CN105985037A - Method of producing gypsum and method of producing cement composition - Google Patents
Method of producing gypsum and method of producing cement composition Download PDFInfo
- Publication number
- CN105985037A CN105985037A CN201610152728.5A CN201610152728A CN105985037A CN 105985037 A CN105985037 A CN 105985037A CN 201610152728 A CN201610152728 A CN 201610152728A CN 105985037 A CN105985037 A CN 105985037A
- Authority
- CN
- China
- Prior art keywords
- sulfuric acid
- waste sulfuric
- gypsum fibrosum
- hydroxide
- gypsum
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 58
- 239000000203 mixture Substances 0.000 title claims abstract description 30
- 239000004568 cement Substances 0.000 title claims abstract description 29
- 239000010440 gypsum Substances 0.000 title abstract description 15
- 229910052602 gypsum Inorganic materials 0.000 title abstract description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 281
- 239000002699 waste material Substances 0.000 claims abstract description 141
- 239000011575 calcium Substances 0.000 claims abstract description 48
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 44
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 43
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 111
- 238000004519 manufacturing process Methods 0.000 claims description 64
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 56
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 29
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 17
- 239000000347 magnesium hydroxide Substances 0.000 claims description 17
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 17
- 238000000926 separation method Methods 0.000 claims description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 239000011593 sulfur Substances 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims description 2
- 229910001950 potassium oxide Inorganic materials 0.000 claims description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 20
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 18
- 235000011121 sodium hydroxide Nutrition 0.000 description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- 239000002244 precipitate Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 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
- 239000011651 chromium Substances 0.000 description 10
- 229910052804 chromium Inorganic materials 0.000 description 10
- 229910052725 zinc Inorganic materials 0.000 description 10
- 239000011701 zinc Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 7
- 239000000706 filtrate Substances 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
- 239000001117 sulphuric acid Substances 0.000 description 7
- 235000011149 sulphuric acid Nutrition 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 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- 229910052749 magnesium Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 239000011591 potassium Substances 0.000 description 5
- 229910052700 potassium Inorganic materials 0.000 description 5
- 238000003672 processing method Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 4
- LDHBWEYLDHLIBQ-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide;hydrate Chemical compound O.[OH-].[O-2].[Fe+3] LDHBWEYLDHLIBQ-UHFFFAOYSA-M 0.000 description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 3
- 239000001110 calcium chloride Substances 0.000 description 3
- 229910001628 calcium chloride Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 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
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 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
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 239000007864 aqueous solution Substances 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
- 239000000470 constituent Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910000358 iron sulfate Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012797 qualification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002893 slag Substances 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
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method 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
- -1 calcium chloride Chemical class 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
- FYHXNYLLNIKZMR-UHFFFAOYSA-N calcium;carbonic acid Chemical compound [Ca].OC(O)=O FYHXNYLLNIKZMR-UHFFFAOYSA-N 0.000 description 1
- LXMQZGGLHVSEBA-UHFFFAOYSA-N chromium;trihydrate Chemical compound O.O.O.[Cr] LXMQZGGLHVSEBA-UHFFFAOYSA-N 0.000 description 1
- 239000000701 coagulant Substances 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
- 230000008021 deposition Effects 0.000 description 1
- 150000004683 dihydrates Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 150000002500 ions 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
- 238000005259 measurement Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000005554 pickling Methods 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
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- CBXWGGFGZDVPNV-UHFFFAOYSA-N so4-so4 Chemical compound OS(O)(=O)=O.OS(O)(=O)=O CBXWGGFGZDVPNV-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 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
- 238000012800 visualization Methods 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 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
The present invention provides a method of producing gypsum and a method of producing a cement composition by using the gypsum produced by the method of producing gypsum. The method of producing the gypsum comprises a step (A) of adding calcium sources to waste sulfuric acid containing heavy metal to precipitate the gypsum, and in the step (A), the pH value of the waste sulfuric acid when the calcium sources are added to the waste sulfuric acid to precipitate the gypsum becomes below 3.0. The method of producing the cement composition comprises a step of producing the gypsum through the method of producing the gypsum, and a step of producing the cement composition by using the gypsum produced in the step of producing the gypsum. The method of producing gypsum can directly use waste sulfuric acid containing heavy metal to produce gypsum containing a low content of the heavy metal.
Description
Technical field
The present invention relates to Waste Sulfuric Acid that a kind of effective utilization contains heavy metal to manufacture the Gypsum Fibrosum manufacture of Gypsum Fibrosum
Method and use manufacture the cement of cement composition by the Gypsum Fibrosum manufactured by this Gypsum Fibrosum manufacture method
The manufacture method of compositions.
Background technology
Utilize calcium compounds that sulphuric acid produced in various industrial steps is neutralized process,
And the method being manufactured as the Gypsum Fibrosum of its by-product is widely known by the people.But, about containing many heavy metals
Waste Sulfuric Acid, the content of the heavy metal in Gypsum Fibrosum also uprises, and therefore the utilization as Gypsum Fibrosum is limited to.
Therefore, it has been suggested that have the various of the Gypsum Fibrosum that the content by the Waste Sulfuric Acid manufacture heavy metal containing heavy metal is low
Method.Such as, when using the content manufacturing ferrous components containing ferrous components as the Waste Sulfuric Acid of heavy metal
During low Gypsum Fibrosum, use Waste Sulfuric Acid after implementing to cut down the process of ferrous components in advance or only will not analyse at ferrum
The reaction in the low pH region gone out manufactures Gypsum Fibrosum.Become as reducing ferrum from the Waste Sulfuric Acid containing ferrous components
Point, the method thus Waste Sulfuric Acid containing ferrous components processed, such as patent documentation 1 are remembered
The processing method of Waste Sulfuric Acid described in the processing method of the Waste Sulfuric Acid carried and patent documentation 2 is as existing
There is technology and known.According to the processing method of Waste Sulfuric Acid described in patent documentation 1, to containing
The Waste Sulfuric Acid having ferrous components cools down, and makes ferrous sulfate separate out and separates removal, and reducing Waste Sulfuric Acid
In ferrous components concentration.It addition, according to the processing method of Waste Sulfuric Acid described in patent documentation 2,
Concentrated sulphuric acid is mixed into Waste Sulfuric Acid, thus makes the sulfuric acid concentration of this Waste Sulfuric Acid become the highest, and make
The dissolubility of ferrous components declines, and makes iron sulfate crystallization separate out from the Waste Sulfuric Acid being dissolved with ferrous components,
And the crystallization of this iron sulfate is removed, thus cut down the ferrous components being dissolved in Waste Sulfuric Acid.
[prior art literature]
[patent documentation]
[patent documentation 1] Japanese Patent Laid-Open 2004-256334 publication
[patent documentation 2] Japanese Patent Laid-Open 2002-284509 publication
Summary of the invention
[inventing problem to be solved]
But, when using the Waste Sulfuric Acid manufacture Gypsum Fibrosum being reduced ferrous components by the processing method of Waste Sulfuric Acid
Time, the manufacture that there is Gypsum Fibrosum becomes this problem numerous and diverse.It is difficult to become ferrum it addition, be also possible to generation
Content is divided to be reduced to the situation till being enough to manufacture the level of Gypsum Fibrosum.On the other hand, when only will not at ferrum
When manufacturing Gypsum Fibrosum in the reaction in the low pH region separated out, the quantitative change that can manufacture Gypsum Fibrosum is few, it is impossible to fully
Utilize sulphuric acid.Therefore, it is an object of the invention to provide and a kind of be not limited to the Waste Sulfuric Acid containing ferrous components,
Waste Sulfuric Acid containing heavy metal Gypsum Fibrosum manufacture to the content that manufactures heavy metal low Gypsum Fibrosum be can be used directly
Method, and use the cement being manufactured cement composition by the Gypsum Fibrosum manufactured by this Gypsum Fibrosum manufacture method
The manufacture method of compositions.
[solving the technological means of problem]
Present inventors etc. carry out making great efforts the result of research, find by adjusting to the sulfur waste containing heavy metal
The pH of Waste Sulfuric Acid when directly interpolation calcium source makes Gypsum Fibrosum separate out in acid, it is possible to decrease in the Gypsum Fibrosum separated out
The content of heavy metal, thus complete the present invention.That is, the present invention is as described below.
[1] a kind of Gypsum Fibrosum manufacture method, it is characterised in that: include adding in the Waste Sulfuric Acid containing heavy metal
Add calcium source to the step (A) making Gypsum Fibrosum separate out, and in step (A), make to add in Waste Sulfuric Acid
The pH of Waste Sulfuric Acid when calcium source makes Gypsum Fibrosum separate out becomes less than 3.0.
[2] according to the Gypsum Fibrosum manufacture method described in described [1], it is characterised in that: also include step
(A) Gypsum Fibrosum separated out in separates the step (B) of removal from Waste Sulfuric Acid, and eliminates to separation
The Waste Sulfuric Acid of Gypsum Fibrosum adds the group selecting free sodium hydroxide, potassium hydroxide and magnesium hydroxide to be formed
In at least one make the step (C) that the hydroxide of heavy metal separates out, and in step (C),
Make to add in Waste Sulfuric Acid to select in the group that free sodium hydroxide, potassium hydroxide and magnesium hydroxide are formed
The pH of at least one Waste Sulfuric Acid when making hydroxide separate out become more than 3.5, less than 10.0.
[3] according to the Gypsum Fibrosum manufacture method described in described [2], it is characterised in that: also include step
(C) hydroxide separated out in separates the step (D) of removal from Waste Sulfuric Acid and goes to separation
Except the Waste Sulfuric Acid of hydroxide adds the step (E) that calcium source makes Gypsum Fibrosum separate out.
[4] manufacture method of a kind of cement composition, it is characterised in that: include by according to described [1]
Manufacture the step of Gypsum Fibrosum to the Gypsum Fibrosum manufacture method recorded any one of [3] and use manufacture Gypsum Fibrosum
Step in manufactured Gypsum Fibrosum manufacture the step of cement composition.
(effect of invention)
According to the present invention, it is possible to provide a kind of can directly use the Waste Sulfuric Acid containing heavy metal manufacture weight
The Gypsum Fibrosum manufacture method of the Gypsum Fibrosum that the content of metal is low and using by manufactured by this Gypsum Fibrosum manufacture method
Gypsum Fibrosum manufacture the manufacture method of cement composition of cement composition.
Detailed description of the invention
[manufacture method of Gypsum Fibrosum]
Hereinafter, the Gypsum Fibrosum manufacture method of the present invention is illustrated.The Gypsum Fibrosum manufacture method bag of the present invention
Include and in the Waste Sulfuric Acid containing heavy metal, add calcium source to the step (A) making Gypsum Fibrosum separate out.
Step (A)
In step (A), in the Waste Sulfuric Acid containing heavy metal, add calcium source make Gypsum Fibrosum separate out.
(heavy metal)
The heavy metal of the present invention is the proportion metal more than 5, and heavy metal include, for example: ferrum, zinc,
Chromium, lead, cadmium, copper, stannum, hydrargyrum, nickel and cobalt etc..Containing ferrum, zinc and the situation of chromium in Waste Sulfuric Acid
Many.
(Waste Sulfuric Acid)
Step (A) as long as used in Waste Sulfuric Acid containing heavy metal person, then be not particularly limited.
Waste Sulfuric Acid containing heavy metal is for example, used in the sulphuric acid after the pickling of steel plate and copper refining produced
Sulphuric acid etc..
(calcium source)
Calcium source used in step (A) be the compound containing calcium and using these compounds as main one-tenth
The various materials divided, as long as Gypsum Fibrosum is with epigenesist, are then not particularly limited.Calcium source include, for example:
Calcium oxide, calcium hydroxide, calcium carbonate, calcium phosphate, calcium fluoride and calcium chloride etc..These calcium sources can be single
Solely use one or be used in combination of two or more.Among these calcium sources, preferred calcium source can be enumerated
Calcium oxide and calcium carbonate etc..Alternatively, it is also possible to by shell or unprocessed concrete mud (concrete
Etc. sludge) garbage that the content of calcium is big is used as calcium source.These illustrated calcium sources can be used alone one
Plant or be used in combination of two or more.
(addition in calcium source)
The addition in calcium source is that the pH of the Waste Sulfuric Acid being added with calcium source is converged in less than 3.0, preferably receives
Holding back below 2.5, the mode being more preferably converged in the scope of less than 2.0 is controlled.
(Gypsum Fibrosum)
The Gypsum Fibrosum separated out in step (A) is dihydrate gypsum and/or anhydrous gypsum.Weight in Waste Sulfuric Acid
Metal separates out hardly, and remains in Waste Sulfuric Acid, in the Gypsum Fibrosum therefore separated out in step (A)
The content of heavy metal little.
In the step (A), make Waste Sulfuric Acid when adding calcium source to make Gypsum Fibrosum separate out in Waste Sulfuric Acid
PH becomes less than 3.0, preferably becomes less than 2.5, more preferably becomes less than 2.0.If Waste Sulfuric Acid
PH is more than 3.0, then the amount of precipitation of the compound of the heavy metal together separated out with Gypsum Fibrosum uprises, in Gypsum Fibrosum
The content of heavy metal uprise.As long as it addition, Gypsum Fibrosum separates out, then in Waste Sulfuric Acid, add calcium source make
The lower limit of the pH of Waste Sulfuric Acid when Gypsum Fibrosum separates out is not particularly limited.The lower limit of the pH of Waste Sulfuric Acid
For example, 1.0.
(water)
In step (A), in order to adjust the viscosity etc. of the Waste Sulfuric Acid being added with calcium source, it is also possible to mixed
Compound adds water.The water of the Gypsum Fibrosum manufacture method that can be used for the present invention include, for example: ion exchanges
Water, pure water, distilled water and tap water etc..These water can be used alone one or by two or more groups
Close and use.Produced alternatively, it is also possible to utilize when separating and remove Gypsum Fibrosum in step described later (F)
Filtrate carry out processing obtained draining.
The Gypsum Fibrosum manufacture method of the present invention can farther include: by the Gypsum Fibrosum that separated out in step (A) from
Waste Sulfuric Acid separates the step (B) of removal, and eliminates interpolation choosing in the Waste Sulfuric Acid of Gypsum Fibrosum to separation
At least one in the group that free sodium hydroxide, potassium hydroxide and magnesium hydroxide are formed makes a huge sum of money
The step (C) that the hydroxide belonged to separates out.
Step (B)
In step (B), the Gypsum Fibrosum separated out in step (A) is separated removal from Waste Sulfuric Acid.
(separate and remove)
By making gypsum deposition, Gypsum Fibrosum can be separated from Waste Sulfuric Acid removal, it is also possible to by containing
The Waste Sulfuric Acid of Gypsum Fibrosum carries out filtration and Gypsum Fibrosum separates from Waste Sulfuric Acid removal.Alternatively, it is also possible to use
Use the separation side of the equipment for separating liquid from solid such as liquid cyclone, decanter, centrifugal separator, pressure filter
Gypsum Fibrosum is separated removal from Waste Sulfuric Acid by method.These separate minimizing technology and can individually implement, it is also possible to
Two or more combinations are implemented.
Step (C)
In step (C), eliminate to separation in the Waste Sulfuric Acid of Gypsum Fibrosum add select free sodium hydroxide,
At least one in the group that potassium hydroxide and magnesium hydroxide are formed is analysed making the hydroxide of heavy metal
Go out.
(selecting at least one in the group that free sodium hydroxide, potassium hydroxide and magnesium hydroxide formed)
Select in the group that free sodium hydroxide, potassium hydroxide and magnesium hydroxide formed at least one with
Heavy metal in Waste Sulfuric Acid carries out reacting and making the hydroxide of heavy metal separate out, and with in Waste Sulfuric Acid
Sulphuric acid carry out reacting and generating water miscible sulfate.
(pH of Waste Sulfuric Acid)
In step (C), select free sodium hydroxide, potassium hydroxide and hydrogen so that adding in Waste Sulfuric Acid
Waste Sulfuric Acid when at least one in the group that magnesium oxide is formed is to make the hydroxide of heavy metal separate out
PH preferably become more than 3.5, less than 10.0, more preferably become the mode of more than 3.5, less than 5.0,
At least one in the group that free sodium hydroxide, potassium hydroxide and magnesium hydroxide are formed is selected in adjustment
Addition.By making the pH of Waste Sulfuric Acid become more than 3.5, less than 10.0, can make in Waste Sulfuric Acid is big
Part heavy metal separates out as hydroxide.
Such as, when making hydrated ferric oxide. separate out from containing ferrous components as the Waste Sulfuric Acid of heavy metal, also
The pH that can make Waste Sulfuric Acid preferably becomes more than 5.0, less than 10.0, more preferably become more than 6.0,
The mode of less than 8.0, adjusts the group selecting free sodium hydroxide, potassium hydroxide and magnesium hydroxide to be formed
In the addition of at least one.By making the pH of Waste Sulfuric Acid become more than 5.0, less than 10.0, can
The most of ferrum in Waste Sulfuric Acid is made to separate out as hydroxide.Furthermore, select free sodium hydroxide, hydrogen-oxygen
Change the sodium of at least one, potassium and the magnesium in the group that potassium and magnesium hydroxide are formed in Waste Sulfuric Acid with from
The state of son exists.Therefore, the described hydroxide separated out is filtered, thus can reduce institute
The content of sodium, potassium and magnesium in the hydroxide separated out, and then, utilize the water hydroxide to being separated out
Thing is carried out, and thus can reduce the content of sodium, potassium and magnesium in separated out hydroxide further.
Such as, when making zinc hydroxide separate out from containing zinc composition as the Waste Sulfuric Acid of heavy metal, also
The pH that can make Waste Sulfuric Acid preferably becomes more than 4.5, less than 10.0, more preferably become more than 5.0,
The mode of less than 10.0, adjusts the group selecting free sodium hydroxide, potassium hydroxide and magnesium hydroxide to be formed
The addition of at least one in group.By making the pH of Waste Sulfuric Acid become more than 4.5, less than 10.0,
The most of zinc in Waste Sulfuric Acid can be made to separate out as hydroxide.
Such as, when making chromic oxide gel separate out from containing chromium component as the Waste Sulfuric Acid of heavy metal, also
The pH that can make Waste Sulfuric Acid preferably becomes more than 3.5, less than 10.0, more preferably become more than 4.0,
Less than 10.0, and then more preferably become the mode of more than 4.5, less than 10.0, adjust and select free hydroxide
The addition of at least one in the group that sodium, potassium hydroxide and magnesium hydroxide are formed.Give up by making
The pH of sulphuric acid becomes more than 3.5, less than 10.0, and the most of chromium in Waste Sulfuric Acid can be made as hydroxide
Thing separates out.
The Gypsum Fibrosum manufacture method of the present invention can farther include the hydroxide that will be separated out in step (C)
The step (D) of removal is separated and to separating in the Waste Sulfuric Acid eliminating hydroxide from Waste Sulfuric Acid
Add the step (E) that calcium source makes Gypsum Fibrosum separate out.
Step (D)
In step (D), by the hydroxide of heavy metal that separated out in step (C) from Waste Sulfuric Acid
Middle separation is removed.
(separate and remove)
The explanation that separating in step (D) is removed is identical with the explanation separating removal in step (B),
Therefore the explanation separating removal in step (D) is omitted.Furthermore, the separation in step (D) is removed
Method can with in step (B) to separate the method removed identical, it is also possible to different.It addition, in order to
Separation is made to become faster, it is also possible to add polymer coagulant.
Step (E)
In step (E), the Waste Sulfuric Acid of the hydroxide eliminating heavy metal to separation adds calcium source
Gypsum Fibrosum is made to separate out.
The Waste Sulfuric Acid of hydroxide of heavy metal (separation eliminate)
In step (E), the heavy metal in the Waste Sulfuric Acid of the hydroxide that separation eliminates heavy metal
Containing ratio step-down fully, therefore makes Gypsum Fibrosum separate out by interpolation calcium source in Waste Sulfuric Acid, can obtain
The Gypsum Fibrosum that the containing ratio of heavy metal is low.It addition, in step (E), make Gypsum Fibrosum separate out further, by
This can effectively utilize the most of SO in Waste Sulfuric Acid4Composition.
(calcium source)
As the calcium source used in step (E), include, for example: the water-soluble Ca salts such as calcium chloride,
Or the aqueous solution etc. containing calcium ion.
(addition in calcium source)
About the addition in the calcium source added in step (E) to Waste Sulfuric Acid, by by calcium source
Ca and the SO in Waste Sulfuric Acid4 2-Mol ratio (Ca/SO4 2-) the calcium source of amount close to 1 adds to sulfur waste
In acid, can be by the most of SO in Waste Sulfuric Acid4 2-Change into Gypsum Fibrosum.If mol ratio is higher than this, then calcium becomes
Obtaining superfluous, if mol ratio is less than this, then sulfate ion becomes superfluous, and needs drainage sunk well, because of
This is the most uneconomical.Furthermore, the Ca in calcium source and the SO in Waste Sulfuric Acid4 2-Mol ratio (Ca/SO4 2-)
Preferably 0.9～1.0, more preferably 0.9～0.95.
The Gypsum Fibrosum manufacture method of the present invention can farther include the Gypsum Fibrosum separated out in step (E) from giving up
Sulphuric acid separates the step (F) of removal.
Step (F)
In step (F), the Gypsum Fibrosum separated out in step (E) is separated removal from Waste Sulfuric Acid.
(separate and remove)
The explanation that separating in step (F) is removed is identical with the explanation separating removal in step (B),
Therefore the explanation separating removal in step (F) is omitted.Furthermore, the separation in step (F) is removed
Method can with in step (B) to separate the method removed identical, it is also possible to different.
As it has been described above, the free sodium hydroxide of choosing, potassium hydroxide and the hydroxide added in step (C)
The sodium of at least one, potassium and magnesium in the group that magnesium is formed state with ion in Waste Sulfuric Acid is deposited
?.Therefore, utilize water that the Gypsum Fibrosum separated out in step (F) is carried out, thus can reduce and be analysed
The content of sodium, potassium and magnesium in the Gypsum Fibrosum gone out.
[manufacture method of cement composition]
The manufacture method of the cement composition of the present invention includes: come by the Gypsum Fibrosum manufacture method of the present invention
Manufacture the step of Gypsum Fibrosum and use Gypsum Fibrosum manufactured in the step manufacturing Gypsum Fibrosum to manufacture cement group
The step of compound.That is, the manufacture method of the cement composition of the present invention uses the Gypsum Fibrosum by the present invention
Gypsum Fibrosum manufactured by manufacture method manufactures cement composition.For example, it is also possible to cement clinker (cement
Clinker) add in be come with a small amount of blending constituent by the Gypsum Fibrosum manufactured by the Gypsum Fibrosum manufacture method of the present invention
Manufacture cement composition.Alternatively, it is also possible to by by manufactured by the Gypsum Fibrosum manufacture method of the present invention
Gypsum Fibrosum is used as in the cement clinker that one of molten slag raw material is manufactured, adds the Gypsum Fibrosum manufacture by the present invention
Gypsum Fibrosum or other Gypsum Fibrosum manufactured by method manufacture cement composition with a small amount of blending constituent.
It addition, when heavy metal contained in Waste Sulfuric Acid is ferrum, except by the Gypsum Fibrosum manufacture of the present invention
Beyond Gypsum Fibrosum manufactured by method, the manufacture method of the cement composition of the present invention and then can use this
The hydrated ferric oxide. separated out in the step (C) of bright Gypsum Fibrosum manufacture method is to manufacture cement composition.Example
As, one of molten slag raw material of the cement clinker used in the manufacture as cement composition, it is also possible to
Use the hydrated ferric oxide. separated out in step (C) or by the ferrum made by this hydrated ferric oxide. or ferrum chemical combination
Thing.
[embodiment]
Then, illustrate in greater detail the present invention by embodiment, but the present invention is not implemented by these
Any restriction of example.
[measure and evaluate]
As following, measure and evaluate the Gypsum Fibrosum of embodiment and comparative example.
(1) pH of Waste Sulfuric Acid
Use pH meter (hole field makes institute's (share) and manufactures, trade name: pH meter D-51), pH electricity
Pole (hole field makes institute's (share) and manufactures, trade name: Sleeve Touph electrode 9681-10D), surveys
Surely it is added with calcium source, or selects in the group that free sodium hydroxide, potassium hydroxide and magnesium hydroxide are formed
The pH of the Waste Sulfuric Acid of at least one.
(2) qualification of precipitate
(PANalytical (PANalytical) company manufactures, trade name: X ' Pert around injection device to use X-ray
Pro), carry out adding calcium source in Waste Sulfuric Acid, or select free sodium hydroxide, potassium hydroxide and magnesium hydroxide
The qualification of the precipitate separated out from Waste Sulfuric Acid after at least one in the group formed.
(3) content of the heavy metal in precipitate
Use energy dispersion type fluorescent x-ray analyzer (Spike (SPECTRO) company manufactures,
Trade name: XEPOS), measure in Waste Sulfuric Acid, add calcium source, or choosing free sodium hydroxide, hydroxide
In the precipitate separated out from Waste Sulfuric Acid after at least one in the group that potassium and magnesium hydroxide are formed
The content of ferrum, zinc and chromium.
(4) SO in filtrate4 2-Content
Use ion chromatography apparatus (wearing peace (Dionex) company to manufacture, trade name: ICS-2000),
Measure and Waste Sulfuric Acid is filtered the SO in obtained filtrate4 2-Content.
(5) color of precipitate
With visualization, Waste Sulfuric Acid is filtered the color of obtained precipitate.
[making of the precipitate of embodiment 1～embodiment 7 and comparative example 1～comparative example 5]
One side uses described pH meter to measure pH, simultaneously to 1000mL's in the way of pH becomes 0.5
Waste Sulfuric Acid adds calcium carbonate slurry, and stirs 3 hours.Then, one side is stirred, and one side is entered
And in described Waste Sulfuric Acid, little by little add calcium carbonate slurry.And, when the value of the pH making Waste Sulfuric Acid
Become the setting shown in table 1 and at the end of, the Waste Sulfuric Acid of 30mL is sampled.To being adopted
The Waste Sulfuric Acid of sample carries out filtering and obtaining precipitate and the filtrate of sampled Waste Sulfuric Acid.Furthermore, carbonic acid
Calcium slurry makes by adding the calcium carbonate of 100g in the water of 1L.It addition, before interpolation calcium carbonate
Waste Sulfuric Acid in the content of Fe be 5.8 mass %, the content of zinc is 3300mg/kg, the content of chromium
For 150mg/kg, SO4 2-Content be 19.4 mass %.
[making of the precipitate of embodiment 8 and embodiment 9]
In the interpolation of described calcium carbonate slurry, separate taking-up 200 when the pH of Waste Sulfuric Acid becomes 2.0
The Waste Sulfuric Acid of mL also filters, and adds sodium hydrate aqueous solution until sulfur waste in the filtrate obtained
Till the pH of acid becomes 6.5, and make the Waste Sulfuric Acid of embodiment 8.The Waste Sulfuric Acid of embodiment 8 is entered
Row filters, and is derived from the precipitate of embodiment 8.Calcium chloride water is added in the filtrate of residual
After be stirred, and make the Waste Sulfuric Acid of embodiment 9.The Waste Sulfuric Acid of embodiment 9 is filtered and
Obtain the precipitate of embodiment 9.
[measurement result and evaluation result]
By being adopted of embodiment 1～the Waste Sulfuric Acid sampled of embodiment 7 and comparative example 1～comparative example 5
The evaluation result of the Waste Sulfuric Acid of sample is shown in Table 1, by commenting of the Waste Sulfuric Acid of embodiment 8 and embodiment 9
Valency result is shown in Table 2.
[table 1]
Embodiment 1～embodiment 7 and comparative example 1～the evaluation result of comparative example 5
[table 2]
Embodiment 8 and the evaluation result of embodiment 9
By embodiment 1～embodiment 7 are compared with comparative example 1～comparative example 5, it is known that pass through
PH when adding calcium carbonate slurry to make Gypsum Fibrosum separate out in Waste Sulfuric Acid is made to become less than 3.0, it is possible to decrease
Ferrous components, zinc composition and the content of chromium component in the Gypsum Fibrosum separated out.Further, since embodiment 1
～the color of the precipitate of embodiment 5 is white, therefore will also realize that the ferrous components in separated out Gypsum Fibrosum
Content low.And then, by the SO in the Waste Sulfuric Acid before interpolation calcium carbonate slurry4 2-Content and reality
Execute the SO in the filtrate of example 2～embodiment 74 2-Content compare, it is known that by making to Waste Sulfuric Acid
Middle interpolation calcium carbonate slurry makes the pH of Waste Sulfuric Acid become more than 1.0, the most of SO in Waste Sulfuric Acid4 2-
It is converted to Gypsum Fibrosum.It addition, by embodiment 8, it is known that in Waste Sulfuric Acid, add calcium source make Waste Sulfuric Acid
PH become less than 3.0 and make Gypsum Fibrosum separate out after, in Waste Sulfuric Acid add choosing free sodium hydroxide, hydrogen
At least one in the group that potassium oxide and magnesium hydroxide are formed to make the pH of Waste Sulfuric Acid become 3.5 with
Upper, less than 10.0, the ferrous components in Waste Sulfuric Acid, zinc composition and chromium component thus can be made to separate out.And then,
By embodiment 9, it is known that the Waste Sulfuric Acid after can separating out to making ferrous components, zinc composition and chromium component adds
Calcium source, and make the Gypsum Fibrosum that the content of ferrous components, zinc composition and chromium component is little separate out.
Claims (4)
1. a Gypsum Fibrosum manufacture method, it is characterised in that: include adding in the Waste Sulfuric Acid containing heavy metal
Add calcium source to the step (A) making Gypsum Fibrosum separate out, and in described step (A), make to described sulfur waste
The pH of described Waste Sulfuric Acid when adding described calcium source in acid to make described Gypsum Fibrosum separate out becomes less than 3.0.
Gypsum Fibrosum manufacture method the most according to claim 1, it is characterised in that: also include described
The described Gypsum Fibrosum separated out in step (A) separates the step (B) of removal from described Waste Sulfuric Acid, and
To separation eliminate in the Waste Sulfuric Acid of described Gypsum Fibrosum add select free sodium hydroxide, potassium hydroxide and
The step that at least one in the group that magnesium hydroxide is formed separates out to make the hydroxide of described heavy metal
Suddenly (C), and
In described step (C), make in described Waste Sulfuric Acid, add choosing freely described sodium hydroxide, hydrogen
When at least one in the group that potassium oxide and magnesium hydroxide are formed is to make described hydroxide separate out
The pH of described Waste Sulfuric Acid becomes more than 3.5, less than 10.0.
Gypsum Fibrosum manufacture method the most according to claim 2, it is characterised in that: also include described
The described hydroxide separated out in step (C) separate from described Waste Sulfuric Acid removal step (D),
And
Eliminate to separation and the described Waste Sulfuric Acid of described hydroxide adds calcium source to make Gypsum Fibrosum separate out
Step (E).
4. the manufacture method of a cement composition, it is characterised in that: include by according to claim
Gypsum Fibrosum manufacture method according to any one of 1 to 3 manufacture Gypsum Fibrosum step and
Gypsum Fibrosum manufactured in the step of the described Gypsum Fibrosum of manufacture is used to manufacture the step of cement composition.
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| JP2015-053401 | 2015-03-17 | ||
| JP2015053401 | 2015-03-17 | ||
| JP2015-224641 | 2015-11-17 | ||
| JP2015224641A JP6638345B2 (en) | 2015-03-17 | 2015-11-17 | Method for producing gypsum and method for producing cement composition |
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| CN105985037A true CN105985037A (en) | 2016-10-05 |
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| JP (1) | JP6638345B2 (en) |
| KR (1) | KR102449716B1 (en) |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107417148A (en) * | 2017-09-04 | 2017-12-01 | 青川县天运金属开发有限公司 | In a kind of electroplating sludge after METAL EXTRACTION tailings processing method |
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| 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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Also Published As
| Publication number | Publication date |
|---|---|
| TWI694057B (en) | 2020-05-21 |
| KR20160111875A (en) | 2016-09-27 |
| JP2016172682A (en) | 2016-09-29 |
| KR102449716B1 (en) | 2022-09-30 |
| TW201634391A (en) | 2016-10-01 |
| JP6638345B2 (en) | 2020-01-29 |
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Application publication date: 20161005 |