重金屬是比重超過5的金屬，重金屬例如可列舉：鐵、鋅、鉻、鉛、鎘、銅、錫、汞、鎳及鈷等。在廢硫酸中含有鐵、鋅及鉻的情況多。(Heavy metal) The heavy metal of the present invention is a metal having a specific gravity exceeding 5, and examples of the heavy metal include iron, zinc, chromium, lead, cadmium, copper, tin, mercury, nickel, and cobalt. The waste sulfuric acid often contains iron, zinc and chromium.
（廢硫酸） 步驟（A）中所使用的廢硫酸只要是含有重金屬者，則並無特別限定。含有重金屬的廢硫酸例如為用於鋼板的酸洗後的硫酸及銅精煉中所產生的硫酸等。(Waste sulfuric acid) The waste sulfuric acid used in step (A) is not particularly limited as long as it contains heavy metals. The waste sulfuric acid containing heavy metals is, for example, sulfuric acid used for pickling steel plates and sulfuric acid generated in copper refining.
（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、磷酸鈣、氟化鈣及氯化鈣等。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，優選的鈣源可列舉氧化鈣及碳酸鈣等。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。這些所例示的鈣源可單獨使用一種、或將兩種以上組合使用。(Calcium Source) The calcium source used in step (A) is a compound containing calcium and various materials having these compounds as main components, and it is not particularly limited as long as it is other than gypsum. Examples of calcium sources include calcium oxide, calcium hydroxide, calcium carbonate, calcium phosphate, calcium fluoride, and calcium chloride. These calcium sources can be used alone or in combination of two or more. Among these calcium sources, preferred calcium sources include calcium oxide and calcium carbonate. In addition, wastes with a large calcium content such as shells or unprocessed concrete sludge (concrete sludge) can also be used as a calcium source. These exemplified calcium sources may be used alone or in combination of two or more.
（鈣源的添加量） 鈣源的添加量是以添加有鈣源的廢硫酸的pH收斂在3.0以下，優選收斂在2.5以下，更優選收斂在2.0以下的範圍內的方式進行控制。(Amount of calcium source added) The amount of calcium source added is controlled so that the pH of the waste sulfuric acid added with the calcium source converges to 3.0 or less, preferably 2.5 or less, and more preferably 2.0 or less.
（石膏） 步驟（A）中所析出的石膏為二水石膏及/或無水石膏。廢硫酸中的重金屬幾乎不會析出，而殘留在廢硫酸中，因此步驟（A）中所析出的石膏中的重金屬的含量小。(Gypsum) The gypsum precipitated in step (A) is dihydrate gypsum and/or anhydrous gypsum. The heavy metals in the waste sulfuric acid hardly precipitate, but remain in the waste sulfuric acid, so the content of heavy metals in the gypsum precipitated in step (A) is small.
在步驟（A）中，使向廢硫酸中添加鈣源來使石膏析出時的廢硫酸的pH變成3.0以下，優選變成2.5以下，更優選變成2.0以下。若廢硫酸的pH大於3.0，則與石膏一同析出的重金屬的化合物的析出量變高，石膏中的重金屬的含量變高。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。廢硫酸的pH的下限值例如為1.0。In step (A), the calcium source is added to the waste sulfuric acid to make the pH of the waste sulfuric acid at the time of gypsum precipitation 3.0 or less, preferably 2.5 or less, and more preferably 2.0 or less. When the pH of the waste sulfuric acid is greater than 3.0, the precipitation amount of the heavy metal compound precipitated together with gypsum becomes high, and the content of the heavy metal in the gypsum becomes high. In addition, as long as gypsum is precipitated, the lower limit of the pH of the waste sulfuric acid at the time of precipitation of gypsum by adding a calcium source to the waste sulfuric acid is not particularly limited. The lower limit of the pH of waste sulfuric acid is, for example, 1.0.
（水） 在步驟（A）中，為了調整添加有鈣源的廢硫酸的黏度等，也可以向混合物中添加水。可用於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。另外，也可以利用對在後述的步驟（F）中分離去除石膏時所產生的濾液進行處理所獲得的排水。(Water) In step (A), water may be added to the mixture in order to adjust the viscosity of waste sulfuric acid added with a calcium source. Examples of water that can be used in the method for producing gypsum of the present invention include ion-exchanged water, pure water, distilled water, and tap water. These waters can be used alone or in combination of two or more. In addition, drainage obtained by treating the filtrate generated when gypsum is separated and removed in step (F) described later may be used.
本發明的石膏的製造方法可進一步包括：將步驟（A）中所析出的石膏從廢硫酸中分離去除的步驟（B），以及向分離去除了石膏的廢硫酸中添加選自由氫氧化鈉、氫氧化鉀及氫氧化鎂所組成的群組中的至少一種來使重金屬的氫氧化物析出的步驟（C）。The method for producing gypsum of the present invention may further include the step (B) of separating and removing the gypsum precipitated in step (A) from the waste sulfuric acid, and adding the Step (C) of precipitating heavy metal hydroxide by at least one of the group consisting of potassium hydroxide and magnesium hydroxide.
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 step (B), the gypsum precipitated in step (A) is separated and removed from the waste 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 and removed from waste sulfuric acid by precipitating gypsum, and gypsum can be separated and removed from waste sulfuric acid by filtering waste sulfuric acid containing gypsum. In addition, a separation method using a solid-liquid separation device such as a liquid splitter, a decanter, a centrifugal separator, and a filter press may also be used to separate and remove gypsum from waste sulfuric acid. These separation and removal methods may be implemented individually or in combination of two or more.
步驟（C） 在步驟（C）中，向分離去除了石膏的廢硫酸中添加選自由氫氧化鈉、氫氧化鉀及氫氧化鎂所組成的群組中的至少一種來使重金屬的氫氧化物析出。Step (C) In step (C), at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, and magnesium hydroxide is added to the waste sulfuric acid from which gypsum is separated and removed to make heavy metal hydroxide Precipitate.
（選自由氫氧化鈉、氫氧化鉀及氫氧化鎂所組成的群組中的至少一種） 選自由氫氧化鈉、氫氧化鉀及氫氧化鎂所組成的群組中的至少一種與廢硫酸中的重金屬進行反應而使重金屬的氫氧化物析出，並且與廢硫酸中的硫酸進行反應而生成水溶性的硫酸鹽。(At least one selected from the group consisting of sodium hydroxide, potassium hydroxide and magnesium hydroxide) At least one selected from the group consisting of sodium hydroxide, potassium hydroxide and magnesium hydroxide and waste sulfuric acid The heavy metals reacted to precipitate the hydroxides of the heavy metals, and reacted with the sulfuric acid in the waste sulfuric acid to produce water-soluble sulfates.
（廢硫酸的pH） 在步驟（C）中，以使向廢硫酸中添加選自由氫氧化鈉、氫氧化鉀及氫氧化鎂所組成的群組中的至少一種來使重金屬的氫氧化物析出時的廢硫酸的pH優選變成3.5以上、10.0以下，更優選變成3.5以上、5.0以下的方式，調整選自由氫氧化鈉、氫氧化鉀及氫氧化鎂所組成的群組中的至少一種的添加量。通過使廢硫酸的pH變成3.5以上、10.0以下，可使廢硫酸中的大部分重金屬作為氫氧化物析出。(PH of waste sulfuric acid) In step (C), at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, and magnesium hydroxide is added to waste sulfuric acid to precipitate heavy metal hydroxides The pH of the waste sulfuric acid at that time is preferably 3.5 or more and 10.0 or less, more preferably 3.5 or more and 5.0 or less, and the addition of at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, and magnesium hydroxide is adjusted the amount. By changing the pH of the waste sulfuric acid to 3.5 or more and 10.0 or less, most of the heavy metals in the waste sulfuric acid can be precipitated as hydroxides.
例如，當使氫氧化鐵從含有鐵成分作為重金屬的廢硫酸中析出時，也可以使廢硫酸的pH優選變成5.0以上、10.0以下，更優選變成6.0以上、8.0以下的方式，調整選自由氫氧化鈉、氫氧化鉀及氫氧化鎂所組成的群組中的至少一種的添加量。通過使廢硫酸的pH變成5.0以上、10.0以下，可使廢硫酸中的大部分鐵作為氫氧化物析出。再者，選自由氫氧化鈉、氫氧化鉀及氫氧化鎂所組成的群組中的至少一種的鈉、鉀及鎂在廢硫酸中以離子的狀態存在。因此，對所析出的所述氫氧化物進行過濾，由此可減少所析出的氫氧化物中的鈉、鉀及鎂的含量，進而，利用水對所析出的氫氧化物進行清洗，由此可進一步減少所析出的氫氧化物中的鈉、鉀及鎂的含量。For example, when iron hydroxide is precipitated from waste sulfuric acid containing iron as a heavy metal, the pH of the waste sulfuric acid may be preferably adjusted to 5.0 or more and 10.0 or less, more preferably 6.0 or more and 8.0 or less, and adjusted to be selected from hydrogen The amount of addition of at least one of the group consisting of sodium oxide, potassium hydroxide, and magnesium hydroxide. By changing the pH of the waste sulfuric acid to 5.0 or more and 10.0 or less, most of the iron in the waste sulfuric acid can be precipitated as a hydroxide. In addition, at least one of sodium, potassium, and magnesium selected from the group consisting of sodium hydroxide, potassium hydroxide, and magnesium hydroxide exists in an ion state in the waste sulfuric acid. Therefore, by filtering the precipitated hydroxide, the content of sodium, potassium, and magnesium in the precipitated hydroxide can be reduced, and further, the precipitated hydroxide can be washed with water, thereby The content of sodium, potassium and magnesium in the precipitated hydroxide can be further reduced.
例如，當使氫氧化鋅從含有鋅成分作為重金屬的廢硫酸中析出時，也可以使廢硫酸的pH優選變成4.5以上、10.0以下，更優選變成5.0以上、10.0以下的方式，調整選自由氫氧化鈉、氫氧化鉀及氫氧化鎂所組成的群組中的至少一種的添加量。通過使廢硫酸的pH變成4.5以上、10.0以下，可使廢硫酸中的大部分鋅作為氫氧化物析出。For example, when zinc hydroxide is precipitated from waste sulfuric acid containing a zinc component as a heavy metal, the pH of the waste sulfuric acid may be preferably adjusted to 4.5 or more and 10.0 or less, more preferably 5.0 or more and 10.0 or less. The amount of addition of at least one of the group consisting of sodium oxide, potassium hydroxide, and magnesium hydroxide. By changing the pH of the waste sulfuric acid to 4.5 or more and 10.0 or less, most of the zinc in the waste sulfuric acid can be precipitated as a hydroxide.
例如，當使氫氧化鉻從含有鉻成分作為重金屬的廢硫酸中析出時，也可以使廢硫酸的pH優選變成3.5以上、10.0以下，更優選變成4.0以上、10.0以下，進而更優選變成4.5以上、10.0以下的方式，調整選自由氫氧化鈉、氫氧化鉀及氫氧化鎂所組成的群組中的至少一種的添加量。通過使廢硫酸的pH變成3.5以上、10.0以下，可使廢硫酸中的大部分鉻作為氫氧化物析出。For example, when chromium hydroxide is precipitated from waste sulfuric acid containing a chromium component as a heavy metal, the pH of the waste sulfuric acid may preferably be 3.5 or more and 10.0 or less, more preferably 4.0 or more and 10.0 or less, and even more preferably 4.5 or more 1. The amount of at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, and magnesium hydroxide is adjusted in a manner of 10.0 or less. By changing the pH of the waste sulfuric acid to 3.5 or more and 10.0 or less, most of the chromium in the waste sulfuric acid can be precipitated as a hydroxide.
本發明的石膏的製造方法可進一步包括將步驟（C）中所析出的氫氧化物從廢硫酸中分離去除的步驟（D）、以及向分離去除了氫氧化物的廢硫酸中添加鈣源來使石膏析出的步驟（E）。The method for producing gypsum of the present invention may further include the step (D) of separating and removing the hydroxide precipitated in step (C) from the waste sulfuric acid, and adding a calcium source to the waste sulfuric acid from which the hydroxide is separated and removed. Step (E) to precipitate gypsum.
步驟（D） 在步驟（D）中，將步驟（C）中所析出的重金屬的氫氧化物從廢硫酸中分離去除。Step (D) In step (D), the hydroxide of the heavy metal precipitated in step (C) is separated and removed from the waste 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 step (D) is the same as the description of the separation and removal in step (B), so the description of the separation and removal in step (D) is omitted. Furthermore, the method of separation and removal in step (D) may be the same as or different from the method of separation and removal in step (B). In addition, in order to make the separation faster, a polymer coagulant may be added.
步驟（E） 在步驟（E）中，向分離去除了重金屬的氫氧化物的廢硫酸中添加鈣源來使石膏析出。Step (E) In step (E), a calcium source is added to the waste sulfuric acid from which the hydroxide of the heavy metal has been removed to precipitate gypsum.
（分離去除了重金屬的氫氧化物的廢硫酸） 在步驟（E）中，分離去除了重金屬的氫氧化物的廢硫酸中的重金屬的含有率充分地變低，因此通過向廢硫酸中添加鈣源來使石膏析出，可獲得重金屬的含有率低的石膏。另外，在步驟（E）中，進一步使石膏析出，由此可有效地利用廢硫酸中的大部分SO4 成分。(Waste sulfuric acid from which hydroxides of heavy metals are separated) In step (E), the content of heavy metals in waste sulfuric acid from which hydroxides of heavy metals are separated is sufficiently low, so by adding calcium to waste sulfuric acid Gypsum is precipitated from the source to obtain gypsum with a low heavy metal content. In addition, in step (E), gypsum is further precipitated, so that most of the SO 4 component in the waste sulfuric acid can be effectively used.
（鈣源） 作為步驟（E）中所使用的鈣源，例如可列舉：氯化鈣等水溶性鈣鹽、或含有鈣離子的水溶液等。(Calcium Source) Examples of the calcium source used in step (E) include water-soluble calcium salts such as calcium chloride, and aqueous solutions containing calcium ions.
（鈣源的添加量） 關於步驟（E）中添加至廢硫酸中的鈣源的添加量，通過將鈣源中的Ca與廢硫酸中的SO4 2- 的莫耳比（Ca/SO4 2- ）接近1的量的鈣源添加至廢硫酸中，可將廢硫酸中的大部分SO4 2- 轉化成石膏。若莫耳比高於此，則鈣變得過剩，若莫耳比低於此，則硫酸根離子變得過剩，而需要排水處理，因此並不經濟。再者，鈣源中的Ca與廢硫酸中的SO4 2- 的莫耳比（Ca/SO4 2- ）優選0.9～1.0，更優選0.9～0.95。(Addition amount of calcium source) Regarding the addition amount of calcium source added to the waste sulfuric acid in step (E), the molar ratio of Ca in the calcium source to SO 4 2- in the waste sulfuric acid (Ca/SO 4 2- ) A calcium source close to 1 is added to the waste sulfuric acid, and most of the SO 4 2- in the waste sulfuric acid can be converted into gypsum. If the molar ratio is higher than this, calcium becomes excessive. If the molar ratio is lower than this, sulfate ions become excessive and drainage treatment is required, which is not economical. Furthermore, the molar ratio of Ca in the calcium source to SO 4 2- in the waste sulfuric acid (Ca/SO 4 2- ) is preferably 0.9 to 1.0, and more preferably 0.9 to 0.95.
本發明的石膏的製造方法可進一步包括將步驟（E）中所析出的石膏從廢硫酸中分離去除的步驟（F）。The method for producing gypsum of the present invention may further include the step (F) of separating and removing the gypsum precipitated in step (E) from waste sulfuric acid.
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 step (F), the gypsum precipitated in step (E) is separated and removed from the waste 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。(Separation and removal) The description of the separation and removal in step (F) is the same as the description of the separation and removal in step (B), so the description of the separation and removal in step (F) is omitted. Furthermore, the method of separation and removal in step (F) may be the same as or different from the method of separation and removal in step (B).
如上所述，步驟（C）中所添加的選自由氫氧化鈉、氫氧化鉀及氫氧化鎂所組成的群組中的至少一種的鈉、鉀及鎂在廢硫酸中以離子的狀態存在。因此，利用水對步驟（F）中所析出的石膏進行清洗，由此可減少所析出的石膏中的鈉、鉀及鎂的含量。As described above, at least one of sodium, potassium, and magnesium selected from the group consisting of sodium hydroxide, potassium hydroxide, and magnesium hydroxide added in step (C) exists in the state of ions in the waste sulfuric acid. Therefore, the gypsum precipitated in the step (F) is washed with water, thereby reducing the contents of sodium, potassium, and magnesium in the precipitated gypsum.
[水泥組成物的製造方法] 本發明的水泥組成物的製造方法包括：通過本發明的石膏的製造方法來製造石膏的步驟、以及使用製造石膏的步驟中所製造的石膏來製造水泥組成物的步驟。即，本發明的水泥組成物的製造方法使用通過本發明的石膏的製造方法所製造的石膏來製造水泥組成物。例如，也可以向水泥溶渣（cement clinker）中添加通過本發明的石膏的製造方法所製造的石膏與少量混合成分來製造水泥組成物。另外，也可以向將通過本發明的石膏的製造方法所製造的石膏用作溶渣原料之一所製造的水泥溶渣中，添加通過本發明的石膏的製造方法所製造的石膏或其他石膏與少量混合成分來製造水泥組成物。[Method for producing cement composition] The method for producing cement composition of the present invention includes the steps of producing gypsum by the method of producing gypsum of the present invention, and producing the cement composition using the gypsum produced in the step of producing gypsum. step. That is, the method for producing the cement composition of the present invention uses the gypsum produced by the method for producing gypsum of the present invention to produce the cement composition. For example, a cement composition may be produced by adding gypsum produced by the method for producing gypsum of the present invention and a small amount of mixed components to cement clinker. In addition, to the cement slag produced by using the gypsum produced by the method for producing gypsum of the present invention as one of the raw materials for dissolving slag, gypsum produced by the method for producing gypsum of the present invention or other gypsum may be added A small amount of ingredients are mixed to make a cement composition.
另外，當廢硫酸中所含有的重金屬為鐵時，除通過本發明的石膏的製造方法所製造的石膏以外，本發明的水泥組成物的製造方法可進而使用本發明的石膏的製造方法的步驟（C）中所析出的氫氧化鐵來製造水泥組成物。例如，作為水泥組成物的製造中所使用的水泥溶渣的溶渣原料之一，也可以使用步驟（C）中所析出的氫氧化鐵或者由該氫氧化鐵所製作的鐵或鐵化合物。 [實施例]In addition, when the heavy metal contained in the waste sulfuric acid is iron, in addition to the gypsum produced by the method for producing gypsum of the present invention, the method for producing the cement composition of the present invention can further use the steps of the method for producing gypsum of the present invention The iron hydroxide precipitated in (C) is used to produce a cement composition. For example, as one of the slag-dissolving raw materials for the cement slag used in the production of the cement composition, the iron hydroxide precipitated in the step (C) or iron or iron compounds produced from the iron hydroxide may be used. [Example]
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。Next, the present invention will be described in more detail with examples, but the present invention is not limited by these examples.
[測定及評價] 如以下般測定及評價實施例及比較例的石膏。 （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，或選自由氫氧化鈉、氫氧化鉀及氫氧化鎂所組成的群組中的至少一種的廢硫酸的pH。 （2）析出物的鑒定 使用X射線繞射裝置（帕納科（PANalytical）公司製造，商品名：X'Pert Pro），進行向廢硫酸中添加鈣源，或選自由氫氧化鈉、氫氧化鉀及氫氧化鎂所組成的群組中的至少一種後從廢硫酸中析出的析出物的鑒定。 （3）析出物中的重金屬的含量 使用能量分散型螢光X射線分析裝置（斯派克（SPECTRO）公司製造，商品名：XEPOS），測定向廢硫酸中添加鈣源，或選自由氫氧化鈉、氫氧化鉀及氫氧化鎂所組成的群組中的至少一種後從廢硫酸中析出的析出物中的鐵、鋅及鉻的含量。 （4）濾液中的SO4 2- 的含量 使用離子色譜裝置（戴安（Dionex）公司製造，商品名：ICS-2000），測定對廢硫酸進行過濾所獲得的濾液中的SO4 2- 的含量。 （5）析出物的顏色 以目視觀察對廢硫酸進行過濾所獲得的析出物的顏色。[Measurement and Evaluation] The gypsum of Examples and Comparative Examples was measured and evaluated as follows. (1) The pH of waste sulfuric acid was measured using a pH meter (Horiba Manufacturing Co., Ltd., trade name: pH meter D-51), pH electrode (Horiba Manufacturing Co., Ltd., trade name: Sleeve Touph electrode 9681-10D) The pH of waste sulfuric acid to which a calcium source is added, or at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, and magnesium hydroxide. (2) The identification of precipitates is carried out using an X-ray diffraction device (made by PANalytical, trade name: X'Pert Pro) to add a calcium source to waste sulfuric acid, or selected from sodium hydroxide, hydroxide Identification of precipitates precipitated from waste sulfuric acid after at least one of the group consisting of potassium and magnesium hydroxide. (3) The content of heavy metals in the precipitates was measured using an energy-dispersed fluorescent X-ray analyzer (manufactured by SPECTRO, trade name: XEPOS). The calcium source was added to the waste sulfuric acid, or selected from sodium hydroxide , At least one of the group consisting of potassium hydroxide and magnesium hydroxide, and the content of iron, zinc and chromium in the precipitate precipitated from the waste sulfuric acid. (4) The content of SO 4 2- in the filtrate was measured by using an ion chromatography device (made by Dionex, trade name: ICS-2000), and the SO 4 2- in the filtrate obtained by filtering waste sulfuric acid content. (5) Color of precipitates The color of the precipitates obtained by filtering waste sulfuric acid was visually observed.
[實施例1～實施例7及比較例1～比較例5的析出物的製作] 一面使用所述pH計測定pH，一面以pH變成0.5的方式向1000 mL的廢硫酸中添加碳酸鈣漿料，並攪拌3小時。繼而，一面進行攪拌，一面進而向所述廢硫酸中一點點地添加碳酸鈣漿料。而且，當使廢硫酸的pH的值變成表1中所示的規定值而結束時，對30 mL的廢硫酸進行採樣。對所採樣的廢硫酸進行過濾而獲得所採樣的廢硫酸的析出物及濾液。再者，碳酸鈣漿料通過向1 L的水中添加100 g的碳酸鈣來製作。另外，添加碳酸鈣前的廢硫酸中的Fe的含量為5.8質量%，鋅的含量為3300 mg/kg，鉻的含量為150 mg/kg，SO4 2- 的含量為19.4質量%。[Preparation of precipitates in Examples 1 to 7 and Comparative Examples 1 to 5] While measuring the pH using the pH meter, a calcium carbonate slurry was added to 1000 mL of waste sulfuric acid so that the pH became 0.5 And stir for 3 hours. Then, while stirring, calcium carbonate slurry was added to the waste sulfuric acid little by little. Then, when the pH value of the waste sulfuric acid was changed to the predetermined value shown in Table 1 and ended, 30 mL of waste sulfuric acid was sampled. The waste sulfuric acid sampled is filtered to obtain the precipitates and filtrate of the waste sulfuric acid sampled. Furthermore, the calcium carbonate slurry was prepared by adding 100 g of calcium carbonate to 1 L of water. In addition, the content of Fe in the waste sulfuric acid before adding calcium carbonate was 5.8% by mass, the content of zinc was 3300 mg/kg, the content of chromium was 150 mg/kg, and the content of SO 4 2- was 19.4% by mass.
[實施例8及實施例9的析出物的製作] 在所述碳酸鈣漿料的添加中，當廢硫酸的pH變成2.0時分離取出200 mL的廢硫酸並進行過濾，向所獲得的濾液中添加氫氧化鈉水溶液直至廢硫酸的pH變成6.5為止，而製成實施例8的廢硫酸。對實施例8的廢硫酸進行過濾，由此獲得實施例8的析出物。向殘留的濾液中添加氯化鈣水溶液後進行攪拌，而製成實施例9的廢硫酸。對實施例9的廢硫酸進行過濾而獲得實施例9的析出物。[Preparation of precipitates in Example 8 and Example 9] In the addition of the calcium carbonate slurry, when the pH of the waste sulfuric acid became 2.0, 200 mL of the waste sulfuric acid was separated and filtered, and the resulting filtrate was added to the filtrate An aqueous solution of sodium hydroxide was added until the pH of the waste sulfuric acid became 6.5 to prepare waste sulfuric acid of Example 8. The waste sulfuric acid of Example 8 was filtered, thereby obtaining the precipitate of Example 8. A calcium chloride aqueous solution was added to the remaining filtrate, followed by stirring to obtain waste sulfuric acid of Example 9. The waste sulfuric acid of Example 9 was filtered to obtain the precipitate of Example 9.
[測定結果及評價結果] 將實施例1～實施例7的所採樣的廢硫酸及比較例1～比較例5的所採樣的廢硫酸的評價結果示於表1中，將實施例8及實施例9的廢硫酸的評價結果示於表2中。[Measurement results and evaluation results] The evaluation results of the sampled waste sulfuric acid of Examples 1 to 7 and the sampled waste sulfuric acid of Comparative Examples 1 to 5 are shown in Table 1, and Example 8 and implementation The evaluation results of the waste sulfuric acid of Example 9 are shown in Table 2.
[表1] 表1 實施例1～實施例7及比較例1～比較例5的評價結果
[表2] 表2 實施例8及實施例9的評價結果
通過對實施例1～實施例7與比較例1～比較例5進行比較，可知通過使向廢硫酸中添加碳酸鈣漿料來使石膏析出時的pH變成3.0以下，可降低所析出的石膏中的鐵成分、鋅成分及鉻成分的含量。另外，由於實施例1～實施例5的析出物的顏色為白色，因此也可知所析出的石膏中的鐵成分的含量低。進而，通過對添加碳酸鈣漿料前的廢硫酸中的SO4 2- 的含量與實施例2～實施例7的濾液中的SO4 2- 的含量進行比較，可知通過使向廢硫酸中添加碳酸鈣漿料來使廢硫酸的pH變成1.0以上，廢硫酸中的大部分SO4 2- 被轉化成石膏。另外，通過實施例8，可知向廢硫酸中添加鈣源來使廢硫酸的pH變成3.0以下並使石膏析出後，向廢硫酸中添加選自由氫氧化鈉、氫氧化鉀及氫氧化鎂所組成的群組中的至少一種來使廢硫酸的pH變成3.5以上、10.0以下，由此可使廢硫酸中的鐵成分、鋅成分及鉻成分析出。進而，通過實施例9，可知可向使鐵成分、鋅成分及鉻成分析出後的廢硫酸中添加鈣源，而使鐵成分、鋅成分及鉻成分的含量小的石膏析出。By comparing Examples 1 to 7 and Comparative Examples 1 to 5, it was found that by adding calcium carbonate slurry to waste sulfuric acid, the pH at the time of gypsum precipitation becomes 3.0 or less, and the precipitation of gypsum can be reduced Content of iron, zinc and chromium. In addition, since the color of the precipitates of Examples 1 to 5 is white, it can also be seen that the content of the iron component in the precipitated gypsum is low. Furthermore, by comparing the content of SO 4 2- in the spent sulfuric acid before addition of calcium carbonate slurry of Example 4 2- content of filtrate to Example 2 in 7 SO, found by adding sulfuric acid to the spent The calcium carbonate slurry changes the pH of the waste sulfuric acid to 1.0 or more, and most of the SO 4 2- in the waste sulfuric acid is converted into gypsum. In addition, according to Example 8, it is known that adding a calcium source to the waste sulfuric acid to make the pH of the waste sulfuric acid below 3.0 and precipitating gypsum, the waste sulfuric acid is added to a composition selected from the group consisting of sodium hydroxide, potassium hydroxide, and magnesium hydroxide At least one of the groups changes the pH of the waste sulfuric acid to 3.5 or more and 10.0 or less, whereby the iron component, zinc component, and chromium component in the waste sulfuric acid can be analyzed. Furthermore, according to Example 9, it was found that a calcium source was added to the waste sulfuric acid after the iron component, zinc component, and chromium component were analyzed to precipitate gypsum having a small content of the iron component, zinc component, and chromium component.
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