CN110550927A - Industrial waste gypsum mortar prepared by industrial tail gas synergy and toxicity solving method - Google Patents
Industrial waste gypsum mortar prepared by industrial tail gas synergy and toxicity solving method Download PDFInfo
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- CN110550927A CN110550927A CN201910949136.XA CN201910949136A CN110550927A CN 110550927 A CN110550927 A CN 110550927A CN 201910949136 A CN201910949136 A CN 201910949136A CN 110550927 A CN110550927 A CN 110550927A
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- industrial waste
- waste gypsum
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- 239000002440 industrial waste Substances 0.000 title claims abstract description 141
- 230000001988 toxicity Effects 0.000 title claims abstract description 21
- 231100000419 toxicity Toxicity 0.000 title claims abstract description 21
- 239000011426 gypsum mortar Substances 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 title claims abstract description 11
- 239000010440 gypsum Substances 0.000 claims abstract description 182
- 229910052602 gypsum Inorganic materials 0.000 claims abstract description 182
- 239000007789 gas Substances 0.000 claims abstract description 51
- 239000004576 sand Substances 0.000 claims abstract description 45
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims abstract description 39
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims abstract description 38
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims abstract description 23
- 235000019838 diammonium phosphate Nutrition 0.000 claims abstract description 23
- 239000002994 raw material Substances 0.000 claims abstract description 16
- ZOMBKNNSYQHRCA-UHFFFAOYSA-J calcium sulfate hemihydrate Chemical compound O.[Ca+2].[Ca+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZOMBKNNSYQHRCA-UHFFFAOYSA-J 0.000 claims abstract description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 50
- 239000004568 cement Substances 0.000 claims description 33
- 239000004570 mortar (masonry) Substances 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 18
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 15
- 229920003086 cellulose ether Polymers 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 238000000227 grinding Methods 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 13
- 239000002243 precursor Substances 0.000 claims description 12
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 claims description 10
- 230000000694 effects Effects 0.000 claims description 10
- 239000013078 crystal Substances 0.000 claims description 9
- 150000007524 organic acids Chemical group 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 235000012255 calcium oxide Nutrition 0.000 claims description 8
- 239000000292 calcium oxide Substances 0.000 claims description 8
- 239000004567 concrete Substances 0.000 claims description 8
- 238000006477 desulfuration reaction Methods 0.000 claims description 8
- 230000023556 desulfurization Effects 0.000 claims description 8
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 7
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 7
- 229910019142 PO4 Inorganic materials 0.000 claims description 7
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 7
- YLGXILFCIXHCMC-JHGZEJCSSA-N methyl cellulose Chemical compound COC1C(OC)C(OC)C(COC)O[C@H]1O[C@H]1C(OC)C(OC)C(OC)OC1COC YLGXILFCIXHCMC-JHGZEJCSSA-N 0.000 claims description 7
- 238000000465 moulding Methods 0.000 claims description 7
- 239000010452 phosphate Substances 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 7
- 102000004169 proteins and genes Human genes 0.000 claims description 7
- 108090000623 proteins and genes Proteins 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- 239000006004 Quartz sand Substances 0.000 claims description 6
- 230000002195 synergetic effect Effects 0.000 claims description 6
- 239000002699 waste material Substances 0.000 claims description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims 1
- 239000000701 coagulant Substances 0.000 claims 1
- 239000003546 flue gas Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 10
- 150000004683 dihydrates Chemical class 0.000 abstract description 6
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 abstract description 4
- 229910001424 calcium ion Inorganic materials 0.000 abstract description 4
- 229910021645 metal ion Inorganic materials 0.000 abstract description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 abstract description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 abstract description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052586 apatite Inorganic materials 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 229910052587 fluorapatite Inorganic materials 0.000 abstract description 2
- 238000005342 ion exchange Methods 0.000 abstract description 2
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 abstract description 2
- 239000002918 waste heat Substances 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- 229910001385 heavy metal Inorganic materials 0.000 description 9
- 229910000831 Steel Inorganic materials 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- 239000002912 waste gas Substances 0.000 description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 5
- 238000001354 calcination Methods 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- 238000011065 in-situ storage Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000003340 retarding agent Substances 0.000 description 5
- 230000036571 hydration Effects 0.000 description 4
- 238000006703 hydration reaction Methods 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- 239000002910 solid waste Substances 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 210000000988 bone and bone Anatomy 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000011505 plaster Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 210000001519 tissue Anatomy 0.000 description 2
- 229910014497 Ca10(PO4)6(OH)2 Inorganic materials 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910052925 anhydrite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000010883 osseointegration Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002520 smart material Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B11/00—Calcium sulfate cements
- C04B11/02—Methods and apparatus for dehydrating gypsum
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B11/00—Calcium sulfate cements
- C04B11/26—Calcium sulfate cements strating from chemical gypsum; starting from phosphogypsum or from waste, e.g. purification products of smoke
- C04B11/262—Calcium sulfate cements strating from chemical gypsum; starting from phosphogypsum or from waste, e.g. purification products of smoke waste gypsum other than phosphogypsum
- C04B11/264—Gypsum from the desulfurisation of flue gases
-
- 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
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/14—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements
- C04B28/142—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements containing synthetic or waste calcium sulfate cements
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/14—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements
- C04B28/142—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements containing synthetic or waste calcium sulfate cements
- C04B28/143—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements containing synthetic or waste calcium sulfate cements the synthetic calcium sulfate being phosphogypsum
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/14—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements
- C04B28/142—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements containing synthetic or waste calcium sulfate cements
- C04B28/144—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements containing synthetic or waste calcium sulfate cements the synthetic calcium sulfate being a flue gas desulfurization product
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00767—Uses not provided for elsewhere in C04B2111/00 for waste stabilisation purposes
- C04B2111/00784—Uses not provided for elsewhere in C04B2111/00 for waste stabilisation purposes for disposal only
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
本发明公开了一种工业尾气协同制备工业废石膏砂浆及毒性解决方法，利用工业尾气中的余温将工业废石膏中的二水石膏转变成半水石膏制备成脱硫石膏胶凝材料。该方法以工业废石膏和尾矿砂为基本原材料，利用工业废气余热使得工业废石膏具有胶凝性，同时加入的磷酸氢二铵和工业废石膏中的钙离子生成羟基磷灰石，可显著的提高工业废石膏基胶凝材料的力学性能，同时羟基磷灰石中的OH‑基能被氟化物、氯化物和碳酸根离子代替，生成氟基磷灰石或氯基磷灰石，其中的钙离子被多种金属离子通过发生离子交换反应代替形成对应金属离子的M磷灰石，对工业废石膏和尾矿砂溶出的有害物质进行吸附，可有效解决其毒性问题。The invention discloses a method for synergistically preparing industrial waste gypsum mortar from industrial tail gas and its toxicity solution. The residual temperature in industrial tail gas is used to convert dihydrate gypsum in industrial waste gypsum into hemihydrate gypsum to prepare desulfurized gypsum gelling material. The method uses industrial waste gypsum and tailings sand as basic raw materials, utilizes the waste heat of industrial waste gas to make the industrial waste gypsum gelatinous, and at the same time adds diammonium hydrogen phosphate and calcium ions in the industrial waste gypsum to form hydroxyapatite, which can significantly Improve the mechanical properties of industrial waste gypsum-based cementitious materials, and at the same time, the OH - group in hydroxyapatite can be replaced by fluoride, chloride and carbonate ions to form fluoroapatite or chloroapatite, of which Calcium ions are replaced by a variety of metal ions through ion exchange reactions to form M apatite corresponding to metal ions, and the harmful substances dissolved in industrial waste gypsum and tailings sand can be adsorbed, which can effectively solve their toxicity problems.
Description
技术领域technical field
本发明涉及一种工业尾气协同制备工业废石膏砂浆及毒性解决方法，涉及固体废弃物利用领域。The invention relates to a method for synergistically preparing industrial waste gypsum mortar from industrial tail gas and a toxicity solution, and relates to the field of solid waste utilization.
背景技术Background technique
工业废石膏是以硫酸钙为主的工业废渣。废石膏呈现粉末状，其中80％为硫酸钙，还有硅、铝及铁等成分。工业废石膏有烧结脱硫石膏、磷石膏和氟石膏。通常情况下，每生产一吨磷酸，会排出五吨的磷石膏。Industrial waste gypsum is industrial waste residue mainly composed of calcium sulfate. The waste gypsum is in powder form, 80% of which is calcium sulfate, as well as silicon, aluminum and iron. Industrial waste gypsum includes sintered desulfurization gypsum, phosphogypsum and fluorine gypsum. Typically, for every ton of phosphoric acid produced, five tons of phosphogypsum are discharged.
石膏在不同的脱水条件下形成不同类型半水石膏和无水石膏，Christensen认为，石膏存在五种不同的基本相：二水石膏CaSO4·2H2O、脱水形成高强石膏α-CaSO4·0.5H2O、建筑石膏β-CaSO4·0.5H2O、可溶性硬石膏CaSO4与难溶性硬石膏CaSO4，其中半水石膏和可溶性硬石膏具有胶凝活性，可作为胶凝材料使用。不同的石膏胶凝材料在水化时表现出不同的水化特点，硬化后也具有不同的宏观性能。脱硫石膏与天然石膏形成条件不同，脱硫建筑石膏在应用时具有水化速度快，对缓凝剂不敏感的特点。Gypsum forms different types of hemihydrate and anhydrite under different dehydration conditions. Christensen believes that there are five different basic phases of gypsum: dihydrate gypsum CaSO 4 ·2H 2 O, dehydration to form high-strength gypsum α-CaSO 4 ·0.5 H 2 O, building gypsum β-CaSO 4 ·0.5H 2 O, soluble anhydrite CaSO 4 and insoluble anhydrite CaSO 4 , among which hemihydrate gypsum and soluble anhydrite have gelling activity and can be used as gelling materials. Different gypsum cementitious materials show different hydration characteristics during hydration, and also have different macroscopic properties after hardening. The formation conditions of desulfurized gypsum and natural gypsum are different. When applied, desulfurized building gypsum has the characteristics of fast hydration and insensitivity to retarders.
工业废石膏的主要成分为二水硫酸钙，其用途有建筑石膏和水泥缓凝剂。工业废石膏通过烘干、煅烧、陈化、改性等，使二水石膏脱水分解,脱掉1.5个结晶水，得到的以β半水石膏为主要成分的产品，即为建筑石膏粉。处理后的脱硫石膏可做墙体材料、石膏砌块、粉刷石膏和石膏板。脱硫石膏和天然石膏成分很接近，二水硫酸钙的含量比较高，通过对脱硫石膏去除杂质、改性，完全可以替代天然石膏作为水泥缓凝剂。The main component of industrial waste gypsum is calcium sulfate dihydrate, which is used as construction gypsum and cement retarder. Industrial waste gypsum is dried, calcined, aged, modified, etc. to dehydrate and decompose dihydrate gypsum, remove 1.5 crystal water, and obtain a product with β hemihydrate gypsum as the main component, which is construction gypsum powder. The treated desulfurized gypsum can be used as wall material, gypsum block, plaster plaster and gypsum board. The components of desulfurized gypsum and natural gypsum are very close, and the content of calcium sulfate dihydrate is relatively high. By removing impurities and modifying desulfurized gypsum, it can completely replace natural gypsum as a cement retarder.
羟基磷灰石(Ca10(PO4)6(OH)2,HAP)具有良好的生物相容性和生物活性,能与骨形成直接的骨性结合,是理想的硬组织替代材料,被广泛应用于骨组织的修复与替代技术。最近，人们研究还发现，纳米羟基磷灰石对眼角膜组织的形成有细胞诱导作用，有望用于人工眼角膜材料。羟基磷灰石中的OH-基能被氟化物、氯化物和碳酸根离子代替，生成氟基磷灰石或氯基磷灰石，其中的钙离子可以被多种金属离子通过发生离子交换反应代替形成对应金属离子的M磷灰石，所以羟基磷灰石是一种高效的重金属吸附剂，可以有效地清除或分离微生物，具有低水溶性和高稳定性等特点，是一种绿色环保和智能材料。Hydroxyapatite (Ca 10 (PO 4 ) 6 (OH) 2 , HAP) has good biocompatibility and bioactivity, and can form direct osseointegration with bone. It is an ideal hard tissue replacement material and is widely used. Repair and replacement techniques applied to bone tissue. Recently, people have also found that nano-hydroxyapatite has a cell-inducing effect on the formation of corneal tissue, and it is expected to be used in artificial corneal materials. The OH - group in hydroxyapatite can be replaced by fluoride, chloride and carbonate ions to form fluoroapatite or chloroapatite, in which calcium ions can be exchanged by various metal ions through ion exchange reactions Instead of forming M apatite corresponding to metal ions, hydroxyapatite is an efficient heavy metal adsorbent, which can effectively remove or separate microorganisms, has the characteristics of low water solubility and high stability, and is a green and environmentally friendly Smart Materials.
工业废石膏中硫酸钙含量一般在80％以上。以脱硫石膏作为钙源和磷酸氢二铵反应可制备出羟基磷灰石吸附剂。目前已有关于脱硫石膏制备羟基磷灰石的报道，但利用工业废石膏生成羟基磷灰石固结尾矿砂，并原位解决其毒性的研究还没有。The content of calcium sulfate in industrial waste gypsum is generally above 80%. Hydroxyapatite adsorbent can be prepared by reacting desulfurized gypsum as calcium source with diammonium hydrogen phosphate. At present, there have been reports on the preparation of hydroxyapatite from desulfurized gypsum, but there is no research on the use of industrial waste gypsum to generate hydroxyapatite to consolidate the tailing ore and solve its toxicity in situ.
发明内容Contents of the invention
为了解决现有技术中存在的技术问题，本发明利用工业尾气中的余温将工业废石膏中的二水石膏转变成半水石膏制备成脱硫石膏胶凝材料，然后以工业石膏提供钙源和磷酸氢二铵生成羟基磷灰石，增强工业废石膏的胶凝能力，并利用羟基磷灰石吸附重金属的特性原位解决工业固体废弃物的毒性问题。In order to solve the technical problems existing in the prior art, the present invention utilizes the residual temperature in the industrial tail gas to convert the dihydrate gypsum in the industrial waste gypsum into hemihydrate gypsum to prepare desulfurized gypsum gelling material, and then provide calcium source and Diammonium hydrogen phosphate generates hydroxyapatite, enhances the gelling ability of industrial waste gypsum, and uses the characteristics of hydroxyapatite to adsorb heavy metals to solve the toxicity problem of industrial solid waste in situ.
本发明的具体方案如下：Concrete scheme of the present invention is as follows:
一种工业尾气协同制备工业废石膏砂浆及毒性解决方法，如下：A kind of industrial tail gas collaborative preparation of industrial waste gypsum mortar and toxicity solution, as follows:
步骤1.工业废石膏首先经过工业尾气的烘干去除工业废石膏中的水分和部分结晶水，使得工业废石膏的主要成分二水硫酸钙转变成半水硫酸钙，使得工业废石膏具有胶凝活性，在经过一定的粉磨得到预处理工业废石膏；Step 1. The industrial waste gypsum is firstly dried to remove the moisture and part of the crystal water in the industrial waste gypsum, so that the main component of the industrial waste gypsum, calcium sulfate dihydrate, is transformed into calcium sulfate hemihydrate, so that the industrial waste gypsum has gelling properties. Activity, after a certain amount of grinding to obtain pretreated industrial waste gypsum;
步骤2：将磷酸氢二铵溶于水制备出羟基磷灰石前驱液；Step 2: Dissolving diammonium hydrogen phosphate in water to prepare a hydroxyapatite precursor;
步骤3将步骤1中得到的预处理工业废石膏、水泥、生石灰、缓凝剂、纤维素醚粉体放入到砂浆搅拌机中搅拌混合均匀，然后加入羟基磷灰石前驱液，搅拌；Step 3: Put the pretreated industrial waste gypsum, cement, quicklime, retarder, and cellulose ether powder obtained in step 1 into a mortar mixer and stir to mix evenly, then add the hydroxyapatite precursor, and stir;
步骤4将尾矿砂加入到搅拌机中搅拌，得到所述的羟基磷灰石增强工业废石膏基尾矿砂砂浆。Step 4: Put the tailings sand into a mixer and stir to obtain the hydroxyapatite-reinforced industrial waste gypsum-based tailings sand mortar.
步骤5将混凝土拌合物放入到模具中成型，凝结后拆模，并在标准状况下养护。Step 5 Put the concrete mixture into the mold for molding, remove the mold after setting, and maintain it under standard conditions.
本发明所提供的工业废石膏尾矿砂砂浆的原料组成是：预处理工业废石膏100份、生石灰0-10份、磷酸氢二铵5-30份、尾矿砂50-200份、石英砂50-200份、水40-70份、水泥0-20份、石膏缓凝剂0.1-1份、纤维素醚0.05-0.6份。The raw material composition of the industrial waste gypsum tailings sand mortar provided by the present invention is: 100 parts of pretreated industrial waste gypsum, 0-10 parts of quicklime, 5-30 parts of diammonium hydrogen phosphate, 50-200 parts of tailings sand, 50-50 parts of quartz sand 200 parts, 40-70 parts of water, 0-20 parts of cement, 0.1-1 part of gypsum retarder, and 0.05-0.6 parts of cellulose ether.
需要进一步说明的，工业废石膏为烧结脱硫石膏、磷石膏和氟石膏的一种。It should be further explained that industrial waste gypsum is one of sintered desulfurization gypsum, phosphogypsum and fluorogypsum.
进一步的，所述的工业尾气为钢厂、水泥厂等工业排放的废烟气，其温度在100-200℃之间，其预处理时间可根据尾气的温度调整。Further, the industrial tail gas is waste gas discharged from industries such as steel mills and cement plants, and its temperature is between 100-200°C, and the pretreatment time can be adjusted according to the temperature of the tail gas.
进一步的，工业废石膏预处理的设备为炒锅、回转窑、沸腾炉的一种。Further, the equipment for pretreatment of industrial waste gypsum is one of frying pan, rotary kiln and fluidized fluidized furnace.
进一步的，经工业尾气处理后的石膏经过粉磨得到预处理工业废石膏，其比表面积应大于280m2/kg。Further, the gypsum treated with industrial tail gas is ground to obtain pretreated industrial waste gypsum, and its specific surface area should be greater than 280m 2 /kg.
进一步的，水泥为P.O 42.5水泥，符合国标GB 175-2007，其比表面积应大于280m2/kg。Further, the cement is PO 42.5 cement, conforming to the national standard GB 175-2007, and its specific surface area should be greater than 280m 2 /kg.
进一步的，石膏缓凝剂为有机酸和有机酸可溶盐、碱性磷酸盐以及蛋白质类等缓凝剂的一种。Further, the gypsum retarder is a kind of retarder such as organic acid and organic acid soluble salt, alkaline phosphate and protein.
进一步的，纤维素醚为甲基纤维素醚或羟乙基纤维素醚的一种。Further, the cellulose ether is a kind of methyl cellulose ether or hydroxyethyl cellulose ether.
进一步的，尾矿砂细度模数在2.8，含泥量小于1.5％。天然骨料为Ⅱ区中级砂，细度模数为3.05，符合GB/T14685-2011。Further, the fineness modulus of the tailings sand is 2.8, and the mud content is less than 1.5%. The natural aggregate is medium-grade sand in Zone II, with a fineness modulus of 3.05, which complies with GB/T14685-2011.
进一步的，不同质量磷酸氢二铵在水中充分溶解，制备出不同浓度的磷酸氢二铵溶液，在与脱硫石膏混合。Further, diammonium hydrogen phosphate of different quality is fully dissolved in water to prepare diammonium hydrogen phosphate solutions of different concentrations, which are then mixed with desulfurized gypsum.
进一步的，该方法还包括以下步骤：将所得面层砂浆放入到模具中成型，凝结后拆模，并按照标准要求养护。Further, the method also includes the following steps: putting the obtained surface layer mortar into a mold for molding, removing the mold after setting, and curing according to standard requirements.
本发明具有如下有益效果：The present invention has following beneficial effect:
(1)利用工业尾气处理工业废石膏，尾气处理脱硫石膏低能耗，充分利用工业尾气的余热将工业废石膏中的二水石膏转变成半水石膏，使得工业废石膏具有胶凝性，使得工业废气和工业固废两种工业副产物结合形成具有胶凝性的绿色环保建筑材料。(1) Use industrial tail gas to treat industrial waste gypsum. Tail gas treatment of desulfurized gypsum has low energy consumption, and the waste heat of industrial tail gas is fully used to convert dihydrate gypsum in industrial waste gypsum into hemihydrate gypsum, so that industrial waste gypsum has gelling properties, making industrial The two industrial by-products of exhaust gas and industrial solid waste are combined to form a gelling green and environmentally friendly building material.
(2)工业废石膏中80％以上的成分为CaSO4可以为羟基磷灰石提供充足的钙源，所以在工业废石膏中加入磷酸氢二铵可以生成羟基磷灰石，一方面羟基磷灰石可以形成纳米空间网状结构可以有效的提高工业废石膏的强度。另一方面羟基磷灰石的吸附重金属离子的特性又可以原位解决工业废石膏和尾矿砂毒性的问题。(2) More than 80% of the industrial waste gypsum is CaSO 4 , which can provide sufficient calcium source for hydroxyapatite, so adding diammonium hydrogen phosphate to industrial waste gypsum can generate hydroxyapatite. On the one hand, hydroxyapatite Gypsum can form a nano-space network structure, which can effectively improve the strength of industrial waste gypsum. On the other hand, the property of hydroxyapatite to adsorb heavy metal ions can solve the problem of toxicity of industrial waste gypsum and tailings sand in situ.
具体实施方式Detailed ways
应该指出，以下详细说明都是例示性的，旨在对本申请提供进一步的说明。除非另有指明，本文使用的所有技术和科学术语具有与本申请所属技术领域的普通技术人员通常理解的相同含义。It should be pointed out that the following detailed description is exemplary and intended to provide further explanation to the present application. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
正如背景技术部分所描述的，工业废石膏中硫酸钙含量一般在80％以上。以脱硫石膏作为钙源和磷酸氢二铵反应可制备出羟基磷灰石吸附剂。目前已有关于脱硫石膏制备羟基磷灰石的报道，但利用工业废石膏生成羟基磷灰石固结尾矿砂，并原位解决其毒性的研究还没有；因此本申请提出了利用工业尾气中的余温将工业废石膏中的二水石膏转变成半水石膏制备成脱硫石膏胶凝材料，然后以工业石膏提供钙源和磷酸氢二铵生成羟基磷灰石，增强工业废石膏的胶凝能力，并利用羟基磷灰石吸附重金属的特性原位解决工业固体废弃物的毒性问题；具体的如下：As described in the background technology section, the content of calcium sulfate in industrial waste gypsum is generally above 80%. Hydroxyapatite adsorbent can be prepared by reacting desulfurized gypsum as calcium source with diammonium hydrogen phosphate. At present, there have been reports on the preparation of hydroxyapatite from desulfurized gypsum, but there is no research on using industrial waste gypsum to generate hydroxyapatite to consolidate the tailing ore, and to solve its toxicity in situ; Warmly convert dihydrate gypsum in industrial waste gypsum into hemihydrate gypsum to prepare desulfurized gypsum gelling material, and then use industrial gypsum to provide calcium source and diammonium hydrogen phosphate to generate hydroxyapatite to enhance the gelling ability of industrial waste gypsum. And use the characteristics of hydroxyapatite to adsorb heavy metals to solve the toxicity problem of industrial solid waste in situ; the details are as follows:
需要说明的是在下述实施例中，如非特别说明，所用试剂和材料均为常规市售可得。It should be noted that in the following examples, unless otherwise specified, all reagents and materials used are commercially available.
对比案例：Comparison case:
先利用工业废气预处理工业废石膏，工业废石膏首先经过工业尾气的烘干去除工业废石膏中的水分和部分结晶水的，使得工业废石膏的主要成分二水硫酸钙转变成半水硫酸钙，使得工业废石膏具有胶凝活性，在经过一定的粉磨得到预处理工业废石膏；First use industrial waste gas to pretreat industrial waste gypsum. Industrial waste gypsum is firstly dried by industrial tail gas to remove moisture and part of crystal water in industrial waste gypsum, so that the main component of industrial waste gypsum, calcium sulfate dihydrate, is transformed into calcium sulfate hemihydrate. , so that the industrial waste gypsum has gelling activity, and the pretreated industrial waste gypsum can be obtained after certain grinding;
然后准备工业废石膏尾矿砂砂浆的原料，将原料按照以下配合比称量：预处理工业废石膏100份、尾矿砂150份、石英砂150份、水55份、石膏缓凝剂0.3份、纤维素醚0.2份；Then prepare raw materials for industrial waste gypsum tailings sand mortar, and weigh the raw materials according to the following proportions: 100 parts of pretreated industrial waste gypsum, 150 parts of tailings sand, 150 parts of quartz sand, 55 parts of water, 0.3 parts of gypsum retarder, fiber 0.2 parts of plain ether;
再次制备工业废石膏基砂浆：Prepare industrial waste gypsum-based mortar again:
将预处理工业废石膏、缓凝剂等粉体放入到砂浆搅拌机中搅拌混合均匀，然后加入水，搅拌1min。Put the pretreated industrial waste gypsum, retarder and other powders into the mortar mixer and mix well, then add water and stir for 1min.
将尾矿砂加入到搅拌机中，搅拌2min，得到所述的工业废石膏基尾矿砂砂浆。Put the tailings sand into the mixer and stir for 2 minutes to obtain the industrial waste gypsum-based tailings sand mortar.
需要进一步说明的，本实施例中的工业废石膏为烧结脱硫石膏、磷石膏和氟石膏的一种。It should be further explained that the industrial waste gypsum in this embodiment is one of sintered desulfurization gypsum, phosphogypsum and fluorogypsum.
需要进一步说明的，本实施例中的工业尾气为钢厂、水泥厂等工业排放的废烟气，其温度在100-200℃之间，其预处理时间可根据尾气的温度调整。It should be further explained that the industrial tail gas in this embodiment is waste gas discharged from industries such as steel mills and cement plants, and its temperature is between 100-200°C, and its pretreatment time can be adjusted according to the temperature of the tail gas.
需要进一步说明的，本实施例中的工业废石膏预处理的生产煅烧设备为炒锅、回转窑、沸腾炉的一种。It should be further explained that the production and calcination equipment for the pretreatment of industrial waste gypsum in this embodiment is a kind of frying pan, rotary kiln and fluidized fluidized furnace.
需要进一步说明的，本实施例中的经工业尾气处理后的石膏经过粉磨得到预处理工业废石膏，其比表面积应大于280m2/kg。It should be further explained that the specific surface area of the pretreated industrial waste gypsum obtained by grinding the gypsum treated with industrial tail gas in this embodiment should be greater than 280 m 2 /kg.
需要进一步说明的，本实施例中的水泥为P.O 42.5水泥，符合国标GB175-2007，其比表面积应大于280m2/kg。It should be further explained that the cement in this example is PO 42.5 cement, which conforms to the national standard GB175-2007, and its specific surface area should be greater than 280m 2 /kg.
需要进一步说明的，本实施例中的缓凝剂为有机酸及其可溶盐、碱性磷酸盐以及蛋白质类等缓凝剂的一种。It should be further explained that the setting retarder in this embodiment is a kind of retarding agent such as organic acid and its soluble salt, alkaline phosphate and protein.
需要进一步说明的，本实施例中的纤维素醚为甲基纤维素醚或羟乙基纤维素醚的一种。It should be further explained that the cellulose ether in this embodiment is a kind of methyl cellulose ether or hydroxyethyl cellulose ether.
需要进一步说明的，本实施例中的铁尾矿砂细度模数在2.8，含泥量小于1.5％。天然骨料为Ⅱ区中级砂，细度模数为3.05，符合GB/T14685-2011。It should be further explained that the fineness modulus of the iron tailings sand in this embodiment is 2.8, and the mud content is less than 1.5%. The natural aggregate is medium-grade sand in Zone II, with a fineness modulus of 3.05, which complies with GB/T14685-2011.
实施案例1Implementation Case 1
先利用工业废气预处理工业废石膏，工业废石膏首先经过工业尾气的烘干去除工业废石膏中的水分和部分结晶水的，使得工业废石膏的主要成分二水硫酸钙转变成半水硫酸钙，使得工业废石膏具有胶凝活性，在经过一定的粉磨得到预处理工业废石膏；First use industrial waste gas to pretreat industrial waste gypsum. Industrial waste gypsum is firstly dried by industrial tail gas to remove moisture and part of crystal water in industrial waste gypsum, so that the main component of industrial waste gypsum, calcium sulfate dihydrate, is transformed into calcium sulfate hemihydrate. , so that the industrial waste gypsum has gelling activity, and the pretreated industrial waste gypsum can be obtained after certain grinding;
然后准备工业废石膏尾矿砂砂浆的原料，将原料按照以下配合比称量：预处理工业废石膏100份、磷酸氢二铵10份、尾矿砂150份、石英砂150份、水55份、石膏缓凝剂0.3份、纤维素醚0.2份。Then prepare raw materials for industrial waste gypsum tailings sand mortar, and weigh the raw materials according to the following proportions: 100 parts of pretreated industrial waste gypsum, 10 parts of diammonium hydrogen phosphate, 150 parts of tailings sand, 150 parts of quartz sand, 55 parts of water, gypsum 0.3 parts of retarder, 0.2 parts of cellulose ether.
再次制备工业废石膏基砂浆：Prepare industrial waste gypsum-based mortar again:
(1)首先将磷酸氢二铵溶于水制备出羟基磷灰石前驱液。(1) First, diammonium hydrogen phosphate was dissolved in water to prepare a hydroxyapatite precursor.
(2)然后预处理工业废石膏、水泥、缓凝剂等粉体放入到砂浆搅拌机中搅拌混合均匀，然后加入羟基磷灰石前驱液，搅拌1min。(2) Then put the pretreated industrial waste gypsum, cement, retarder and other powders into the mortar mixer and mix evenly, then add the hydroxyapatite precursor solution and stir for 1 min.
(3)将尾矿砂加入到搅拌机中，搅拌2min，得到所述的羟基磷灰石增强工业废石膏基尾矿砂砂浆。(3) Put the tailings sand into the mixer and stir for 2 minutes to obtain the hydroxyapatite reinforced industrial waste gypsum-based tailings sand mortar.
(4)将混凝土拌合物放入到模具中成型，凝结后拆模，并在标准状况下养护。(4) Put the concrete mixture into the mold for molding, remove the mold after setting, and maintain it under standard conditions.
需要进一步说明的，本实施例中的工业废石膏为烧结脱硫石膏、磷石膏和氟石膏的一种。It should be further explained that the industrial waste gypsum in this embodiment is one of sintered desulfurization gypsum, phosphogypsum and fluorogypsum.
需要进一步说明的，本实施例中的工业尾气为钢厂、水泥厂等工业排放的废烟气，其温度在100-200℃之间，其预处理时间可根据尾气的温度调整。It should be further explained that the industrial tail gas in this embodiment is waste gas discharged from industries such as steel mills and cement plants, and its temperature is between 100-200°C, and its pretreatment time can be adjusted according to the temperature of the tail gas.
需要进一步说明的，本实施例中的工业废石膏预处理的生产煅烧设备为炒锅、回转窑、沸腾炉的一种。It should be further explained that the production and calcination equipment for the pretreatment of industrial waste gypsum in this embodiment is a kind of frying pan, rotary kiln and fluidized fluidized furnace.
需要进一步说明的，本实施例中的经工业尾气处理后的石膏经过粉磨得到预处理工业废石膏，其比表面积应大于280m2/kg。It should be further explained that the specific surface area of the pretreated industrial waste gypsum obtained by grinding the gypsum treated with industrial tail gas in this embodiment should be greater than 280 m 2 /kg.
需要进一步说明的，本实施例中的水泥为P.O 42.5水泥，符合国标GB175-2007，其比表面积应大于280m2/kg。It should be further explained that the cement in this example is PO 42.5 cement, which conforms to the national standard GB175-2007, and its specific surface area should be greater than 280m 2 /kg.
需要进一步说明的，本实施例中的缓凝剂为有机酸及其可溶盐、碱性磷酸盐以及蛋白质类等缓凝剂的一种。It should be further explained that the setting retarder in this embodiment is a kind of retarding agent such as organic acid and its soluble salt, alkaline phosphate and protein.
需要进一步说明的，本实施例中的纤维素醚为甲基纤维素醚或羟乙基纤维素醚的一种。It should be further explained that the cellulose ether in this embodiment is a kind of methyl cellulose ether or hydroxyethyl cellulose ether.
需要进一步说明的，本实施例中的铁尾矿砂细度模数在2.8，含泥量小于1.5％。天然骨料为Ⅱ区中级砂，细度模数为3.05，符合GB/T14685-2011。It should be further explained that the fineness modulus of the iron tailings sand in this embodiment is 2.8, and the mud content is less than 1.5%. The natural aggregate is medium-grade sand in Zone II, with a fineness modulus of 3.05, which complies with GB/T14685-2011.
实施案例1相对对比案例掺入了10份的磷酸氢二铵，磷酸氢二铵可以和脱硫石膏中溶出的钙离子反应生成羟基磷灰石纳米空间网状结构，因此砂浆试块的强度提高，同时生成的羟基磷灰石可以吸附重金属离子，试样的重金属离子浸出量减少。Implementation case 1 Relative comparison case mixed with 10 parts of diammonium hydrogen phosphate, diammonium hydrogen phosphate can react with calcium ions dissolved in desulfurized gypsum to form a nano-space network structure of hydroxyapatite, so the strength of the mortar test block is improved, At the same time, the generated hydroxyapatite can adsorb heavy metal ions, and the leaching amount of heavy metal ions in the sample is reduced.
实施案例2Implementation Case 2
先利用工业废气预处理工业废石膏，工业废石膏首先经过工业尾气的烘干去除工业废石膏中的水分和部分结晶水的，使得工业废石膏的主要成分二水硫酸钙转变成半水硫酸钙，使得工业废石膏具有胶凝活性，在经过一定的粉磨得到预处理工业废石膏；First use industrial waste gas to pretreat industrial waste gypsum. Industrial waste gypsum is firstly dried by industrial tail gas to remove moisture and part of crystal water in industrial waste gypsum, so that the main component of industrial waste gypsum, calcium sulfate dihydrate, is transformed into calcium sulfate hemihydrate. , so that the industrial waste gypsum has gelling activity, and the pretreated industrial waste gypsum can be obtained after certain grinding;
然后准备工业废石膏尾矿砂砂浆的原料，将原料按照以下配合比称量：将原料按照以下配合比称量：预处理工业废石膏100份、磷酸氢二铵20份、尾矿砂150份、石英砂150份、水55份、石膏缓凝剂0.3份、纤维素醚0.2份。Then prepare raw materials for industrial waste gypsum tailings sand mortar, and weigh the raw materials according to the following mixing ratio: Weigh the raw materials according to the following mixing ratio: 100 parts of pretreated industrial waste gypsum, 20 parts of diammonium hydrogen phosphate, 150 parts of tailing sand, quartz 150 parts of sand, 55 parts of water, 0.3 parts of gypsum retarder, and 0.2 parts of cellulose ether.
上述工业废石膏基砂浆的制备过程如下：The preparation process of above-mentioned industrial waste gypsum-based mortar is as follows:
(1)首先将磷酸氢二铵溶于水制备出羟基磷灰石前驱液。(1) First, diammonium hydrogen phosphate was dissolved in water to prepare a hydroxyapatite precursor.
(2)然后预处理工业废石膏、水泥、缓凝剂等粉体放入到砂浆搅拌机中搅拌混合均匀，然后加入羟基磷灰石前驱液，搅拌1min。(2) Then put the pretreated industrial waste gypsum, cement, retarder and other powders into the mortar mixer and mix evenly, then add the hydroxyapatite precursor solution and stir for 1 min.
(3)将尾矿砂加入到搅拌机中，搅拌2min，得到所述的羟基磷灰石增强工业废石膏基尾矿砂砂浆。(3) Put the tailings sand into the mixer and stir for 2 minutes to obtain the hydroxyapatite reinforced industrial waste gypsum-based tailings sand mortar.
(4)将混凝土拌合物放入到模具中成型，凝结后拆模，并在标准状况下养护。(4) Put the concrete mixture into the mold for molding, remove the mold after setting, and maintain it under standard conditions.
需要进一步说明的，本实施例中的工业废石膏为烧结脱硫石膏、磷石膏和氟石膏的一种。It should be further explained that the industrial waste gypsum in this embodiment is one of sintered desulfurization gypsum, phosphogypsum and fluorogypsum.
需要进一步说明的，本实施例中的工业尾气为钢厂、水泥厂等工业排放的废烟气，其温度在100-200℃之间，其预处理时间可根据尾气的温度调整。It should be further explained that the industrial tail gas in this embodiment is waste gas discharged from industries such as steel mills and cement plants, and its temperature is between 100-200°C, and its pretreatment time can be adjusted according to the temperature of the tail gas.
需要进一步说明的，本实施例中的工业废石膏预处理的生产煅烧设备为炒锅、回转窑、沸腾炉的一种。It should be further explained that the production and calcination equipment for the pretreatment of industrial waste gypsum in this embodiment is a kind of frying pan, rotary kiln and fluidized fluidized furnace.
需要进一步说明的，本实施例中的经工业尾气处理后的石膏经过粉磨得到预处理工业废石膏，其比表面积应大于280m2/kg。It should be further explained that the specific surface area of the pretreated industrial waste gypsum obtained by grinding the gypsum treated with industrial tail gas in this embodiment should be greater than 280 m 2 /kg.
需要进一步说明的，本实施例中的水泥为P.O 42.5水泥，符合国标GB175-2007，其比表面积应大于280m2/kg。It should be further explained that the cement in this example is PO 42.5 cement, which conforms to the national standard GB175-2007, and its specific surface area should be greater than 280m 2 /kg.
需要进一步说明的，本实施例中的缓凝剂为有机酸及其可溶盐、碱性磷酸盐以及蛋白质类等缓凝剂的一种。It should be further explained that the setting retarder in this embodiment is a kind of retarding agent such as organic acid and its soluble salt, alkaline phosphate and protein.
需要进一步说明的，本实施例中的纤维素醚为甲基纤维素醚或羟乙基纤维素醚的一种。It should be further explained that the cellulose ether in this embodiment is a kind of methyl cellulose ether or hydroxyethyl cellulose ether.
需要进一步说明的，本实施例中的铁尾矿砂细度模数在2.8，含泥量小于1.5％。天然骨料为Ⅱ区中级砂，细度模数为3.05，符合GB/T14685-2011。It should be further explained that the fineness modulus of the iron tailings sand in this embodiment is 2.8, and the mud content is less than 1.5%. The natural aggregate is medium-grade sand in Zone II, with a fineness modulus of 3.05, which complies with GB/T14685-2011.
实施案例2进一步增加了磷酸氢二铵的掺量，砂浆中生成的羟基磷灰石增多，所以强度进一步增加，重金属浸出量进一步减少。In Example 2, the amount of diammonium hydrogen phosphate was further increased, and the hydroxyapatite generated in the mortar increased, so the strength was further increased, and the leached amount of heavy metals was further reduced.
实施案例3Implementation Case 3
先利用工业废气预处理工业废石膏，工业废石膏首先经过工业尾气的烘干去除工业废石膏中的水分和部分结晶水的，使得工业废石膏的主要成分二水硫酸钙转变成半水硫酸钙，使得工业废石膏具有胶凝活性，在经过一定的粉磨得到预处理工业废石膏；First use industrial waste gas to pretreat industrial waste gypsum. Industrial waste gypsum is firstly dried by industrial tail gas to remove moisture and part of crystal water in industrial waste gypsum, so that the main component of industrial waste gypsum, calcium sulfate dihydrate, is transformed into calcium sulfate hemihydrate. , so that the industrial waste gypsum has gelling activity, and the pretreated industrial waste gypsum can be obtained after certain grinding;
然后准备工业废石膏尾矿砂砂浆的原料，将原料按照以下配合比称量：将原料按照以下配合比称量：将原料按照以下配合比称量：预处理工业废石膏100份、磷酸氢二铵10份、水泥10份，尾矿砂150份、石英砂150份、水55份、石膏缓凝剂0.3份、纤维素醚0.2份。Then prepare raw materials for industrial waste gypsum tailings sand mortar, and weigh the raw materials according to the following mixing ratio: Weigh the raw materials according to the following mixing ratio: weigh the raw materials according to the following mixing ratio: 100 parts of pretreated industrial waste gypsum, diammonium hydrogen phosphate 10 parts, 10 parts of cement, 150 parts of tailings sand, 150 parts of quartz sand, 55 parts of water, 0.3 parts of gypsum retarder, and 0.2 parts of cellulose ether.
上述工业废石膏基砂浆的制备过程如下：The preparation process of above-mentioned industrial waste gypsum-based mortar is as follows:
(1)首先将磷酸氢二铵溶于水制备出羟基磷灰石前驱液。(1) First, diammonium hydrogen phosphate was dissolved in water to prepare a hydroxyapatite precursor.
(2)然后预处理工业废石膏、水泥、缓凝剂等粉体放入到砂浆搅拌机中搅拌混合均匀，然后加入羟基磷灰石前驱液，搅拌1min。(2) Then put the pretreated industrial waste gypsum, cement, retarder and other powders into the mortar mixer and mix evenly, then add the hydroxyapatite precursor solution and stir for 1 min.
(3)将尾矿砂加入到搅拌机中，搅拌2min，得到所述的羟基磷灰石增强工业废石膏基尾矿砂砂浆。(3) Put the tailings sand into the mixer and stir for 2 minutes to obtain the hydroxyapatite reinforced industrial waste gypsum-based tailings sand mortar.
(4)将混凝土拌合物放入到模具中成型，凝结后拆模，并在标准状况下养护。(4) Put the concrete mixture into the mold for molding, remove the mold after setting, and maintain it under standard conditions.
需要进一步说明的，本实施例中的工业废石膏为烧结脱硫石膏、磷石膏和氟石膏的一种。It should be further explained that the industrial waste gypsum in this embodiment is one of sintered desulfurization gypsum, phosphogypsum and fluorogypsum.
需要进一步说明的，本实施例中的工业尾气为钢厂、水泥厂等工业排放的废烟气，其温度在100-200℃之间，其预处理时间可根据尾气的温度调整。It should be further explained that the industrial tail gas in this embodiment is waste gas discharged from industries such as steel mills and cement plants, and its temperature is between 100-200°C, and its pretreatment time can be adjusted according to the temperature of the tail gas.
需要进一步说明的，本实施例中的工业废石膏预处理的生产煅烧设备为炒锅、回转窑、沸腾炉的一种。It should be further explained that the production and calcination equipment for the pretreatment of industrial waste gypsum in this embodiment is a kind of frying pan, rotary kiln and fluidized fluidized furnace.
需要进一步说明的，本实施例中的经工业尾气处理后的石膏经过粉磨得到预处理工业废石膏，其比表面积应大于280m2/kg。It should be further explained that the specific surface area of the pretreated industrial waste gypsum obtained by grinding the gypsum treated with industrial tail gas in this embodiment should be greater than 280 m 2 /kg.
需要进一步说明的，本实施例中的水泥为P.O 42.5水泥，符合国标GB175-2007，其比表面积应大于280m2/kg。It should be further explained that the cement in this example is PO 42.5 cement, which conforms to the national standard GB175-2007, and its specific surface area should be greater than 280m 2 /kg.
需要进一步说明的，本实施例中的缓凝剂为有机酸及其可溶盐、碱性磷酸盐以及蛋白质类等缓凝剂的一种。It should be further explained that the setting retarder in this embodiment is a kind of retarding agent such as organic acid and its soluble salt, alkaline phosphate and protein.
需要进一步说明的，本实施例中的纤维素醚为甲基纤维素醚或羟乙基纤维素醚的一种。It should be further explained that the cellulose ether in this embodiment is a kind of methyl cellulose ether or hydroxyethyl cellulose ether.
需要进一步说明的，本实施例中的铁尾矿砂细度模数在2.8，含泥量小于1.5％。天然骨料为Ⅱ区中级砂，细度模数为3.05，符合GB/T14685-2011。It should be further explained that the fineness modulus of the iron tailings sand in this embodiment is 2.8, and the mud content is less than 1.5%. The natural aggregate is medium-grade sand in Zone II, with a fineness modulus of 3.05, which complies with GB/T14685-2011.
实施案例3相对于实施案例1掺入了水泥，增加了脱硫石膏砂浆的胶凝活性，使得砂浆试块的强度增加，同时水泥生成的水化产物本身就有固化重金属离子的作用，因此重金属离子浸出量减少，强度增大。Compared with Example 1, Example 3 is mixed with cement, which increases the gelling activity of desulfurized gypsum mortar and increases the strength of the mortar test block. At the same time, the hydration products generated by cement itself have the effect of solidifying heavy metal ions, so heavy metal ions The amount of leaching decreases and the strength increases.
实施案例4Implementation Case 4
先利用工业废气预处理工业废石膏，工业废石膏首先经过工业尾气的烘干去除工业废石膏中的水分和部分结晶水的，使得工业废石膏的主要成分二水硫酸钙转变成半水硫酸钙，使得工业废石膏具有胶凝活性，在经过一定的粉磨得到预处理工业废石膏；然后准备工业废石膏尾矿砂砂浆的原料；First use industrial waste gas to pretreat industrial waste gypsum. Industrial waste gypsum is firstly dried by industrial tail gas to remove moisture and part of crystal water in industrial waste gypsum, so that the main component of industrial waste gypsum, calcium sulfate dihydrate, is transformed into calcium sulfate hemihydrate. , so that the industrial waste gypsum has gelling activity, and after a certain amount of grinding, the pretreated industrial waste gypsum is obtained; and then the raw material of the industrial waste gypsum tailings sand mortar is prepared;
将原料按照以下配合比称量：预处理工业废石膏100份、磷酸氢二铵10份、生石灰5份，尾矿砂150份、石英砂150份、水55份、石膏缓凝剂0.3份、纤维素醚0.2份。Weigh the raw materials according to the following mixing ratio: 100 parts of pretreated industrial waste gypsum, 10 parts of diammonium hydrogen phosphate, 5 parts of quicklime, 150 parts of tailings sand, 150 parts of quartz sand, 55 parts of water, 0.3 parts of gypsum retarder, fiber 0.2 parts of plain ether.
上述工业废石膏基砂浆的制备过程如下：The preparation process of above-mentioned industrial waste gypsum-based mortar is as follows:
(1)首先将磷酸氢二铵溶于水制备出羟基磷灰石前驱液。(1) First, diammonium hydrogen phosphate was dissolved in water to prepare a hydroxyapatite precursor.
(2)然后预处理工业废石膏、水泥、缓凝剂等粉体放入到砂浆搅拌机中搅拌混合均匀，然后加入羟基磷灰石前驱液，搅拌1min。(2) Then put the pretreated industrial waste gypsum, cement, retarder and other powders into the mortar mixer and mix evenly, then add the hydroxyapatite precursor solution and stir for 1 min.
(3)将尾矿砂加入到搅拌机中，搅拌2min，得到所述的羟基磷灰石增强工业废石膏基尾矿砂砂浆。(3) Put the tailings sand into the mixer and stir for 2 minutes to obtain the hydroxyapatite reinforced industrial waste gypsum-based tailings sand mortar.
(4)将混凝土拌合物放入到模具中成型，凝结后拆模，并在标准状况下养护。(4) Put the concrete mixture into the mold for molding, remove the mold after setting, and maintain it under standard conditions.
需要进一步说明的，本实施例中的工业废石膏为烧结脱硫石膏、磷石膏和氟石膏的一种。It should be further explained that the industrial waste gypsum in this embodiment is one of sintered desulfurization gypsum, phosphogypsum and fluorogypsum.
需要进一步说明的，本实施例中的工业尾气为钢厂、水泥厂等工业排放的废烟气，其温度在100-200℃之间，其预处理时间可根据尾气的温度调整。It should be further explained that the industrial tail gas in this embodiment is waste gas discharged from industries such as steel mills and cement plants, and its temperature is between 100-200°C, and its pretreatment time can be adjusted according to the temperature of the tail gas.
需要进一步说明的，本实施例中的工业废石膏预处理的生产煅烧设备为炒锅、回转窑、沸腾炉的一种。It should be further explained that the production and calcination equipment for the pretreatment of industrial waste gypsum in this embodiment is a kind of frying pan, rotary kiln and fluidized fluidized furnace.
需要进一步说明的，本实施例中的经工业尾气处理后的石膏经过粉磨得到预处理工业废石膏，其比表面积应大于280m2/kg。It should be further explained that the specific surface area of the pretreated industrial waste gypsum obtained by grinding the gypsum treated with industrial tail gas in this embodiment should be greater than 280 m 2 /kg.
需要进一步说明的，本实施例中的水泥为P.O 42.5水泥，符合国标GB175-2007，其比表面积应大于280m2/kg。It should be further explained that the cement in this example is PO 42.5 cement, which conforms to the national standard GB175-2007, and its specific surface area should be greater than 280m 2 /kg.
需要进一步说明的，本实施例中的缓凝剂为有机酸及其可溶盐、碱性磷酸盐以及蛋白质类等缓凝剂的一种。It should be further explained that the setting retarder in this embodiment is a kind of retarding agent such as organic acid and its soluble salt, alkaline phosphate and protein.
需要进一步说明的，本实施例中的纤维素醚为甲基纤维素醚或羟乙基纤维素醚的一种。It should be further explained that the cellulose ether in this embodiment is a kind of methyl cellulose ether or hydroxyethyl cellulose ether.
需要进一步说明的，本实施例中的铁尾矿砂细度模数在2.8，含泥量小于1.5％。天然骨料为Ⅱ区中级砂，细度模数为3.05，符合GB/T14685-2011。It should be further explained that the fineness modulus of the iron tailings sand in this embodiment is 2.8, and the mud content is less than 1.5%. The natural aggregate is medium-grade sand in Zone II, with a fineness modulus of 3.05, which complies with GB/T14685-2011.
实施案例4相对于实施案例1掺入了生石灰通过脱硫石膏的附着水与生石灰反应放热脱去结晶水，此水再与生石灰反应放热使其继续脱水，增加了脱硫石膏砂浆的强度。In Example 4, compared with Example 1, quicklime is mixed with desulfurized gypsum. The attached water of desulfurized gypsum reacts with quicklime to exothermically remove crystal water, and this water reacts with quicklime to exothermicly dehydrate it, increasing the strength of desulfurized gypsum mortar.
上述四个实施例的具体的对比数据如下：The concrete comparison data of above-mentioned four embodiments are as follows:
以上对本发明所提供的工业尾气协同制备工业废石膏砂浆及毒性解决方法进行了详细介绍。本文中应用了具体个例对本发明的原理及实施方式进行了阐述，以上实施例的说明只是用于帮助理解本发明的方法及其核心思想。应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以对本发明进行若干改进和修饰，这些改进和修饰也落入本发明权利要求的保护范围内。The method for synergistic preparation of industrial waste gypsum mortar and toxicity solution provided by the present invention has been described above. In this paper, specific examples are used to illustrate the principle and implementation of the present invention, and the descriptions of the above embodiments are only used to help understand the method and core idea of the present invention. It should be pointed out that for those skilled in the art, without departing from the principles of the present invention, some improvements and modifications can be made to the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention.
Claims (10)
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