JP2016172682A - Manufacturing method of gypsum and manufacturing method of cement composition - Google Patents
Manufacturing method of gypsum and manufacturing method of cement composition Download PDFInfo
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- JP2016172682A JP2016172682A JP2015224641A JP2015224641A JP2016172682A JP 2016172682 A JP2016172682 A JP 2016172682A JP 2015224641 A JP2015224641 A JP 2015224641A JP 2015224641 A JP2015224641 A JP 2015224641A JP 2016172682 A JP2016172682 A JP 2016172682A
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- sulfuric acid
- gypsum
- waste sulfuric
- hydroxide
- manufacturing
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- 239000010440 gypsum Substances 0.000 title claims abstract description 118
- 229910052602 gypsum Inorganic materials 0.000 title claims abstract description 118
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 52
- 239000004568 cement Substances 0.000 title claims abstract description 26
- 239000000203 mixture Substances 0.000 title claims abstract description 26
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 299
- 239000002699 waste material Substances 0.000 claims abstract description 143
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 46
- 239000011575 calcium Substances 0.000 claims abstract description 45
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 41
- 238000000151 deposition Methods 0.000 claims abstract description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 57
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 57
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 18
- 239000000347 magnesium hydroxide Substances 0.000 claims description 18
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 15
- 150000004692 metal hydroxides Chemical class 0.000 claims description 10
- 238000000034 method Methods 0.000 abstract description 28
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 57
- 229910052742 iron Inorganic materials 0.000 description 28
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 20
- 238000000926 separation method Methods 0.000 description 17
- 239000002244 precipitate Substances 0.000 description 15
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 10
- 229910000019 calcium carbonate Inorganic materials 0.000 description 10
- 229910052804 chromium Inorganic materials 0.000 description 10
- 239000011651 chromium Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 229910052725 zinc Inorganic materials 0.000 description 10
- 239000011701 zinc Substances 0.000 description 10
- 229910001868 water Inorganic materials 0.000 description 9
- 239000000706 filtrate Substances 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 229910052749 magnesium Inorganic materials 0.000 description 5
- 239000011591 potassium Substances 0.000 description 5
- 229910052700 potassium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 235000014413 iron hydroxide Nutrition 0.000 description 4
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- -1 and in step (A) Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910000358 iron sulfate Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- HNSDLXPSAYFUHK-UHFFFAOYSA-N 1,4-bis(2-ethylhexyl) sulfosuccinate Chemical compound CCCCC(CC)COC(=O)CC(S(O)(=O)=O)C(=O)OCC(CC)CCCC HNSDLXPSAYFUHK-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229940043430 calcium compound Drugs 0.000 description 1
- 150000001674 calcium compounds Chemical class 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 1
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 150000004683 dihydrates Chemical class 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000011505 plaster Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
Classifications
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Civil Engineering (AREA)
- Removal Of Specific Substances (AREA)
Abstract
Description
本発明は、重金属を含む廃硫酸を有効利用して石膏を製造する石膏の製造方法およびその石膏の製造方法によって製造された石膏を用いてセメント組成物を製造するセメント組成物の製造方法に関する。 The present invention relates to a method for producing gypsum for producing gypsum by effectively using waste sulfuric acid containing heavy metals, and a method for producing a cement composition using gypsum produced by the method for producing gypsum.
様々な工業生産の工程で発生する硫酸をカルシウム化合物によって中和処理し、その副産物として石膏を製造する方法は広く知られている。しかし重金属を多く含む廃硫酸については、石膏中の重金属の含有量も高くなってしまうため石膏としての利用は限定的となってしまう。このため、重金属を含む廃硫酸から重金属の含有量が低い石膏を製造する様々な方法が提案されている。たとえば、重金属として鉄分を含む廃硫酸を使用して鉄分の含有量が低い石膏を製造する場合、予め鉄分を削減する処理を施して廃硫酸を用いるか、あるいは鉄が析出しない低ｐＨ域の反応に止めて石膏を製造していた。鉄分を含有する廃硫酸から鉄分を減少させることによって、鉄分を含有する廃硫酸を処理する方法として、たとえば、特許文献１に記載の廃硫酸の処理方法および特許文献２に記載の廃硫酸の処理方法が従来技術として知られている。特許文献１に記載の廃硫酸の処理方法によれば、鉄分を含む廃硫酸を冷却し、硫酸第一鉄を析出させて分離除去し、廃硫酸中の鉄分濃度を低下させる。また、特許文献２に記載の廃硫酸の処理方法によれば、廃硫酸に濃硫酸を混入することにより、その廃硫酸の硫酸濃度を非常に高くして、鉄分の溶解度を低下させ、鉄分の溶解している廃硫酸から硫酸鉄結晶を析出させ、その硫酸鉄結晶を除去することによって、廃硫酸に溶解している鉄分を削減する。 A method of neutralizing sulfuric acid generated in various industrial production processes with a calcium compound and producing gypsum as a byproduct is widely known. However, the use of waste sulfuric acid containing a large amount of heavy metal as a gypsum is limited because the content of heavy metal in the gypsum increases. For this reason, various methods for producing gypsum having a low content of heavy metal from waste sulfuric acid containing heavy metal have been proposed. For example, when producing gypsum with a low iron content using waste sulfuric acid containing iron as a heavy metal, use waste sulfuric acid with a treatment to reduce iron content in advance, or a reaction in a low pH range where iron does not precipitate The gypsum was produced. As a method of treating the waste sulfuric acid containing iron by reducing the iron content from the waste sulfuric acid containing iron, for example, the method for treating waste sulfuric acid described in Patent Document 1 and the treatment of waste sulfuric acid described in Patent Document 2 The method is known as prior art. According to the method for treating waste sulfuric acid described in Patent Document 1, waste sulfuric acid containing iron is cooled, ferrous sulfate is precipitated and separated and removed, and the concentration of iron in the waste sulfuric acid is reduced. Moreover, according to the processing method of waste sulfuric acid described in Patent Document 2, by mixing concentrated sulfuric acid with waste sulfuric acid, the sulfuric acid concentration of the waste sulfuric acid is made extremely high, the solubility of iron is reduced, and the iron content is reduced. The iron content dissolved in the waste sulfuric acid is reduced by precipitating iron sulfate crystals from the dissolved waste sulfuric acid and removing the iron sulfate crystals.
しかし、廃硫酸の処理方法によって鉄分を削減した廃硫酸を用いて石膏を製造した場合、石膏の製造が煩雑になってしまうという問題がある。また鉄分含有量を石膏製造に十分なレベルまで下げることが難しい場合も生じる可能性がある。一方、鉄が析出してこない低ｐＨ域の反応に止めて石膏を製造する場合は、石膏を製造できる量が少なくなってしまい、硫酸を十分に利用することができない。そこで、本発明は、鉄分を含む廃硫酸に限らず、重金属を含む廃硫酸をそのまま使用して重金属の含有量が低い石膏を製造できる石膏の製造方法およびその石膏の製造方法により製造された石膏を用いてセメント組成物を製造するセメント組成物の製造方法を提供することを目的とする。 However, when gypsum is produced using waste sulfuric acid whose iron content is reduced by the waste sulfuric acid treatment method, there is a problem that the production of gypsum becomes complicated. It may also be difficult to reduce the iron content to a level sufficient for gypsum production. On the other hand, when producing gypsum by stopping the reaction in a low pH range where iron does not precipitate, the amount of gypsum that can be produced decreases and sulfuric acid cannot be fully utilized. Therefore, the present invention is not limited to waste sulfuric acid containing iron, but a gypsum produced by a method for producing gypsum that can produce gypsum with a low content of heavy metal using waste sulfuric acid containing heavy metals as they are, It aims at providing the manufacturing method of the cement composition which manufactures a cement composition using.
本発明者等は、鋭意研究を行った結果、重金属を含む廃硫酸にそのままカルシウム源を添加して石膏を析出させたときの廃硫酸のｐＨを調整することによって、析出する石膏中の重金属の含有量を低くすることができることを見出し、本発明を完成させた。すなわち、本発明は以下のとおりである。
［１］重金属を含む廃硫酸にカルシウム源を添加して石膏を析出させる工程（Ａ）を含み、工程（Ａ）では、廃硫酸にカルシウム源を添加して石膏を析出させたときの廃硫酸のｐＨを３．０以下にする石膏の製造方法。
［２］工程（Ａ）で析出した石膏を廃硫酸から分離除去する工程（Ｂ）、および水酸化ナトリウム、水酸化カリウムおよび水酸化マグネシウムからなる群から選択される少なくとも１種を、石膏を分離除去した廃硫酸に添加して重金属の水酸化物を析出させる工程（Ｃ）をさらに含み、工程（Ｃ）では、水酸化ナトリウム、水酸化カリウムおよび水酸化マグネシウムからなる群から選択される少なくとも１種を廃硫酸に添加して水酸化物を析出させたときの廃硫酸のｐＨを３．５以上１０．０以下にする上記［１］に記載の石膏の製造方法。
［３］工程（Ｃ）で析出した水酸化物を廃硫酸から分離除去する工程（Ｄ）、および水酸化物を分離除去した廃硫酸にカルシウム源を添加して石膏を析出させる工程（Ｅ）をさらに含む上記［２］に記載の石膏の製造方法。
［４］上記［１］〜［３］のいずれか１つに記載の石膏の製造方法により石膏を製造する工程、および石膏を製造する工程で製造された石膏を用いてセメント組成物を製造する工程を含むセメント組成物の製造方法。
As a result of diligent research, the present inventors, as a result of adjusting the pH of the waste sulfuric acid when adding the calcium source to the waste sulfuric acid containing heavy metal and precipitating the gypsum, the heavy metal in the precipitated gypsum. The present inventors have found that the content can be lowered and completed the present invention. That is, the present invention is as follows.
[1] including a step (A) of adding a calcium source to waste sulfuric acid containing heavy metal to precipitate gypsum, and in step (A), waste sulfuric acid when adding a calcium source to waste sulfuric acid to precipitate gypsum A method for producing gypsum having a pH of 3.0 or less.
[2] Separate the gypsum precipitated in the step (A) from the waste sulfuric acid (B) and separate at least one selected from the group consisting of sodium hydroxide, potassium hydroxide and magnesium hydroxide. The method further includes a step (C) of adding to the removed waste sulfuric acid to precipitate a heavy metal hydroxide, wherein the step (C) includes at least one selected from the group consisting of sodium hydroxide, potassium hydroxide and magnesium hydroxide. The method for producing gypsum according to the above [1], wherein the pH of the waste sulfuric acid when the seed is added to the waste sulfuric acid to precipitate a hydroxide is 3.5 or more and 10.0 or less.
[3] A step (D) of separating and removing the hydroxide precipitated in step (C) from the waste sulfuric acid, and a step of depositing gypsum by adding a calcium source to the waste sulfuric acid from which the hydroxide has been separated and removed (E) The method for producing gypsum according to the above [2], further comprising:
[4] A cement composition is produced using the gypsum produced in the gypsum production method according to any one of the above [1] to [3] and the gypsum produced in the gypsum production step. The manufacturing method of the cement composition including a process.
本発明によれば、重金属を含む廃硫酸をそのまま使用して重金属の含有量が低い石膏を製造することができる石膏の製造方法およびその石膏の製造方法により製造された石膏を用いてセメント組成物を製造するセメント組成物の製造方法を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the cement composition using the gypsum manufactured by the manufacturing method of the gypsum which can manufacture the gypsum with low content of heavy metal using the waste sulfuric acid containing a heavy metal as it is, and the manufacturing method of the gypsum The manufacturing method of the cement composition which manufactures can be provided.
［石膏の製造方法］
以下、本発明の石膏の製造方法を説明する。本発明の石膏の製造方法は、重金属を含む廃硫酸にカルシウム源を添加して石膏を析出させる工程（Ａ）を含む。
[Gypsum production method]
Hereinafter, the manufacturing method of the gypsum of this invention is demonstrated. The manufacturing method of gypsum of this invention includes the process (A) which adds a calcium source to the waste sulfuric acid containing a heavy metal, and precipitates gypsum.
工程（Ａ）
工程（Ａ）では、重金属を含む廃硫酸にカルシウム源を添加して石膏を析出させる。
Process (A)
In the step (A), a calcium source is added to waste sulfuric acid containing heavy metals to precipitate gypsum.
（重金属）
本発明の重金属は、比重が５を超える金属であり、重金属には、たとえば、鉄、亜鉛、クロム、鉛、カドミウム、銅、スズ、水銀、ニッケルおよびコバルトなどが挙げられる。廃硫酸には、鉄、亜鉛およびクロムが含まれていることが多い。
(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. Waste sulfuric acid often contains iron, zinc and chromium.
（廃硫酸）
工程（Ａ）で使用される廃硫酸は重金属を含むものであれば、とくに限定されない。重金属を含む廃硫酸は、たとえば、鋼板の酸洗に使用した後の硫酸および銅精錬で発生する硫酸などである。
(Waste sulfuric acid)
The waste sulfuric acid used in the step (A) is not particularly limited as long as it contains heavy metals. The waste sulfuric acid containing a heavy metal is, for example, sulfuric acid after being used for pickling of a steel plate, sulfuric acid generated by copper refining, or the like.
（カルシウム源）
工程（Ａ）で使用されるカルシウム源は、カルシウムを含む化合物およびそれらを主成分とする各種材料であり、石膏以外のものであれば、とくに限定されない。カルシウム源には、たとえば、酸化カルシウム、水酸化カルシウム、炭酸カルシウム、リン酸カルシウム、フッ化カルシウムおよび塩化カルシウムなどが挙げられる。これらは、１種を単独で、または２種以上を組み合わせて使用することができる。これらの中で、好ましいカルシウム源には、酸化カルシウムおよび炭酸カルシウムなどが挙げられる。また、貝殻や生コンスラッジなどのカルシウムの含有量の大きな廃棄物をカルシウム源として使用してもよい。これらの例示されたカルシウム源は、１種を単独で、または２種以上を組み合わせて使用することができる。
(Calcium source)
The calcium source used in the step (A) is a compound containing calcium and various materials mainly containing them, 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, calcium phosphate, calcium fluoride and calcium chloride. These can be used individually by 1 type or in combination of 2 or more types. Among these, preferable calcium sources include calcium oxide and calcium carbonate. Moreover, wastes with a high calcium content such as shells and raw consludge may be used as the calcium source. These exemplified calcium sources can be used individually by 1 type or in combination of 2 or more types.
（カルシウム源の添加量）
カルシウム源の添加量は、カルシウム源を添加した廃硫酸のｐＨが３.０以下、好ましくは２．５以下、より好ましくは２．０以下になる範囲に収まるよう、制御する。
(Amount of calcium source added)
The addition amount of the calcium source is controlled so that the pH of the waste sulfuric acid to which the calcium source is added is within a range of 3.0 or less, preferably 2.5 or less, more preferably 2.0 or less.
（石膏）
工程（Ａ）で析出する石膏は、二水石膏および／または無水石膏である。廃硫酸中の重金属はほとんど析出せずに、廃硫酸中に残っているので、工程（Ａ）で析出する石膏中の重金属の含有量は小さい。
(plaster)
The gypsum precipitated in the step (A) is dihydrate gypsum and / or anhydrous gypsum. Since the heavy metal in the waste sulfuric acid is hardly precipitated and remains in the waste sulfuric acid, the content of heavy metal in the gypsum deposited in the step (A) is small.
工程（Ａ）では、廃硫酸にカルシウム源を添加して石膏を析出させたときの廃硫酸のｐＨを３．０以下にし、好ましくは２．５以下にし、より好ましくは２．０以下にする。廃硫酸のｐＨが３．０よりも大きいと、石膏と一緒に析出する重金属の化合物の析出量が高くなり、石膏中の重金属の含有量が高くなってしまう。また、廃硫酸にカルシウム源を添加して石膏を析出させたときの廃硫酸のｐＨの下限値は、石膏が析出すれば、とくに限定されない。廃硫酸のｐＨの下限値は、たとえば１．０である。 In step (A), the pH of the waste sulfuric acid when gypsum is precipitated by adding a calcium source to the waste sulfuric acid is 3.0 or less, preferably 2.5 or less, more preferably 2.0 or less. . If the pH of the waste sulfuric acid is greater than 3.0, the amount of heavy metal compound precipitated together with the gypsum increases, and the content of heavy metal in the gypsum increases. Moreover, the lower limit of pH of waste sulfuric acid when adding a calcium source to waste sulfuric acid and precipitating gypsum will not be specifically limited if gypsum precipitates. The lower limit of the pH of the waste sulfuric acid is 1.0, for example.
（水）
工程（Ａ）では、カルシウム源を添加した廃硫酸の粘度などを調整する目的で、混合物に水を添加してもよい。本発明の石膏の製造方法で使用することができる水には、たとえば、イオン交換水、純水、蒸留水および水道水などが挙げられる。これらは、１種を単独で、または２種以上を組み合わせて使用することができる。また、後述の工程（Ｆ）で石膏を分離除去したときに発生するろ液を処理して得た排水を利用してもよい。
(water)
In the step (A), water may be added to the mixture for the purpose of adjusting 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-exchanged water, pure water, distilled water, and tap water. These can be used individually by 1 type or in combination of 2 or more types. Moreover, you may utilize the waste_water | drain obtained by processing the filtrate which generate | occur | produces when the gypsum is separated and removed by the below-mentioned process (F).
本発明の石膏の製造方法は、工程（Ａ）で析出した石膏を廃硫酸から分離除去する工程（Ｂ）、および水酸化ナトリウム、水酸化カリウムおよび水酸化マグネシウムからなる群から選択される少なくとも１種を、石膏を分離除去した廃硫酸に添加して重金属の水酸化物を析出させる工程（Ｃ）をさらに含んでもよい。 The method for producing gypsum of the present invention comprises at least one selected from the group consisting of a step (B) of separating and removing the gypsum precipitated in step (A) from waste sulfuric acid, and sodium hydroxide, potassium hydroxide and magnesium hydroxide. The method may further include a step (C) of adding seeds to the waste sulfuric acid from which the gypsum has been separated and removed to precipitate heavy metal hydroxides.
工程（Ｂ）
工程（Ｂ）では、工程（Ａ）で析出した石膏を廃硫酸から分離除去する。
Process (B)
In the step (B), the gypsum deposited in the step (A) is separated and removed from the waste sulfuric acid.
（分離除去）
石膏を沈降させることによって、廃硫酸から石膏を分離除去してもよいし、石膏を含有する廃硫酸をろ過することによって廃硫酸から石膏を分離除去してもよい。また、液体サイクロン、デカンター、遠心分離機、フィルタープレスなどの固液分離装置を用いる分離方法を採用して廃硫酸から石膏を分離除去してもよい。これらの分離除去方法は、単独で実施してもよいし、２種以上を組み合わせて実施してもよい。
(Separation removal)
The gypsum may be separated and removed from the waste sulfuric acid by settling the gypsum, or the gypsum may be separated and removed from the waste sulfuric acid by filtering the waste sulfuric acid containing gypsum. Alternatively, gypsum may be separated and removed from the waste sulfuric acid by employing a separation method using a solid-liquid separation device such as a liquid cyclone, a decanter, a centrifuge, or a filter press. These separation / removal methods may be carried out singly or in combination of two or more.
工程（Ｃ）
工程（Ｃ）では、水酸化ナトリウム、水酸化カリウムおよび水酸化マグネシウムからなる群から選択される少なくとも１種を、石膏を分離除去した廃硫酸に添加して重金属の水酸化物を析出させる。
Process (C)
In the step (C), at least one selected from the group consisting of sodium hydroxide, potassium hydroxide and magnesium hydroxide is added to waste sulfuric acid from which gypsum has been separated and removed to precipitate heavy metal hydroxides.
（水酸化ナトリウム、水酸化カリウムおよび水酸化マグネシウムからなる群から選択される少なくとも１種）
水酸化ナトリウム、水酸化カリウムおよび水酸化マグネシウムからなる群から選択される少なくとも１種は、廃硫酸中の重金属と反応して重金属の水酸化物を析出させるとともに、廃硫酸中の硫酸と反応して水溶性の硫酸塩を生成する。
(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 reacts with the heavy metal in the waste sulfuric acid to precipitate a heavy metal hydroxide, and reacts with the sulfuric acid in the waste sulfuric acid. To produce water-soluble sulfates.
（廃硫酸のｐＨ）
工程（Ｃ）では、水酸化ナトリウム、水酸化カリウムおよび水酸化マグネシウムからなる群から選択される少なくとも１種を廃硫酸に添加して重金属の水酸化物を析出させたときの廃硫酸のｐＨを、好ましくは３．５以上１０．０以下にし、より好ましくは３．５以上５．０以下となるように水酸化ナトリウム、水酸化カリウムおよび水酸化マグネシウムからなる群から選択される少なくとも１種の添加量を調整する。廃硫酸のｐＨを３．５以上１０．０以下にすることにより、廃硫酸中の重金属の多くを水酸化物として析出させることができる。
(PH of waste sulfuric acid)
In the 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 precipitate the pH of the waste sulfuric acid when the heavy metal hydroxide is precipitated. At least one selected from the group consisting of sodium hydroxide, potassium hydroxide and magnesium hydroxide, preferably from 3.5 to 10.0, more preferably from 3.5 to 5.0 Adjust the amount added. By setting 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.
たとえば、重金属として鉄分を含む廃硫酸から水酸化鉄を析出させる場合は、廃硫酸のｐＨを、好ましくは５.０以上１０.０以下、より好ましくは６.０以上８.０以下となるように水酸化ナトリウム、水酸化カリウムおよび水酸化マグネシウムからなる群から選択される少なくとも１種の添加量を調整してもよい。廃硫酸のｐＨを５.０以上１０.０以下にすることにより、廃硫酸中の鉄の多くを水酸化物として析出させることができる。なお、水酸化ナトリウム、水酸化カリウムおよび水酸化マグネシウムからなる群から選択される少なくとも１種のナトリウム、カリウムおよびマグネシウムは、廃硫酸中にイオンの状態で存在する。このため、析出した上記水酸化物を濾過することにより、析出した水酸化物中のナトリウム、カリウムおよびマグネシウムの含有量を低減させることができ、さらに析出した水酸化物を水で洗浄することにより、析出した水酸化物中のナトリウム、カリウムおよびマグネシウムの含有量をさらに低減させることができる。 For example, when iron hydroxide is precipitated from waste sulfuric acid containing iron as a heavy metal, the pH of the waste sulfuric acid is preferably 5.0 or higher and 10.0 or lower, more preferably 6.0 or higher and 8.0 or lower. The addition amount of at least one selected from the group consisting of sodium hydroxide, potassium hydroxide and magnesium hydroxide may be adjusted. By setting 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 1 sort (s) of sodium, potassium, and magnesium selected from the group which consists of sodium hydroxide, potassium hydroxide, and magnesium hydroxide exists in the state of an ion in waste sulfuric acid. For this reason, it is possible to reduce the content of sodium, potassium and magnesium in the precipitated hydroxide by filtering the precipitated hydroxide, and further by washing the precipitated hydroxide with water. The content of sodium, potassium and magnesium in the precipitated hydroxide can be further reduced.
たとえば、重金属として亜鉛分を含む廃硫酸から水酸化亜鉛を析出させる場合は、廃硫酸のｐＨを、好ましくは４．５以上１０．０以下、より好ましくは５．０以上１０．０となるように水酸化ナトリウム、水酸化カリウムおよび水酸化マグネシウムからなる群から選択される少なくとも１種の添加量を調整してもよい。廃硫酸のｐＨを４．５以上１０.０以下にすることにより、廃硫酸中の亜鉛の多くを水酸化物として析出させることができる。 For example, when zinc hydroxide is precipitated from waste sulfuric acid containing zinc as a heavy metal, the pH of the waste sulfuric acid is preferably 4.5 or more and 10.0 or less, more preferably 5.0 or more and 10.0. The addition amount of at least one selected from the group consisting of sodium hydroxide, potassium hydroxide and magnesium hydroxide may be adjusted. By setting 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.
たとえば、重金属としてクロム分を含む廃硫酸から水酸化クロムを析出させる場合は、廃硫酸のｐＨを、好ましくは３．５以上１０．０以下、より好ましくは４．０以上１０．０以下、さらに好ましくは４．５以上１０．０以下となるように水酸化ナトリウム、水酸化カリウムおよび水酸化マグネシウムからなる群から選択される少なくとも１種の添加量を調整してもよい。廃硫酸のｐＨを３.５以上１０．０以下にすることにより、廃硫酸中のクロムの多くを水酸化物として析出させることができる。 For example, when chromium hydroxide is precipitated from waste sulfuric acid containing chromium as a heavy metal, the pH of the waste sulfuric acid is preferably 3.5 or more and 10.0 or less, more preferably 4.0 or more and 10.0 or less, You may adjust the addition amount of at least 1 sort (s) selected from the group which consists of sodium hydroxide, potassium hydroxide, and magnesium hydroxide so that it may become 4.5 or more and 10.0 or less preferably. By setting the pH of the waste sulfuric acid to 3.5 or more and 10.0 or less, most of chromium in the waste sulfuric acid can be precipitated as a hydroxide.
本発明の石膏の製造方法は、工程（Ｃ）で析出した水酸化物を廃硫酸から分離除去する工程（Ｄ）、および水酸化物を分離除去した廃硫酸にカルシウム源を添加して石膏を析出させる工程（Ｅ）をさらに含んでもよい。 The method for producing gypsum of the present invention comprises a step (D) of separating and removing the hydroxide precipitated in step (C) from waste sulfuric acid, and a calcium source added to the waste sulfuric acid from which the hydroxide has been separated and removed. A step (E) of precipitation may be further included.
工程（Ｄ）
工程（Ｄ）では、工程（Ｃ）で析出した重金属の水酸化物を廃硫酸から分離除去する。
Process (D)
In the step (D), the heavy metal hydroxide precipitated in the step (C) is separated and removed from the waste sulfuric acid.
（分離除去）
工程（Ｄ）における分離除去の説明は、工程（Ｂ）における分離除去の説明と同様であるので、工程（Ｄ）における分離除去の説明は省略する。なお、工程（Ｄ）における分離除去の方法は、工程（Ｂ）における分離除去の方法と同じであってもよいし、異なっていてもよい。また、分離をより速やかにするために高分子凝集剤を添加してもよい。
(Separation removal)
Since the description of the separation / removal in the step (D) is the same as the description of the separation / removal in the step (B), the description of the separation / removal in the step (D) is omitted. The separation / removal method in step (D) may be the same as or different from the separation / removal method in step (B). Further, a polymer flocculant may be added in order to make the separation faster.
工程（Ｅ）
工程（Ｅ）では、重金属の水酸化物を分離除去した廃硫酸にカルシウム源を添加して石膏を析出させる。
Process (E)
In the step (E), a calcium source is added to the waste sulfuric acid from which the heavy metal hydroxide is separated and removed to precipitate gypsum.
（重金属の水酸化物を分離除去した廃硫酸）
工程（Ｅ）では、重金属の水酸化物を分離除去した廃硫酸における重金属の含有率は、十分に低くなっているので、廃硫酸にカルシウム源を添加して石膏を析出させることによって、重金属の含有率が低い石膏を得ることができる。また、工程（Ｅ）で、石膏をさらに析出させることによって、廃硫酸中のＳＯ４成分の大部分を活用することができる。
(Waste sulfuric acid from which heavy metal hydroxides are separated and removed)
In step (E), the content of heavy metal in the waste sulfuric acid from which the heavy metal hydroxide has been separated and removed is sufficiently low. Therefore, by adding a calcium source to the waste sulfuric acid to precipitate gypsum, Gypsum with a low content can be obtained. Moreover, most of the SO 4 component in the waste sulfuric acid can be utilized by further depositing gypsum in the step (E).
（カルシウム源）
工程（Ｅ）で用いるカルシウム源としては、たとえば、塩化カルシウムなどの水溶性カルシウム塩、もしくはカルシウムイオンを含有する水溶液などが挙げられる。
(Calcium source)
Examples of the calcium source used in the step (E) include a water-soluble calcium salt such as calcium chloride or an aqueous solution containing calcium ions.
（カルシウム源の添加量）
工程（Ｅ）で廃硫酸に添加するカルシウム源の添加量は、カルシウム源中のＣａと廃硫酸中のＳＯ４ ２−とのモル比（Ｃａ／ＳＯ４ ２−）が１に近い量のカルシウム源を廃硫酸に添加することにより、廃硫酸中のＳＯ４ ２−のほとんどを石膏へと転化できる。これよりもモル比が高くなるとカルシウムが余剰となり、低くなると硫酸イオンが余剰となり、排水処理が必要となるので経済的ではない。なお、カルシウム源中のＣａと廃硫酸中のＳＯ４ ２−とのモル比（Ｃａ／ＳＯ４ ２−）は、好ましくは０．９〜１．０であり、より好ましくは０．９〜０．９５である。
(Amount of calcium source added)
The amount of calcium source added to the waste sulfuric acid in step (E) is such that the molar ratio of Ca in the calcium source to SO 4 2− in the waste sulfuric acid (Ca / SO 4 2− ) is close to 1. By adding the source to the waste sulfuric acid, most of the SO 4 2− in the waste sulfuric acid can be converted to gypsum. If the molar ratio becomes higher than this, calcium becomes excessive, and if it becomes lower, sulfate ions become excessive and wastewater treatment is required, which is not economical. The molar ratio (Ca / SO 4 2− ) between Ca in the calcium source and SO 4 2− in the waste sulfuric acid is preferably 0.9 to 1.0, more preferably 0.9 to 0. .95.
本発明の石膏の製造方法は、工程（Ｅ）で析出した石膏を廃硫酸から分離除去する工程（Ｆ）をさらに含んでもよい。 The method for producing gypsum of the present invention may further include a step (F) of separating and removing the gypsum precipitated in the step (E) from the waste sulfuric acid.
工程（Ｆ）
工程（Ｆ）では、工程（Ｅ）で析出した石膏を廃硫酸から分離除去する。
Process (F)
In the step (F), the gypsum precipitated in the step (E) is separated and removed from the waste sulfuric acid.
（分離除去）
工程（Ｆ）における分離除去の説明は、工程（Ｂ）における分離除去の説明と同様であるので、工程（Ｆ）における分離除去の説明は省略する。なお、工程（Ｆ）における分離除去の方法は、工程（Ｂ）における分離除去の方法と同じであってもよいし、異なっていてもよい。
(Separation removal)
Since the description of the separation / removal in the step (F) is the same as the description of the separation / removal in the step (B), the description of the separation / removal in the step (F) is omitted. The separation / removal method in step (F) may be the same as or different from the separation / removal method in step (B).
上述したように、工程（Ｃ）で添加した水酸化ナトリウム、水酸化カリウムおよび水酸化マグネシウムからなる群から選択される少なくとも１種のナトリウム、カリウムおよびマグネシウムは、廃硫酸中にイオンの状態で存在する。このため、工程（Ｆ）で析出させた石膏を水で洗浄することにより、析出した石膏中のナトリウム、カリウムおよびマグネシウムの含有量を低減させることができる。 As described above, at least one sodium, potassium and magnesium selected from the group consisting of sodium hydroxide, potassium hydroxide and magnesium hydroxide added in the step (C) is present in an ionic state in the waste sulfuric acid. To do. For this reason, the content of sodium, potassium, and magnesium in the precipitated gypsum can be reduced by washing the gypsum precipitated in the step (F) with water.
［セメント組成物の製造方法］
本発明のセメント組成物の製造方法は、本発明の石膏の製造方法により石膏を製造する工程、および石膏を製造する工程で製造された石膏を用いてセメント組成物を製造する工程を含む。すなわち、本発明のセメント組成物の製造方法は、本発明の石膏の製造方法により製造された石膏を用いてセメント組成物を製造する。たとえば、セメントクリンカに、本発明の石膏の製造方法により製造された石膏と少量混合成分とを加えて、セメント組成物を製造してもよい。また、本発明の石膏の製造方法により製造された石膏をクリンカ原料の１つとして用いて製造したセメントクリンカに、本発明の石膏の製造方法により製造された石膏またはその他の石膏と少量混合成分とを加えて、セメント組成物を製造してもよい。
[Method for producing cement composition]
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. That is, the method for producing a cement composition of the present invention produces a cement composition using the gypsum produced by the method for producing gypsum of the present invention. For example, a cement composition may be produced by adding gypsum produced by the gypsum production method of the present invention and a small amount of mixed components to a cement clinker. In addition, a cement clinker produced using the gypsum produced by the method for producing gypsum of the present invention as one of the clinker raw materials, gypsum produced by the method for producing gypsum of the present invention or other gypsum and a small amount of mixed components May be added to produce a cement composition.
また、廃硫酸に含まれる重金属が鉄の場合、本発明のセメント組成物の製造方法は、本発明の石膏の製造方法により製造された石膏のほかに、本発明の石膏の製造方法の工程（Ｃ）において析出された水酸化鉄をさらに用いてセメント組成物を製造してもよい。たとえば、セメント組成物の製造で使用するセメントクリンカのクリンカ原料の１つとして、工程（Ｃ）において析出された水酸化鉄またはその水酸化鉄から作製した鉄もしくは鉄化合物を使用してもよい。 When the heavy metal contained in the waste sulfuric acid is iron, the method for producing the cement composition of the present invention includes the steps of the gypsum production method of the present invention in addition to the gypsum produced by the gypsum production method of the present invention ( The cement composition may be produced by further using the iron hydroxide precipitated in C). For example, as one of the clinker raw materials of the cement clinker used in the manufacture of the cement composition, the iron hydroxide precipitated in the step (C) or the iron or iron compound prepared from the iron hydroxide may be used.
次に、本発明を実施例により、さらに詳細に説明するが、本発明は、これらの実施例によってなんら限定されるものではない。 EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these Examples.
［測定および評価］
実施例および比較例の石膏を以下のように測定および評価した。
（１）廃硫酸のｐＨ
ｐＨ計（（株）堀場製作所 製、商品名：ｐＨメータ Ｄ−５１）、ｐＨ電極（（株）堀場製作所 製、商品名：スリーブＴｏｕｇｈ電極 ９６８１−１０Ｄ）を使用して、カルシウム源、または水酸化ナトリウム、水酸化カリウムおよび水酸化マグネシウムからなる群から選択される少なくとも１種を添加した廃硫酸のｐＨを測定した。
（２）析出物の同定
Ｘ線回折装置（ＰＡＮａｌｙｔｉｃａｌ社製、商品名：Ｘ’Ｐｅｒｔ Ｐｒｏ）を使用して、廃硫酸にカルシウム源、または水酸化ナトリウム、水酸化カリウムおよび水酸化マグネシウムからなる群から選択される少なくとも１種を添加して廃硫酸から析出した析出物の同定を行った。
（３）析出物中の重金属の含有量
エネルギー分散型蛍光Ｘ線分析装置（ＳＰＥＣＴＲＯ社製、商品名：ＸＥＰＯＳ）を使用して、廃硫酸にカルシウム源、または水酸化ナトリウム、水酸化カリウムおよび水酸化マグネシウムからなる群から選択される少なくとも１種を添加して廃硫酸から析出した析出物中の鉄、亜鉛およびクロムの含有量を測定した。
（４）濾液中のＳＯ４ ２−の含有量
イオンクロマトグラフ装置（Ｄｉｏｎｅｘ社製、商品名：ＩＣＳ−２０００）を使用して、廃硫酸を濾過して得られた濾液中のＳＯ４ ２−の含有量を測定した。
（５）析出物の色
廃硫酸を濾過して得られた析出物の色を目視で観察した。
[Measurement and evaluation]
The gypsum of Examples and Comparative Examples was measured and evaluated as follows.
(1) pH of waste sulfuric acid
Using a pH meter (Horiba, Ltd., trade name: pH meter D-51), pH electrode (Horiba, Ltd., trade name: sleeve Tough electrode 9681-10D), calcium source or water The pH of waste sulfuric acid to which at least one selected from the group consisting of sodium oxide, potassium hydroxide and magnesium hydroxide was added was measured.
(2) Identification of precipitates Using an X-ray diffractometer (manufactured by PANalytical, trade name: X'Pert Pro), waste sulfuric acid is a calcium source, or a group consisting of sodium hydroxide, potassium hydroxide and magnesium hydroxide At least one selected from the above was added to identify precipitates deposited from the waste sulfuric acid.
(3) Content of heavy metal in the precipitate Using an energy dispersive X-ray fluorescence spectrometer (trade name: XEPOS, manufactured by SPECTRO), waste sulfuric acid as a calcium source, or sodium hydroxide, potassium hydroxide and water At least one selected from the group consisting of magnesium oxide was added, and the contents of iron, zinc and chromium in the precipitate deposited from the waste sulfuric acid were measured.
(4) Content of SO 4 2− in the filtrate Using an ion chromatograph (Dionex, trade name: ICS-2000), SO 4 2− in the filtrate obtained by filtering waste sulfuric acid. The content of was measured.
(5) Color of the precipitate The color of the precipitate obtained by filtering the waste sulfuric acid was visually observed.
［実施例１〜７および比較例１〜５の析出物の作製］
上記ｐＨ計を使用してｐＨを測定しながら、ｐＨが０．５になるように炭酸カルシウムスラリーを１０００ｍＬの廃硫酸に添加して、３時間撹拌した。次に、撹拌しながら上記廃硫酸に炭酸カルシウムスラリーを少しずつさらに添加していった。そして、廃硫酸のｐＨの値を表１に示す所定値にさせ終わったとき、３０ｍＬの廃硫酸をサンプリングした。サンプリングした廃硫酸を濾過してサンプリングした廃硫酸の析出物および濾液を得た。なお、炭酸カルシウムスラリーは、１Ｌの水に１００ｇの炭酸カルシウムを添加することにより作製した。また、炭酸カルシウムを添加する前の廃硫酸中のＦｅの含有量は５．８質量％であり、亜鉛の含有量は３３００ｍｇ／ｋｇであり、クロムの含有量は１５０ｍｇ／ｋｇであり、ＳＯ４ ２−の含有量の含有量は１９．４質量％であった。
[Preparation of Precipitates of Examples 1-7 and Comparative Examples 1-5]
While measuring the pH using the pH meter, the calcium carbonate slurry was added to 1000 mL of waste sulfuric acid so that the pH was 0.5, and the mixture was stirred for 3 hours. Next, the calcium carbonate slurry was gradually added to the waste sulfuric acid while stirring. When the pH value of the waste sulfuric acid was adjusted to the predetermined value shown in Table 1, 30 mL of waste sulfuric acid was sampled. The sampled waste sulfuric acid was filtered to obtain a sample of the waste sulfuric acid precipitate and filtrate. The calcium carbonate slurry was prepared by adding 100 g of calcium carbonate to 1 L of water. Further, the content of Fe in the waste sulfuric acid before adding calcium carbonate is 5.8% by mass, the content of zinc is 3300 mg / kg, the content of chromium is 150 mg / kg, and SO 4 The content of the 2- content was 19.4% by mass.
［実施例８および９の析出物の作製］
上記炭酸カルシウムスラリーの添加で、廃硫酸のｐＨが２．０になったときに２００ｍＬの廃硫酸を分取して濾過を行い、得られた濾液に、廃硫酸のｐＨが６．５になるまで水酸化ナトリウム水溶液を添加して実施例８の廃硫酸を作製した。実施例８の廃硫酸を濾過することにより、実施例８の析出物を得た。残った濾液に、塩化カルシウム水溶液を添加して攪拌を行い、実施例９の廃硫酸を作製した。実施例９の廃硫酸を濾過して実施例９の析出物を得た。
[Preparation of Precipitates of Examples 8 and 9]
When the pH of the waste sulfuric acid reaches 2.0 by adding the calcium carbonate slurry, 200 mL of the waste sulfuric acid is collected and filtered, and the pH of the waste sulfuric acid becomes 6.5 in the obtained filtrate. Sodium hydroxide aqueous solution was added until the waste sulfuric acid of Example 8 was produced. The waste sulfuric acid of Example 8 was filtered to obtain the precipitate of Example 8. To the remaining filtrate, an aqueous calcium chloride solution was added and stirred to produce the waste sulfuric acid of Example 9. The waste sulfuric acid of Example 9 was filtered to obtain the precipitate of Example 9.
［測定結果および評価結果］
実施例１〜７のサンプリングした廃硫酸および比較例１〜５のサンプリングした廃硫酸の評価結果を表１に、実施例８および９の廃硫酸の評価結果を表２に示す。
[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 the evaluation results of the waste sulfuric acid of Examples 8 and 9 are shown in Table 2.
実施例１〜７と比較例１〜５とを比較することによって、廃硫酸に炭酸カルシウムスラリーを添加して石膏を析出させたときのｐＨを３．０以下にすることによって、析出する石膏中の鉄分、亜鉛分およびクロム分の含有量を低くできることがわかった。また、実施例１〜５の析出物の色が白色であることからも析出する石膏中の鉄分の含有量が低いことがわかった。さらに、炭酸カルシウムスラリーを添加する前の廃硫酸中のＳＯ４ ２−の含有量と、実施例２〜７の濾液中のＳＯ４ ２−の含有量とを比較することにより、廃硫酸に炭酸カルシウムスラリーを添加して廃硫酸のｐＨを１．０以上にすることによって、廃硫酸中のＳＯ４ ２−の大部分が石膏へと転化されることがわかった。また、実施例８により、廃硫酸にカルシウム源を添加して廃硫酸のｐＨを３．０以下にして石膏を析出させた後、水酸化ナトリウム、水酸化カリウムおよび水酸化マグネシウムからなる群から選択される少なくとも１種を廃硫酸に添加して廃硫酸のｐＨを３．５以上１０.０以下にすることによって、廃硫酸中の鉄分、亜鉛分およびクロム分を析出させることができることがわかった。さらに、実施例９により、鉄分、亜鉛分およびクロム分を析出させた後の廃硫酸にカルシウム源を添加して、鉄分、亜鉛分およびクロム分の含有量が小さい石膏を析出させることができることがわかった。 By comparing Examples 1 to 7 with Comparative Examples 1 to 5, by adding a calcium carbonate slurry to waste sulfuric acid and precipitating gypsum, the pH in the gypsum is 3.0 or less. It was found that the content of iron, zinc and chromium can be reduced. Moreover, since the color of the deposit of Examples 1-5 was white, it turned out that content of the iron content in the gypsum to precipitate is low. Further, by comparing the content of SO 4 2− in the waste sulfuric acid before adding the calcium carbonate slurry with the content of SO 4 2− in the filtrates of Examples 2 to 7, the waste sulfuric acid was carbonated. It was found that most of SO 4 2− in the waste sulfuric acid was converted to gypsum by adding calcium slurry to bring the pH of the waste sulfuric acid to 1.0 or more. Further, according to Example 8, after adding a calcium source to the waste sulfuric acid and setting the pH of the waste sulfuric acid to 3.0 or less to precipitate gypsum, it is selected from the group consisting of sodium hydroxide, potassium hydroxide and magnesium hydroxide. It was found that the iron content, zinc content and chromium content in the waste sulfuric acid can be precipitated by adding at least one of the above to the waste sulfuric acid so that the pH of the waste sulfuric acid is 3.5 or more and 10.0 or less. . Furthermore, according to Example 9, it is possible to add a calcium source to the waste sulfuric acid after depositing iron, zinc and chromium, and to deposit gypsum with a small content of iron, zinc and chromium. all right.
Claims (4)
前記工程（Ａ）では、前記廃硫酸に前記カルシウム源を添加して前記石膏を析出させたときの前記廃硫酸のｐＨを３．０以下にする石膏の製造方法。 Including a step (A) of adding a calcium source to waste sulfuric acid containing heavy metal to precipitate gypsum,
In the step (A), a method for producing gypsum in which the pH of the waste sulfuric acid when the calcium source is added to the waste sulfuric acid to precipitate the gypsum is 3.0 or less.
水酸化ナトリウム、水酸化カリウムおよび水酸化マグネシウムからなる群から選択される少なくとも１種を、前記石膏を分離除去した廃硫酸に添加して前記重金属の水酸化物を析出させる工程（Ｃ）をさらに含み、
前記工程（Ｃ）では、前記水酸化ナトリウム、水酸化カリウムおよび水酸化マグネシウムからなる群から選択される少なくとも１種を前記廃硫酸に添加して前記水酸化物を析出させたときの前記廃硫酸のｐＨを３．５以上１０．０以下にする請求項１に記載の石膏の製造方法。 Separating and removing the gypsum precipitated in the step (A) from the waste sulfuric acid; and at least one selected from the group consisting of sodium hydroxide, potassium hydroxide and magnesium hydroxide, A step (C) of adding to the separated sulfuric acid to precipitate the heavy metal hydroxide,
In the step (C), the waste sulfuric acid when the hydroxide is precipitated by adding at least one selected from the group consisting of sodium hydroxide, potassium hydroxide and magnesium hydroxide to the waste sulfuric acid The method for producing gypsum according to claim 1, wherein the pH of the mixture is 3.5 or more and 10.0 or less.
前記水酸化物を分離除去した前記廃硫酸にカルシウム源を添加して石膏を析出させる工程（Ｅ）をさらに含む請求項２に記載の石膏の製造方法。 A step (D) of separating and removing the hydroxide precipitated in the step (C) from the waste sulfuric acid, and a step of depositing gypsum by adding a calcium source to the waste sulfuric acid from which the hydroxide has been separated and removed ( The method for producing gypsum according to claim 2, further comprising E).
前記石膏を製造する工程で製造された石膏を用いてセメント組成物を製造する工程を含むセメント組成物の製造方法。 A cement composition comprising a step of producing gypsum by the method for producing gypsum according to any one of claims 1 to 3, and a step of producing a cement composition using the gypsum produced in the step of producing the gypsum. Manufacturing method.
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| CN102816931A (en) * | 2012-07-27 | 2012-12-12 | 紫金矿业集团股份有限公司 | Method for recovering copper and iron from copper-containing acid wastewater and producing gypsum |
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| Publication number | Publication date |
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| TWI694057B (en) | 2020-05-21 |
| KR20160111875A (en) | 2016-09-27 |
| KR102449716B1 (en) | 2022-09-30 |
| TW201634391A (en) | 2016-10-01 |
| CN105985037A (en) | 2016-10-05 |
| JP6638345B2 (en) | 2020-01-29 |
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