CN101182140A - Super slow-setting cement - Google Patents
Super slow-setting cement Download PDFInfo
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- CN101182140A CN101182140A CNA2007101566365A CN200710156636A CN101182140A CN 101182140 A CN101182140 A CN 101182140A CN A2007101566365 A CNA2007101566365 A CN A2007101566365A CN 200710156636 A CN200710156636 A CN 200710156636A CN 101182140 A CN101182140 A CN 101182140A
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- cement
- waste water
- acid waste
- sediment
- super slow
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- 239000004568 cement Substances 0.000 title claims abstract description 110
- 239000002351 wastewater Substances 0.000 claims abstract description 74
- 239000002253 acid Substances 0.000 claims abstract description 69
- 239000013049 sediment Substances 0.000 claims abstract description 69
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 47
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 239000002893 slag Substances 0.000 claims description 25
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Inorganic materials [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims 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 description 15
- 239000011507 gypsum plaster Substances 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 10
- 239000000292 calcium oxide Substances 0.000 claims description 9
- 235000012255 calcium oxide Nutrition 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 7
- 239000010881 fly ash Substances 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 5
- 239000003245 coal Substances 0.000 claims description 5
- 238000006386 neutralization reaction Methods 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 239000006004 Quartz sand Substances 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000003723 Smelting Methods 0.000 claims description 3
- 229910021536 Zeolite Inorganic materials 0.000 claims description 3
- 239000002956 ash Substances 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000010457 zeolite Substances 0.000 claims description 3
- 238000000498 ball milling Methods 0.000 claims description 2
- 239000010884 boiler slag Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000010304 firing Methods 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004567 concrete Substances 0.000 abstract description 34
- 238000010276 construction Methods 0.000 abstract description 9
- 239000010440 gypsum Substances 0.000 abstract description 7
- 229910052602 gypsum Inorganic materials 0.000 abstract description 7
- 230000009286 beneficial effect Effects 0.000 abstract description 5
- 230000002035 prolonged effect Effects 0.000 abstract description 3
- 230000009467 reduction Effects 0.000 abstract description 2
- 239000000654 additive Substances 0.000 abstract 1
- 230000000996 additive effect Effects 0.000 abstract 1
- 238000005553 drilling Methods 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- 238000003801 milling Methods 0.000 abstract 1
- 230000015271 coagulation Effects 0.000 description 35
- 238000005345 coagulation Methods 0.000 description 35
- 230000006835 compression Effects 0.000 description 11
- 238000007906 compression Methods 0.000 description 11
- 239000010949 copper Substances 0.000 description 11
- 239000011701 zinc Substances 0.000 description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 7
- 229910052725 zinc Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000000227 grinding Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000011382 roller-compacted concrete Substances 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000011396 hydraulic cement Substances 0.000 description 4
- 238000007689 inspection Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 3
- 235000011941 Tilia x europaea Nutrition 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 230000003111 delayed effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000004571 lime Substances 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 235000010755 mineral Nutrition 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 235000019738 Limestone Nutrition 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 230000002742 anti-folding effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 235000011116 calcium hydroxide Nutrition 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 239000006028 limestone Substances 0.000 description 2
- 238000005065 mining Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 229910000571 Auricupride Inorganic materials 0.000 description 1
- -1 Cu 2+ Chemical class 0.000 description 1
- 241000784726 Lycaena thetis Species 0.000 description 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000003130 blood coagulation factor inhibitor Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000010814 metallic waste Substances 0.000 description 1
- 230000007483 microbial process Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 150000003568 thioethers Chemical class 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
- 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
- C04B28/02—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 hydraulic cements other than calcium sulfates
- C04B28/04—Portland cements
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00017—Aspects relating to the protection of the environment
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Treatment Of Sludge (AREA)
Abstract
The invention provides super-retarding cement, which is obtained from milling mixed dried raw materials with the following ratio: 26-96.2 portions of porland cement clinker and 3.5-10 portions of neutralizing sediments for acid wastewater containing heavy metals. The beneficial effects of the invention are that: firstly, the high efficiency comprehensive utilization of the neutralizing sediments for acid wastewater containing heavy metals can be realized, which is beneficial to the environmental protection; secondly, the natural gypsum consumption is reduced, which is beneficial to the reduction of the natural gypsum resource consumption; thirdly, the settling time of the cement is prolonged, and the invention can be applied to the conditions of delaying the cement concrete setting time, such as constructions in summer, pump transported concrete needing to be transported for a long distance, pile concrete of drilling bitten piles, etc.; the super-retarding cement obtained through the adopting of the invention needs no additive retarder or super retarder, which is beneficial to the cost deduction; fourthly, compared with the natural gypsum adopted, the neutralizing sediments adopted as the retarder can strengthen the cement.
Description
(1) technical field
The present invention relates to a kind of super slow-setting cement, especially a kind of super slow-setting cement for preparing with sediment in the acid waste water containing heavy metal that utilizes relates to the material of construction with the changing rejected material to useful resource comprehensive utilization.
(2) background technology
Along with social economy develops rapidly, human growing to the Mineral resources demand, the discharged volume of industrial waste water that is produced in the mining mineral resource and the course of processing also increases thereupon.What pollution range was the widest in the mine wastewater, hazard rating is maximum is the acid waste water of mine discharging.Ubiquity acidic mine waste water problem all over the world, China is also quite serious, and all there are this type of problem in colliery, metal mine.China's overwhelming majority metal mine is the original sulfides mineral deposit, no matter be that adopt in Lu Cai or hole, the a large amount of sulfide barren rocks that abandon, under air, water and microbial process, take place moltenly to soak, a series of physical-chemical reactions such as oxidation, hydrolysis, formation contains plurality of heavy metal ionic yellowish brown acid waste water, these acidic mine waste waters are low because of the pH value, acidity big, contain the plurality of heavy metal ion, be commonly referred to and contain the heavy metal acid wastewater in mine, also be acid wastewater in mine, generally all directly recycles; If directly enter water body, will cause serious negative impact near ecotope mining industry production and the mine.Therefore, must handle acid wastewater in mine.
Except that bargh, some commercial runs are subjected to the restriction of production technique, also produce a large amount of acid waste water containing heavy metals in process of production, and as Electroplating Production etc., these acid waste water containing heavy metals also must suitably be handled and just can discharge after up to standard.
At present, generally adopt the neutralisation treatment of acidic wastewater both at home and abroad, its advantage is that the neutralizing agent source is wide, price is low, easy and simple to handle, adaptability to acid waste water concentration, the water yield and discharge point is strong, common neutralizing agent has lime, carbide slag, Wingdale, soda, caustic alkali etc., and wherein lime and carbide slag are neutralizing agent commonly used.Contain the heavy metal sediment in a large number but adopt lime or carbide slag etc. still to form after neutralization, press filtration are handled, promptly in the acid waste water containing heavy metal and sediment, its main component is a terra alba, belong to a kind of of waste gypsum, compare with other industrial waste gypsum, its water ratio is big, contain more heavy metal ion, as Cu
2+, Fe
2+, Zn
2+, Pb
2+Deng, if do not handled, will cause very big harm to environment.
In acid waste water containing heavy metal and in the sediment, the content of heavy metal is often lower, adopt special technology that it is reclaimed, all very difficult technically and economically, and still exist after reclaiming a large amount of heavy metal solid waste that contains to need to handle to heavy metal; To containing the more sediment of heavy metal, can take suitable technology to reclaim, but finally equally still exist a large amount of heavy metal solid waste that contains to need to handle.At present to taking the mode of curing/stabilizing to carry out landfill disposal often with the processing mode of sediment in the acid waste water containing heavy metal, the most frequently used curing mode is cement solidification, because the high alkalinity that has of cement, can make nearly all heavy metal form insolubles and be fixed in the cured body.Yet, studies show that, utilize cement to heavy metal waste be cured/during stabilization treatment, heavy metal ion such as Cu
2+, Zn
2+, Pb
2+Have a negative impact Deng to solidified cement body, mainly show as and produce serious retardation phenomenon, finally cause solidified cement body intensity lower; Simultaneously, adopt land-fill method to handle, not only will spend substantial contribution every year, and waste a large amount of land resourcess, have a strong impact on ecotope, and the waste landfill in fact also is the significant wastage to resource.
Utilize various wastes to be considered to a kind of recycling economy pattern of Sustainable development rationally and effectively.For in the acid waste water containing heavy metal and sediment, be to realize comprehensive utilization of resources, must solve the disadvantageous effect that heavy metal ion produces cement-based material.For this reason, Tongji University obliges to give birth to and waits heavy metal zinc and the method that suppresses its delayed coagulation in a kind of solid cement sill of invention, from suppressing the angle of heavy metal ion to the cement-based material disadvantageous effect, adopt sodium sulphite as heavy metal ion delayed coagulation inhibitor, obtained good effect, but this method has increased the waste ' s reclamation cost to a certain extent.
And in cement and concrete production process, on the one hand, when producing cement, add proper amount of gypsum usually to regulate cement setting time, prevent the wink coagulation phenomena; On the other hand, in modern concrete industry, generally adopt commerical ready-mixed concrete, mode by pumping is constructed, usually, in the commerical ready-mixed concrete production process, need to add an amount of retardant, to prevent the pump concrete of the slump-loss in the commerical ready-mixed concrete transportation, particularly hot weather construction, long-distance transportation, rush-hour transportation; And in some large bridge engineerings, for improving the supporting capacity of single pile, the length and the cross section of stake are all bigger, the required dabbling concrete square amount of single pile is bigger, infusion time is longer, especially during the broiling summer, must prolong the concrete presetting period greatly, could guarantee once to pour into successfully; In the engineering that some deep pit diggings employing boring interlock stakes are gone along with sb. to guard him, for the Steel Concrete that guarantees the back construction can cut the plain concrete pile of constructing earlier smoothly, reach the interlock effect, must be the presetting period of the plain concrete pile of construction prolong greatly earlier; In addition, for grinding concrete construction, its process characteristic is also to proposing particular requirement its time of coagulation, it is necessary sufficiently long time of coagulation, with guarantee the upper strata build when rolling below one deck setting and harden not as yet, otherwise it is own through the hardened concrete structure to destroy lower floor when roll on the upper strata, and interlayer is in conjunction with also being affected.Therefore, must guarantee to be longer than every layer of decking and rolling time under the possible unfavourable condition time of coagulation of roller compacted concrete, the time of coagulation that is roller compacted concrete is suitably longer, also effectively controls the release of hydration heat simultaneously, avoids concentrating the heat release formation temperature to impact and thermal cracking occurs.Different with normal concrete, the prolongation of roller compacted concrete time of coagulation is not a thing easily, especially at high temperature season, make and reach 10h or longer very difficult its time of coagulation, reason is that rich moisture seldom in this low, the solid phase component fully contacts, as long as the small portion hydrated cementitious can form gel network and reach setting and harden, and gelling material can be well dispersed in the liquid-phase system after the common plastic concrete admixture water reducer, is easy to prolong time of coagulation thereby the aquation gel is difficult for forming network.Therefore, the slow setting of high temperature area high temperature season roller compacted concrete also is one of its key issue.
And the general goods concrete retarder, usually volume too much can cause the reduction of concrete strength and harden badly, and the slow setting time is shorter, needing generally can not be used for the engineering of long-time continuity concrete coagulation.In recent years, develop a kind of super-retarder both at home and abroad, it is excessive to the influence of slow setting time with to the contradiction between the concrete strength influence to have solved normal concrete retardant volume to a certain extent, but additionally adopt super-retarder to realize concrete super slow setting, must increase concrete production cost.
(3) summary of the invention
The super slow-setting cement that the object of the invention provides a kind of low cost, high-efficiency comprehensive utilization contains in the heavy metal acid wastewater in mine and sediment is produced, prolong cement setting time and strengthened its intensity, can be directly used in the super retarded concrete that preparation need have longer slow setting time requirement, as the pump concrete of hot weather construction, hole interlock stake pile concrete, roller compacted concrete etc.
Technical scheme of the present invention is:
A kind of super slow-setting cement, mainly mixed after ball milling obtains by the following raw material drying of proportioning:
Portland clinker 26~96.2 mass parts
In the acid waste water containing heavy metal and sediment 3.5~10 mass parts.
The present invention adopts in the acid waste water containing heavy metal and sediment substitutes the raw material of the plaster of paris as super slow-setting cement, has not only prolonged its time of coagulation, and in and sediment anti-folding of cement and compressive property are also had enhancement.
In and sediment substitute the plaster of paris as retardant, it substitutes and can be replacing whole, also can be part and substitutes.Also can contain in the raw material of described preparation super slow-setting cement: the plaster of paris 0.1~3 mass parts.
Also can contain in the raw material of described preparation super slow-setting cement: cement mixture 0.1~70 mass parts.Described cement mixture is that common and cement clinker are mixed with the flyash of finished cement or slag etc., among the present invention, described cement mixture can be one of following or two or more mixture wherein: (1) blast-furnace slag, (2) flyash, (3) natural volcanic ash, (4) zeolite, (5) slag, (6) phosphorus ore slag, (7) coal firing boiler slag, (8) calcining coal gangue, (9) boiling furnace slag, (10) Wingdale, (11) calcining metakaolin, (12) quartz sand.
In the described acid waste water containing heavy metal and sediment prepare by following method: adopt one of following or wherein two or more mixture the acid waste water that contains heavy metal is carried out neutralizing treatment to pH=9.0~10.0: 1. Wingdale (can adopt natural limestone or levigate limestone powder), 2. unslaked lime, 3. carbide slag, the acid waste water after the neutralization obtains in the described acid waste water containing heavy metal and sediment through press filtration again.
In the described acid waste water containing heavy metal be: CaO: SO with sediment main component quality proportioning
3: Fe
2O
3: CuO: ZnO: PbO: H
2O: Al
2O
3: SiO
2=18~30: 25~40: 1~10: 0~5.0: 0~8.0: 0~5.0: 20~30: 0~5: 0~10.
In the described acid waste water containing heavy metal be: CaO: SO with sediment main component quality proportioning
3: Fe
2O
3: CuO: ZnO: PbO: H
2O: Al
2O
3: SiO
2=18~25: 25~35: 1~10: 0.5~4.0: 2.0~8.0: 0.3~4.5: 25~30: 1.0~2.0: 2.0~8.0.
The described acid waste water that contains heavy metal is one of following: acid waste water, (4) colliery acid waste water are electroplated in (1) metal mine acid waste water, (2) Metal smelting acid waste water, (3).
Described metal mine can be one of following mine: (1) copper mine, (2) plumbous zinc ore, (3) auricupride, (4) gold mine, (5) silver ore, (6) iron ore.
Described Metal smelting acid waste water can be one of following metallurgical works acid waste water: (1) copper, (2) plumbous zinc, (3) golden copper, (4) gold, (5) silver.
Described plating acid waste water can be one or several the electroplating wastewater of mixture that contains following heavy metal: (1) copper, (2) zinc, (3) lead.
Described super slow-setting cement carries out time of coagulation by measuring method time of coagulation of national Specification to described slow setting cement and measures, and the presetting period that records is 4~18h, and final setting time is 8~35h.
Principle of the present invention is to utilize gypsum and the Cu that contains in the sediment
2+, Zn
2+, pb
2+Etc. the delayed coagulation of heavy metal ion to cement clinker, regulate the time of coagulation of super slow-setting cement, production can be directly used in the super retarded concrete that preparation need have longer slow setting time requirement, as the super slow-setting cement of the pump concrete of hot weather construction, the interlock stake pile concrete of holing etc.
Utilization of the present invention contains in the heavy metal acid wastewater in mine and the beneficial effect of the super slow-setting cement of sediment manufacturing is mainly reflected in: (1) can realize in the acid waste water containing heavy metal and the high-efficiency comprehensive utilization of sediment, and is favourable to environment protection; (2) reduced the consumption of the plaster of paris, favourable to the consumption that reduces plaster of paris resource; (3) prolonged cement setting time, can be applicable to delay the cement concrete situation of time of coagulation, as construction in summer, the pump concrete that needs long distance conveying, boring interlock stake pile concrete etc., the super slow-setting cement that adopts the present invention to obtain does not need additionally to add retardant or super-retarder, and is favourable to reducing cost; (4) compare with adopting the plaster of paris, as retardant cement is also had enhancement with sediment in the employing.
(4) embodiment
The present invention is described further below in conjunction with specific embodiment, but protection scope of the present invention is not limited in this:
Embodiment 1~10:
Adopt in certain cement mill cement clinker and certain copper mine acid waste water and sediment 1 preparation super slow-setting cement, in and sediment 1 be: with H
2SO
4Be main acid waste water, adopt carbide slag as neutralizing agent, acid waste water carries out press filtration after being neutralized to about pH=9.5, and with sediment 1, its chemical constitution is: CaO: SO in obtaining
3: Fe
2O
3: CuO: ZnO: PbO: Al
2O
3: SiO
2=20.71: 31.25: 8.94: 1.36: 4.67: 0.35: 25.27: 1.17: 6.28.With press filtration obtain in and sediment 1 earlier 100 ± 5 ℃ of oven dry down, by prescription in table 1 and the table 2 raw material is mixed to be placed in the little mill of laboratory cement then and carry out grinding, obtain the 0.08mm percentage of sieve residue less than 10% super slow-setting cement, then by national standard " cement normal consistency water consumption, time of coagulation, the stability method of inspection " GB/T1346-2001 measures the time of coagulation of super slow-setting cement, measure 3d and the anti-folding of 28d and the ultimate compression strength of super slow-setting cement by national standard " Test method for strength of hydraulic cement mortar (ISO method) " GB/T17671-1999, measurement result sees Table 1 and table 2.By table 1 as seen, adopt in the acid waste water of the present invention and sediment as cement setting retarder, can prepare super slow-setting cement.Simultaneously, compare as can be seen with Comparative Examples by embodiment 1, embodiment 3, embodiment 4, in the employing and sediment replace the plaster of paris and prepare super slow-setting cement, not only prolong to some extent its time of coagulation, and in and sediment cement is also had enhancement.By table 2 as seen, when fine slag contents reached 65%, its final setting time can reach 31h10m, but the super slow setting that causes with sediment in the admixture acid waste water is little to the later strength influence of cement.
Table 1: adopt super slow-setting cement time of coagulation and the intensity prepared with sediment 1 in the copper mine acid waste water
Embodiment | Grog/% | The plaster of paris | Sediment 1/% | Flyash/% | Slag/% | Presetting period | Final setting time | Folding strength/MPa | Ultimate compression strength/MPa | ||
3d | 28d | 3d | 28d | ||||||||
Comparative Examples | 93.5 | 6.5 | 0 | 0 | 0 | 1h47m | 4h45m | 6.0 | 8.7 | 19.0 | 50.6 |
Embodiment 1 | 93.5 | 0 | 6.5 | 0 | 0 | 6h03m | 10h25m | 6.4 | 9.1 | 24.2 | 58.4 |
Embodiment 2 | 96.2 | 0 | 3.8 | 0 | 0 | 4h17m | 7h00m | 6.8 | 8.0 | 37.6 | 50.3 |
Embodiment 3 | 92.6 | 0 | 7.4 | 0 | 0 | 9h40m | 15h50m | 7.1 | 9.1 | 40.0 | 59.9 |
Embodiment 4 | 90.9 | 0 | 9.1 | 0 | 0 | 12h55m | 21h25m | 6.6 | 8.3 | 38.0 | 59.2 |
Embodiment 5 | 79.4 | 0 | 5.6 | 15.0 | 0 | 6h11m | 11h35m | 5.6 | 8.3 | 28.9 | 42.2 |
Embodiment 6 | 79.4 | 0 | 5.6 | 0 | 15.0 | 8h10m | 13h02m | 5.7 | 8.6 | 27.2 | 42.8 |
Embodiment 7 | 75.0 | 0 | 10.0 | 7.5 | 7.5 | 8h44m | 16h5m | 5.4 | 8.1 | 31.4 | 42.1 |
Embodiment 8 | 58.0 | 0 | 8.0 | 34.0 | 0 | 8h40m | 17h15m | 4.9 | 7.7 | 25.7 | 39.7 |
Embodiment 9 | 40.0 | 0 | 7.0 | 0 | 53.0 | 8h44m | 19h15m | 4.4 | 9.6 | 21.3 | 47.6 |
Table 2: adopt super slow setting slag cement time of coagulation and the intensity prepared with sediment in the copper mine acid waste water
Embodiment | Grog/% | Sediment 1/% | Flyash/% | Slag/% | Presetting period | Final setting time | Folding strength/MPa | Ultimate compression strength/MPa | ||
7d | 28d | 7d | 28d | |||||||
Embodiment 10 | 26.0 | 9.0 | 0 | 65.0 | 8h55m | 34h10m | 6.1 | 9.6 | 33.9 | 51.7 |
Embodiment 11~15:
Adopt in certain cement mill cement clinker and certain plumbous zinc ore acid waste water and sediment 2 preparation super slow-setting cements, in and sediment 2 be with H
2SO
4Be main acid waste water, adopt milk of lime as neutralizing agent, acid waste water carries out press filtration after being neutralized to about pH=9.9, and with sediment 2, its chemical constitution is: CaO: SO in obtaining
3: Fe
2O
3: CuO: ZnO: PbO: Al
2O
3: SiO
2=18.32: 26.46: 9.25: 0.56: 7.54: 4.35: 29.17: 1.17: 3.18.With press filtration obtain in and sediment 2 earlier 100 ± 5 ℃ of oven dry down, place cement little mill in laboratory to carry out grinding raw material by prescription in the table 3 then, obtain the 0.08mm percentage of sieve residue less than 10% super slow-setting cement, measure the time of coagulation of super slow-setting cement then by national standard " cement normal consistency water consumption, time of coagulation, the stability method of inspection " GB/T1346-2001, the 3d and the 28d that measure super slow-setting cement by national standard " Test method for strength of hydraulic cement mortar (ISO method) " GB/T17671-1999 resist folding and ultimate compression strength, and measurement result sees Table 3.By table 3 as seen, adopt in the plumbous zinc ore acid waste water and sediment as cement setting retarder, also can prepare super slow-setting cement.Compare with Comparative Examples and can find by embodiment 11, embodiment 12, in the employing and sediment 2 replace the plasters of paris and prepare super slow-setting cement, not only prolong to some extent its time of coagulation, and in and sediment cement is also had enhancement.
Table 3: adopt super slow setting slag cement time of coagulation and the intensity prepared with sediment in the plumbous zinc ore acid waste water
Embodiment | Grog/% | The plaster of paris | Sediment 1/% | Flyash/% | Slag/% | Presetting period | Final setting time | Folding strength/MPa | Ultimate compression strength/MPa | ||
3d | 28d | 3d | 28d | ||||||||
Comparative Examples | 93.5 | 6.5 | 0 | 0 | 0 | 1h47m | 4h45m | 6.0 | 8.7 | 19.0 | 50.6 |
Embodiment 11 | 93.0 | 0 | 7.0 | 0 | 0 | 11h25m | 18h40m | 6.7 | 9.5 | 43.0 | 61.9 |
Embodiment 12 | 91.0 | 0 | 9.0 | 0 | 0 | 15h40m | 29h15m | 6.9 | 9.3 | 39.0 | 59.8 |
Embodiment 13 | 80.0 | 0 | 6.0 | 14.0 | 0 | 8h32m | 15h25m | 5.4 | 8.5 | 26.9 | 44.5 |
Embodiment 14 | 78.0 | 0 | 7.0 | 0 | 15.0 | 9h40m | 17h52m | 6.0 | 8.8 | 27.6 | 46.8 |
Embodiment 15 | 76.0 | 0 | 9.0 | 7.5 | 7.5 | 17h44m | 32h45m | 5.6 | 8.3 | 29.4 | 48.3 |
Embodiment 16~18:
Adopt certain cement mill cement clinker and certain electroplate acid waste water focus in and sediment 3 preparation super slow-setting cements, in and sediment 3 be with H
2SO
4Be main acid waste water, adopt Wingdale as neutralizing agent earlier, acid waste water is through being neutralized to about pH=4.0, adopt milk of lime as neutralizing agent again, after further being neutralized to about pH=9.9, carry out then that press filtration obtains in and sediment 3, its chemical constitution is: CaO: SO
3: Fe
2O
3: CuO: ZnO: PbO: Al
2O
3: SiO
2=23.16: 32.98: 1.74: 3.56: 2.24: 2.35: 1.54: 2.38.With press filtration obtain in and sediment 3 earlier 100 ± 5 ℃ of oven dry down, place cement little mill in laboratory to carry out grinding raw material by prescription in the table 4 then, obtain the 0.08mm percentage of sieve residue less than 10% super slow-setting cement, measure the time of coagulation of super slow-setting cement then by national standard " cement normal consistency water consumption, time of coagulation, the stability method of inspection " GB/T1346-2001, the 3d and the 28d that measure super slow-setting cement by national standard " Test method for strength of hydraulic cement mortar (ISO method) " GB/T17671-1999 resist folding and ultimate compression strength, and measurement result sees Table 4~table 6.By table 4~table 6 as seen, adopt to electroplate in the acid waste water and sediment as cement setting retarder, also can prepare super slow-setting cement.Compare with Comparative Examples by embodiment 16 and can find equally, in the employing and sediment replace the plaster of paris and prepare super slow-setting cement, not only prolong to some extent its time of coagulation, and in and sediment cement is also had enhancement.
Table 4: adopt and electroplate slow setting cement time of coagulation and the intensity of preparing with sediment 3 in the acid waste water
Embodiment | Grog/% | Sediment 3/% | Flyash/% | Boiling furnace slag/% | Presetting period | Final setting time | Folding strength/MPa | Ultimate compression strength/MPa | ||
3d | 28d | 3d | 28d | |||||||
Embodiment 16 | 93.5 | 6.5 | 0 | 0 | 14h35m | 20h45m | 6.5 | 9.5 | 34.5 | 58.9 |
Embodiment 17 | 70.0 | 7.0 | 15 | 8 | 16h20m | 25h55m | 6.9 | 8.3 | 31.0 | 54.8 |
Table 5: adopt and electroplate super slow-setting cement time of coagulation and the intensity of preparing with sediment 3 in the acid waste water
Embodiment | Grog/% | Sediment 3/% | Slag/% | Phosphorus ore slag/% | Zeolite/% | Presetting period | Final setting time | Folding strength/MPa | Ultimate compression strength/MPa | ||
3d | 28d | 3d | 28d | ||||||||
Embodiment 18 | 63.5 | 6.5 | 4.0 | 20.0 | 6.0 | 16h35m | 24h15m | 5.4 | 8.5 | 24.5 | 47.1 |
Table 6: adopt and electroplate super slow-setting cement time of coagulation and the intensity of preparing with sediment 3 in the acid waste water
Embodiment | Grog/% | Sediment 3/% | Slag/% | Quartz sand/% | Calcining coal gangue/% | Presetting period | Final setting time | Folding strength/MPa | Ultimate compression strength/MPa | ||
3d | 28d | 3d | 28d | ||||||||
Embodiment 19 | 50 | 7.5 | 35.0 | 5.0 | 2.5 | 21h50m | 28h25m | 4.8 | 7.5 | 18.4 | 43.8 |
Embodiment 20~21:
Adopt certain cement mill cement clinker and certain copper mine acid waste water focus in and sediment 1 and the compound preparation super slow-setting cement of the plaster of paris, with press filtration obtain in and sediment 1 earlier 100 ± 5 ℃ of oven dry down, place cement little mill in laboratory to carry out grinding raw material by prescription in the table 7 then, obtain the 0.08mm percentage of sieve residue less than 10% super slow-setting cement, then by national standard " cement normal consistency water consumption, time of coagulation, the stability method of inspection " GB/T1346-2001 measures the time of coagulation of super slow-setting cement, the 3d and the 28d that measure super slow-setting cement by national standard " Test method for strength of hydraulic cement mortar (ISO method) " GB/T17671-1999 resist folding and ultimate compression strength, and measurement result sees Table 7.By table 7 as seen, compound as cement setting retarder in the employing copper mine acid waste water with the sediment 1 and the plaster of paris, can prepare super slow-setting cement.Compare with Comparative Examples by embodiment 20 and can find equally, in the employing and sediment replace the part plaster of paris and prepare super slow-setting cement, not only prolong to some extent its time of coagulation, and in and sediment cement is also had enhancement.
Table 7: adopt and electroplate super slow-setting cement time of coagulation and the intensity of preparing with sediment 1 in the acid waste water
Embodiment | Grog/% | Sediment 1/% | The plaster of paris/% | Wingdale/% | Natural volcanic ash/% | Presetting period | Final setting time | Folding strength/MPa | Ultimate compression strength/MPa | ||
3d | 28d | 3d | 28d | ||||||||
Embodiment 20 | 90 | 3.5 | 3.0 | 0 | 0 | 6 h35m | 11h40m | 6.8 | 9.1 | 25.8 | 56.6 |
Embodiment 21 | 76.5 | 3.5 | 2.5 | 5.0 | 12.5 | 9h30m | 14h55m | 5.8 | 8.6 | 25.4 | 55.8 |
Need to prove that above-mentioned description to embodiment is can understand and apply the invention for ease of those skilled in the art.The person skilled in the art obviously can easily make various modifications to these embodiment, and being applied in the General Principle of this explanation among other embodiment and needn't be through creatively work.Therefore, the present invention is not limited only to the embodiment here, and those skilled in the art should be within protection scope of the present invention for improvement and modification that the present invention makes according to announcement of the present invention.
Claims (7)
1. super slow-setting cement, mainly mixed after ball milling obtains by the following raw material drying of proportioning:
Portland clinker 26~96.2 mass parts
In the acid waste water containing heavy metal and sediment 3.5~10 mass parts.
2. super slow-setting cement as claimed in claim 1 is characterized in that: also contain in the raw material of described preparation super slow-setting cement: the plaster of paris 0.1~3 mass parts.
3. super slow-setting cement as claimed in claim 1 or 2, it is characterized in that: also contain in the raw material of described preparation super slow-setting cement: cement mixture 0.1~70 mass parts, described cement mixture are one of following or two or more mixture wherein: (1) blast-furnace slag, (2) flyash, (3) natural volcanic ash, (4) zeolite, (5) slag, (6) phosphorus ore slag, (7) coal firing boiler slag, (8) calcining coal gangue, (9) boiling furnace slag, (10) Wingdale, (11) calcining metakaolin, (12) quartz sand.
4. super slow-setting cement as claimed in claim 1, it is characterized in that, in the described acid waste water containing heavy metal and sediment prepare by following method: adopt one of following or wherein two or more mixture the acid waste water that contains heavy metal is carried out neutralizing treatment to pH=9.0~10.0: 1. Wingdale, 2. unslaked lime, 3. carbide slag, the acid waste water after the neutralization obtains in the described heavy-metal acid waste water and sediment through press filtration again.
5. super slow-setting cement as claimed in claim 4 is characterized in that in the described acid waste water containing heavy metal and sediment main component quality proportioning is: CaO: SO
3: Fe
2O
3: CuO: ZnO: PbO: H
2O: Al
2O
3: SiO
2=18~30: 25~40: 1~10: 0~5.0: 0~8.0: 0~5.0: 20~30: 0~5: 0~10.
6. super slow-setting cement as claimed in claim 5 is characterized in that in the described acid waste water containing heavy metal and sediment main component quality proportioning is: CaO: SO
3: Fe
2O
3: CuO: ZnO: PbO: H
2O: Al
2O
3: SiO
2=18~25: 25~35: 1~10: 0.5~4.0: 2.0~8.0: 0.3~4.5: 25~30: 1.0~2.0: 2.0~8.0.
7. super slow-setting cement as claimed in claim 4 is characterized in that the described acid waste water that contains heavy metal is one of following: the described acid waste water that contains heavy metal is one of following: acid waste water, (4) colliery acid waste water are electroplated in (1) metal mine acid waste water, (2) Metal smelting acid waste water, (3).
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