CN106477616B - Method for producing gypsum and method for producing cement composition - Google Patents
Method for producing gypsum and method for producing cement composition Download PDFInfo
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- CN106477616B CN106477616B CN201610427972.8A CN201610427972A CN106477616B CN 106477616 B CN106477616 B CN 106477616B CN 201610427972 A CN201610427972 A CN 201610427972A CN 106477616 B CN106477616 B CN 106477616B
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- gypsum
- sulfuric acid
- waste sulfuric
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- calcium source
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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
-
- 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
-
- 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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- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention provides a method for producing gypsum and a method for producing cement composition. The method for producing gypsum of the present invention comprises: a step (A) of adding a calcium source to the fluorine-containing waste sulfuric acid to precipitate gypsum while maintaining the pH of the waste sulfuric acid at 2.0 or less; a step (B) of separating and removing the gypsum precipitated in the step (A) from the waste sulfuric acid; a step (C) of adding a calcium source to the waste sulfuric acid from which gypsum has been removed in the step (B) and precipitating gypsum while maintaining the pH of the waste sulfuric acid at 2.5 to 4.0; a step (D) of separating and removing the gypsum precipitated in the step (C) from the waste sulfuric acid; a step (E) of adding a calcium source to the waste sulfuric acid from which gypsum has been removed in the step (D) and precipitating gypsum while maintaining the pH of the waste sulfuric acid at 6.0 to 8.0; and (F) separating and removing the gypsum precipitated in the step (E) from the waste sulfuric acid. The method of the present invention is more efficient than previous methods.
Description
Technical Field
The present invention relates to a method for producing gypsum and a method for producing a cement composition.
Background
A method for producing gypsum as a by-product by neutralizing waste sulfuric acid produced in various industrial steps with a calcium compound is widely known. However, the use of waste sulfuric acid containing a large amount of fluorine as gypsum is limited because the fluorine content in gypsum increases only by neutralization treatment. Therefore, conventionally, in order to obtain gypsum having a low fluorine content from waste sulfuric acid containing fluorine, a calcium compound is reacted with sulfuric acid while maintaining the pH in the range of 2.5 ± 0.3, thereby producing gypsum from the waste sulfuric acid (see, for example, patent document 1).
[ Prior art documents ]
[ patent document ]
[ patent document 1] Japanese patent application laid-open No. Hei 9-67118
Disclosure of Invention
[ problems to be solved by the invention ]
However, the method described in patent document 1In the method for producing gypsum from waste sulfuric acid, a lot of SO as a raw material of gypsum remains in the waste sulfuric acid treated for producing gypsum4 2-And further effective utilization of the waste sulfuric acid is desired. Accordingly, an object of the present invention is 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, which uses the gypsum produced by the method for producing gypsum to produce a cement composition.
[ means for solving problems ]
As a result of diligent studies, the present inventors have found that SO in waste sulfuric acid can be more effectively utilized by precipitating gypsum having a high fluorine content from waste sulfuric acid in which gypsum having a low fluorine content is precipitated and separated and removed, thereby reducing the fluorine content in the waste sulfuric acid and further precipitating gypsum from the waste sulfuric acid having a reduced fluorine content4 2-As gypsum, the present invention has been completed. Namely, the present invention is as follows.
[1] A method for producing gypsum, characterized by comprising: a step (A) of adding a calcium source to the fluorine-containing waste sulfuric acid to precipitate gypsum while maintaining the pH of the waste sulfuric acid at 2.0 or less; a step (B) of separating and removing the gypsum precipitated in the step (A) from the waste sulfuric acid; a step (C) of adding a calcium source to the waste sulfuric acid from which gypsum has been removed in the step (B) and precipitating gypsum while maintaining the pH of the waste sulfuric acid at 2.5 to 4.0; a step (D) of separating and removing the gypsum precipitated in the step (C) from the waste sulfuric acid; a step (E) of adding a calcium source to the waste sulfuric acid from which gypsum has been removed in the step (D) and precipitating gypsum while maintaining the pH of the waste sulfuric acid at 6.0 to 8.0; and (F) separating and removing the gypsum precipitated in the step (E) from the waste sulfuric acid.
[2] The method for producing gypsum according to the above [1], comprising: in the step (A), a calcium source is added to the waste sulfuric acid containing fluorine, and gypsum is precipitated while maintaining the pH of the waste sulfuric acid at 1.5 or less.
[3] The method for producing gypsum according to the above [1] or [2], comprising: and (C) adding a calcium source to the waste sulfuric acid from which gypsum has been separated and removed, and precipitating gypsum while maintaining the pH of the waste sulfuric acid at 2.5 to 3.0.
[4] The method for producing gypsum according to any one of [1] to [3], characterized in that: the calcium source used in step (a) is calcium carbonate.
[5] The method for producing gypsum according to any one of [1] to [4], comprising: the calcium source used in step (C) is calcium hydroxide.
[6] The method for producing gypsum according to any one of [1] to [5], characterized in that: the calcium source used in step (E) is calcium hydroxide.
[7] A method for producing a cement composition, characterized by comprising: a cement composition is produced by using at least one of the gypsum separated and removed in the step (B) and the gypsum separated and removed in the step (F) in the method for producing gypsum according to any one of [1] to [6 ].
(Effect of the invention)
According to the present invention, there can be provided a method for producing gypsum capable of utilizing 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.
Detailed Description
[ method for producing Gypsum Fibrosum ]
Hereinafter, a method for producing gypsum of the present invention will be described. The method for producing gypsum of the present invention comprises: a step (A) of adding a calcium source to the fluorine-containing waste sulfuric acid to precipitate gypsum while maintaining the pH of the waste sulfuric acid at 2.0 or less; a step (B) of separating and removing the gypsum precipitated in the step (A) from the waste sulfuric acid; a step (C) of adding a calcium source to the waste sulfuric acid from which gypsum has been removed in the step (B) and precipitating gypsum while maintaining the pH of the waste sulfuric acid at 2.5 to 4.0; a step (D) of separating and removing the gypsum precipitated in the step (C) from the waste sulfuric acid; a step (E) of adding a calcium source to the waste sulfuric acid from which gypsum has been removed in the step (D) and precipitating gypsum while maintaining the pH of the waste sulfuric acid at 6.0 to 8.0; and (F) separating and removing the gypsum precipitated in the step (E) from the waste sulfuric acid.
Step (A)
In the step (a), a calcium source is added to the waste sulfuric acid containing fluorine to precipitate gypsum while maintaining the pH of the waste sulfuric acid at 2.0 or less.
(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, SO in the exhaust gas of a nonferrous metal refining furnace for recovering a sulfide concentrate as a raw material2Produced waste sulfuric acid. The exhaust gas contains fluorine, and therefore the spent sulfuric acid also contains fluorine.
(calcium source)
The calcium source used in step (a) is not particularly limited as long as it is a compound containing calcium and various materials containing these compounds as a main component, and is other than gypsum. Examples of the calcium source include: calcium oxide, calcium hydroxide, calcium carbonate, calcium phosphate, and the like. In addition, waste with a large calcium content, such as shells or raw concrete sludge (concoret sludge), may be used as the calcium source. These calcium sources may be used singly or in combination of two or more. Among these calcium sources, the preferred calcium source is calcium carbonate. Further, the calcium source in a powder state may be added to the waste sulfuric acid, or the calcium source in a slurry state may be added to the waste sulfuric acid.
(amount of calcium source added)
The amount of the calcium source to be added is controlled so that the pH of the waste sulfuric acid to which the calcium source is added is maintained at 2.0 or less, preferably 1.5 or less.
(Gypsum)
The gypsum separated out in the step (A) is dihydrate gypsum. Since fluorine in the waste sulfuric acid is not precipitated but remains in the waste sulfuric acid, the content of fluorine in the gypsum precipitated in the step (a) is small.
(pH of waste sulfuric acid)
In the step (a), the pH of the waste sulfuric acid at the time of precipitating gypsum is maintained at 2.0 or less, preferably 1.5 or less by adding a calcium source to the waste sulfuric acid. When the pH of the waste sulfuric acid is more than 2.0, the amount of calcium fluoride precipitated together with gypsum increases, and the fluorine content in the gypsum increases. The lower limit of the pH of the waste sulfuric acid when the gypsum is precipitated by adding a calcium source to the waste sulfuric acid is not particularly limited. For example, the lower limit of the pH of the spent sulfuric acid is 1.0.
(Water)
In the step (a), water may be added to the waste sulfuric acid to adjust the viscosity of the waste sulfuric acid to which the calcium source is added. Examples of water that can be used in the method for producing gypsum of the present invention include: ion exchange water, pure water, distilled water, tap water, and the like. These water may be used singly or in combination of two or more. In addition, water may be added to the waste sulfuric acid in a step other than the step (a).
Step (B)
In step (B), the gypsum precipitated in step (a) is separated and removed from the spent sulfuric acid.
(separation and removal)
The gypsum can be separated and removed from the waste sulfuric acid by precipitating the gypsum, or the gypsum can be separated and removed from the waste sulfuric acid by filtering the waste sulfuric acid containing the gypsum. Further, the gypsum may be separated and removed from the waste sulfuric acid by a separation method using a solid-liquid separator such as a liquid separator, a decanter, a centrifuge, or a filter press. These separation and removal methods may be carried out alone or in combination of two or more.
Step (C)
In the step (C), a calcium source is added to the waste sulfuric acid from which gypsum has been removed in the step (B), and gypsum is precipitated while maintaining the pH of the waste sulfuric acid at 2.5 to 4.0.
(waste sulfuric acid)
The waste sulfuric acid used in the step (C) is the waste sulfuric acid from which gypsum is separated in the step (B).
(calcium source)
The calcium source used in step (C) is not particularly limited as long as it is a compound containing calcium and various materials containing these compounds as a main component, and is other than gypsum. Examples of the calcium source include: calcium oxide, calcium hydroxide, calcium carbonate, calcium phosphate, and the like. In addition, waste with a large calcium content, such as shells or raw concrete sludge, may be used as the calcium source. These calcium sources may be used singly or in combination of two or more. Among these calcium sources, the preferred calcium source is calcium hydroxide. Further, the calcium source in a powder state may be added to the waste sulfuric acid, or the calcium source in a slurry state may be added to the waste sulfuric acid.
(amount of calcium source added)
The amount of the calcium source added is controlled so that the pH of the waste sulfuric acid to which the calcium source is added is maintained at 2.5 to 4.0, preferably 2.5 to 3.0.
(Gypsum)
The gypsum separated out in the step (C) is dihydrate gypsum. Most of the fluorine in the waste sulfuric acid is precipitated as calcium fluoride together with gypsum, and therefore the content of fluorine in the gypsum precipitated in step (C) becomes large, and the content of fluorine in the waste sulfuric acid becomes small.
The gypsum precipitated in step (C) may also be discarded. However, the cement composition contains fluorine as an essential minor component. Therefore, the gypsum precipitated in the step (C) can be used as a raw material for such a cement composition.
(pH of waste sulfuric acid)
In the step (C), the pH of the waste sulfuric acid at the time of precipitating gypsum is maintained at 2.5 to 4.0, preferably 2.5 to 3.0 by adding a calcium source to the waste sulfuric acid. If the pH of the waste sulfuric acid is less than 2.5, most of fluorine in the waste sulfuric acid may not be precipitated as calcium fluoride together with gypsum. In this case, the fluorine content in the waste sulfuric acid after the gypsum precipitated in the step (C) is separated and removed becomes large. In addition, if the pH of the waste sulfuric acid is more than 4.0, the amount of gypsum that can be recovered in step (E) becomes small.
Step (D)
In step (D), the gypsum precipitated in step (C) is separated and removed from the spent sulfuric acid.
(separation and removal)
The description of the separation and removal in step (D) is the same as that in step (B), and therefore, the description of the separation and removal in step (D) is omitted. 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, a polymer flocculant may be added to accelerate the separation.
Step (E)
In the step (E), a calcium source is added to the waste sulfuric acid from which gypsum has been removed in the step (D), and gypsum is precipitated while maintaining the pH of the waste sulfuric acid at 6.0 to 8.0. As a result, SO that is not precipitated as gypsum in the step (A) can be made to be4 2-Further precipitation from the waste sulfuric acid, and the waste sulfuric acid can be more effectively utilized.
(waste sulfuric acid)
The waste sulfuric acid used in the step (E) is the waste sulfuric acid from which gypsum is separated in the step (D).
(calcium source)
The calcium source used in step (E) is not particularly limited as long as it is a calcium-containing compound and various materials containing these compounds as a main component, and is other than gypsum. Examples of the calcium source include: calcium oxide, calcium hydroxide, calcium carbonate, calcium phosphate, and the like. In addition, waste with a large calcium content, such as shells or raw concrete sludge, may be used as the calcium source. These calcium sources may be used singly or in combination of two or more. Among these calcium sources, the preferred calcium source is calcium hydroxide. Further, the calcium source in a powder state may be added to the waste sulfuric acid, or the calcium source in a slurry state may be added to the waste sulfuric acid.
(amount of calcium source added)
The amount of the calcium source is controlled so that the pH of the waste sulfuric acid to which the calcium source is added is maintained at 6.0 to 8.0, preferably 6.5 to 7.5.
(Gypsum)
The gypsum separated out in the step (E) is dihydrate gypsum. As described above, in step (C), most of the fluorine in the waste sulfuric acid is precipitated as calcium fluoride together with gypsum. Therefore, the content of fluorine in the gypsum precipitated in the step (E) becomes small.
(pH of waste sulfuric acid)
In the step (E), the pH of the waste sulfuric acid is maintained at 6.0 to 8.0, preferably 6.5 to 7.5 when the calcium source is added to the waste sulfuric acid. If the pH of the waste sulfuric acid to which the calcium source is added is less than 6.0, there is SO remaining in the waste sulfuric acid4 2-When the pH of the waste sulfuric acid to which the calcium source is added is higher than 8.0, the content of the calcium source remaining without reacting with the waste sulfuric acid may be increased.
Step (F)
In step (F), the gypsum precipitated in step (E) is separated and removed from the waste sulfuric acid.
(separation and removal)
The description of the separation and removal in step (F) is the same as that in step (B), and therefore, the description of the separation and removal in step (F) is omitted. 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). In addition, a polymer flocculant may be added to accelerate the separation.
The waste sulfuric acid from which gypsum is removed in step (F) may be directly treated as a waste liquid. In addition, the waste sulfuric acid from which gypsum is removed in step (F) may be reused for the production of gypsum from the waste sulfuric acid. For example, the waste sulfuric acid from which gypsum is removed in step (F) may be used as a medium for producing a slurry of the calcium source or a medium for adjusting the viscosity of the waste sulfuric acid to which the calcium source is added.
[ method for producing Cement composition ]
The method for producing a cement composition of the present invention uses at least one of the gypsum separated and removed in the step (B) and the gypsum separated and removed in the step (F) in the method for producing a gypsum of the present invention to produce a cement composition. For example, the cement composition can be produced by adding the gypsum separated and removed in the step (B) of the method for producing gypsum of the present invention and a small amount of a mixing component to cement clinker (cement clinker). Further, the cement composition can be produced by adding the gypsum separated and removed in the step (B) of the method for producing gypsum of the present invention or other gypsum to a cement clinker produced using the gypsum separated and removed in the step (B) of the method for producing gypsum of the present invention as one of the clinker raw materials, and a small amount of a mixed component. Further, the gypsum separated and removed in the step (F) in the method for producing gypsum of the present invention may be used instead of the gypsum separated and removed in the step (B), or the gypsum separated and removed in the step (F) in the method for producing gypsum of the present invention may be used together with the gypsum separated and removed in the step (B). Thus, the gypsum produced by the method for producing gypsum of the present invention can be effectively used as a raw material for a cement composition.
[ examples ]
The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
[ measurement and evaluation ]
The gypsum produced by the gypsum production method of examples and the waste sulfuric acid produced in the production were measured and evaluated as follows.
(1) pH of spent sulfuric acid
The pH of the waste sulfuric acid to which the calcium source was added was measured using a pH meter (trade name: pH meter D-51, manufactured by horiba, Ltd.) and a pH electrode (trade name: Sleeve Toup H electrode 9681-10D, manufactured by horiba, Ltd.).
(2) Identification of precipitate
An X-ray diffraction apparatus was used to identify precipitates precipitated from the waste sulfuric acid after adding a calcium source to the waste sulfuric acid.
(3) Fluorine content in the precipitate
The fluorine content in the precipitate precipitated from the waste sulfuric acid after the calcium source was added to the waste sulfuric acid was measured using a combustion type ion chromatography apparatus.
(4) Fluorine content in spent sulfuric acid
The fluorine content in the waste sulfuric acid obtained by filtering the waste sulfuric acid was measured using a flow injection analyzer.
(5) SO in waste sulfuric acid4 2-In an amount of
Measuring the waste obtained by filtering the waste sulfuric acid by using an ion chromatography deviceSO in sulfuric acid4 2-The content of (a).
[ method for producing Gypsum Fibrosum in examples ]
(example 1)
(stage 1)
Calcium carbonate was added to the waste sulfuric acid to make the pH of the waste sulfuric acid 2.0. Then, the waste sulfuric acid is filtered to obtain a precipitate of the waste sulfuric acid and the filtered waste sulfuric acid.
(stage 2)
Calcium hydroxide was added to the filtered waste sulfuric acid obtained in the 1 st stage to bring the pH of the waste sulfuric acid to 3.0. Then, the waste sulfuric acid is filtered to obtain a precipitate of the waste sulfuric acid and the filtered waste sulfuric acid.
(stage 3)
Calcium hydroxide was added to the filtered waste sulfuric acid obtained in the 2 nd stage to bring the pH of the waste sulfuric acid to 6.5. Then, the waste sulfuric acid is filtered to obtain a precipitate of the waste sulfuric acid and the filtered waste sulfuric acid.
[ measurement results and evaluation results ]
The evaluation results of the precipitates and the waste sulfuric acid obtained in the method for producing gypsum of example 1 are shown in table 1.
[ Table 1]
Table 1 method for producing gypsum of example 1
From the evaluation results of example 1, it was found that not only gypsum having a low fluorine content could be obtained in stage 1, but also gypsum having a low fluorine content could be obtained in stage 3. From this, it is understood that the method for producing gypsum of example 1 can more effectively utilize SO in the waste sulfuric acid than the case of using the waste sulfuric acid only in the stage 14 2-。
Claims (4)
1. A method for producing gypsum, characterized by comprising:
a step (A) in which a calcium source is added to a waste sulfuric acid containing fluorine, and gypsum is precipitated while maintaining the pH of the waste sulfuric acid at 2.0 or less;
a step (B) of separating and removing the gypsum precipitated in the step (A) from the waste sulfuric acid;
a step (c) of adding a calcium source to the waste sulfuric acid from which the gypsum has been removed in the step (B), and precipitating the gypsum while maintaining the pH of the waste sulfuric acid at 2.5 to 4.0;
a step (D) of separating and removing the gypsum precipitated in the step (C) from the waste sulfuric acid;
a step (E) of adding a calcium source to the waste sulfuric acid from which the gypsum has been removed in the step (D) and precipitating the gypsum while maintaining the pH of the waste sulfuric acid at 6.0 to 8.0; and
a step (F) of separating and removing the gypsum precipitated in the step (E) from the waste sulfuric acid.
2. The method for producing gypsum according to claim 1, wherein: the step (A) is a step of adding the calcium source to the fluorine-containing waste sulfuric acid to precipitate gypsum while maintaining the pH of the waste sulfuric acid at 1.5 or less.
3. The method for producing gypsum according to claim 1 or 2, characterized in that: and (c) adding the calcium source to the waste sulfuric acid from which the gypsum has been separated and removed, and precipitating the gypsum while maintaining the pH of the waste sulfuric acid at 2.5 to 3.0.
4. A method for producing a cement composition, characterized by comprising: manufacturing a cement composition using at least one of the gypsum separated and removed in the step (B) and the gypsum separated and removed in the step (F) in the manufacturing method of gypsum according to any one of claims 1 to 3.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
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| JP2015-165596 | 2015-08-25 | ||
| JP2015165596A JP6409713B2 (en) | 2015-08-25 | 2015-08-25 | Method for producing gypsum and method for producing cement composition |
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| CN106477616B true CN106477616B (en) | 2020-05-19 |
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| JP (1) | JP6409713B2 (en) |
| KR (1) | KR102474446B1 (en) |
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| JP6975406B2 (en) * | 2018-02-16 | 2021-12-01 | 三菱マテリアル株式会社 | A method for controlling the amount of aluminum dissolved and a method for producing gypsum based on the method. |
| KR102038327B1 (en) * | 2018-03-26 | 2019-10-30 | 신유근 | Manufacturing method of Neutralized gypsum for Cement using Sulfuric acid wastewater |
| KR102156734B1 (en) * | 2019-02-15 | 2020-09-17 | 주식회사 티아이 | Methods To manufacture alkaline waste neutralizer of solids containing large amounts of active calcium oxide by mixing raw lime with bauxite residues and neutralizing sulfuric acid as industrial materials such as cement condensation retardant |
| KR102285409B1 (en) * | 2021-01-21 | 2021-08-03 | 이충수 | A gypsum manufacturing system using waste sulfuric acid and gypsum manufactured by the system |
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| JPH0967118A (en) * | 1995-08-28 | 1997-03-11 | Sumitomo Metal Mining Co Ltd | Production of gypsum from sulfuric acid waste liquid |
| CN101580265A (en) * | 2009-04-08 | 2009-11-18 | 王嘉兴 | Method for preparing gypsum and dry ice from limestone and waste sulfuric acid |
| CN102030354A (en) * | 2010-10-18 | 2011-04-27 | 中蓝连海设计研究院 | Treatment method of waste sulfuric acid |
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| US4374810A (en) * | 1978-06-01 | 1983-02-22 | Agrico Chemical Company | Recovery of fluorine from pond water of wet process phosphoric acid plants and recycling of defluorinated water |
| JPS5934644B2 (en) * | 1980-06-13 | 1984-08-23 | 日本鉱業株式会社 | Fluorine removal method from waste sulfuric acid |
| JPH0910548A (en) * | 1995-06-29 | 1997-01-14 | Mitsubishi Heavy Ind Ltd | Treatment of drain containing fluorine |
| JPH11228134A (en) * | 1998-02-16 | 1999-08-24 | Sumitomo Metal Mining Co Ltd | Production of gypsum dihydrate |
| JP4156390B2 (en) * | 2003-01-31 | 2008-09-24 | 株式会社トクヤマ | Cement production method |
| TW200846096A (en) * | 2006-10-23 | 2008-12-01 | Sumitomo Osaka Cement Co Ltd | Method of treating asbestos-containing waste material |
| JP5138737B2 (en) * | 2010-06-29 | 2013-02-06 | パンパシフィック・カッパー株式会社 | Method for producing waste acid gypsum |
| JP5968524B2 (en) * | 2013-04-25 | 2016-08-10 | 三菱重工業株式会社 | Water treatment method and water treatment system |
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- 2016-06-16 KR KR1020160075013A patent/KR102474446B1/en active IP Right Grant
- 2016-06-17 TW TW105119036A patent/TWI694970B/en active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0967118A (en) * | 1995-08-28 | 1997-03-11 | Sumitomo Metal Mining Co Ltd | Production of gypsum from sulfuric acid waste liquid |
| CN101580265A (en) * | 2009-04-08 | 2009-11-18 | 王嘉兴 | Method for preparing gypsum and dry ice from limestone and waste sulfuric acid |
| CN102030354A (en) * | 2010-10-18 | 2011-04-27 | 中蓝连海设计研究院 | Treatment method of waste sulfuric acid |
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| TWI694970B (en) | 2020-06-01 |
| CN106477616A (en) | 2017-03-08 |
| JP6409713B2 (en) | 2018-10-24 |
| KR102474446B1 (en) | 2022-12-06 |
| TW201708114A (en) | 2017-03-01 |
| KR20170024523A (en) | 2017-03-07 |
| JP2017043503A (en) | 2017-03-02 |
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