CN1311170A - Method for producing building materials using mud from waste water as raw materials - Google Patents
Method for producing building materials using mud from waste water as raw materials Download PDFInfo
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- CN1311170A CN1311170A CN01103309A CN01103309A CN1311170A CN 1311170 A CN1311170 A CN 1311170A CN 01103309 A CN01103309 A CN 01103309A CN 01103309 A CN01103309 A CN 01103309A CN 1311170 A CN1311170 A CN 1311170A
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- Prior art keywords
- mud
- waste water
- weight
- ceramic balls
- heavy metal
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- 239000002351 wastewater Substances 0.000 title claims abstract description 70
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 239000002994 raw material Substances 0.000 title description 2
- 239000004566 building material Substances 0.000 title 1
- 229910001385 heavy metal Inorganic materials 0.000 claims description 41
- 239000000463 material Substances 0.000 claims description 30
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 25
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical group O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 21
- 239000002253 acid Substances 0.000 claims description 19
- 238000010276 construction Methods 0.000 claims description 18
- 239000004927 clay Substances 0.000 claims description 12
- 238000005245 sintering Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 9
- 239000010433 feldspar Substances 0.000 claims description 8
- 238000007493 shaping process Methods 0.000 claims description 8
- 229910052573 porcelain Inorganic materials 0.000 claims description 6
- 239000004575 stone Substances 0.000 claims description 6
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- 229910001570 bauxite Inorganic materials 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 239000006063 cullet Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 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 3
- 239000001095 magnesium carbonate Substances 0.000 claims description 3
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 3
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 3
- 235000014380 magnesium carbonate Nutrition 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims 1
- -1 floats dirt Substances 0.000 claims 1
- 239000000919 ceramic Substances 0.000 abstract description 54
- 239000004035 construction material Substances 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 239000010802 sludge Substances 0.000 abstract 1
- 239000002699 waste material Substances 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 15
- 239000011651 chromium Substances 0.000 description 14
- 239000011575 calcium Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 230000006835 compression Effects 0.000 description 10
- 238000007906 compression Methods 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 8
- 229960002050 hydrofluoric acid Drugs 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 239000004568 cement Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 235000011941 Tilia x europaea Nutrition 0.000 description 6
- 229910052791 calcium Inorganic materials 0.000 description 6
- 239000004571 lime Substances 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- 229910052804 chromium Inorganic materials 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000000428 dust Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229910000859 α-Fe Inorganic materials 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000001815 facial effect Effects 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910004261 CaF 2 Inorganic materials 0.000 description 1
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 241000206607 Porphyra umbilicalis Species 0.000 description 1
- 239000011398 Portland cement Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000000834 fixative Substances 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 238000009408 flooring Methods 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical group [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000010671 solid-state reaction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000003351 stiffener Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
-
- 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
- C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B18/04—Waste materials; Refuse
-
- 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
Abstract
A manufacturing method of construction material using wastewater sludge is provided to prepare construction material, which including artificial gravel, colored ceramic and terazotiles with low absorptivity, high compressive strength, superior light mass and while reducing waste treatment cost and environmental pollution.
Description
The present invention relates to by mixing method from the mud and the cenosphere manufacturing material of construction of waste water.Particularly, the present invention relates to the mud that heavy metal-containing waste water obtains is carried out stabilization treatment the method for the material of construction that the manufacturing construction work is used.
From the waste water of dischargings such as Steel Plant, extraordinary steel mill, Metal plating factory, non-ferrous metal factory, contain plurality of heavy metal.Make such waste water after treatment, heavy metal content is reduced to the level of requirement, uses molysite, aluminium salt, caustic soda, white lime, organic setting accelerator etc. usually.
Processing uses this class chemical through sedimentation and cohesion during from the waste water of these factories discharging, produces the mud that contains heavy metal in a large number.People study the utilization again of this class mud just widely.For example, once attempted with mud as material of construction.This respect because a variety of causes comprises intensity and weight etc., need at high temperature heat mud.Yet this traditional method thereby can not be made useful materials effectively because the thermochemical property instability of material for example ftractures from mud.Therefore, the material of construction that can not use as construction work of this class mud and reclaim effectively and use.Although improved the output of wastewater slurry, also do not reclaim the result of the satisfaction of using mud so far.
In most cases, the mud of by-product can adopt the mode that is similar to the common waste water of processing to handle in handling heavy metal-containing waste water, then landfill.After solidifying for some time, this mud can dissolve and sink in the soil again, therefore can become the secondary pollutant to river, ocean and soil.In addition, the production cost of handling in the required high cost of mud increases.Therefore, should reclaim use mud.
The general metal component that adopts Atomic Absorption Spectrometry from the mud of heavy metal-containing waste water.The results are shown in following table 1.
Table 1
The metal component of the mud of heavy metal-containing waste water
| Component | Content (weight %) | Component | Content (weight %) |
| ????Na | ????1.34 | ????Ca | ????21.90 |
| ????Al | ????0.18 | ????Cr | ????6.16 |
| ????Si | ????1.87 | ????Fe | ????28.00 |
| ????K | ????0.15 | ????Mg | ????0.51 |
In the last table, the waste water during Si, Cr and Fe produce from special steel.And Al, Ca, Na, K and Mg are from handling the additive that heavy metal-containing waste water uses and the component of setting accelerator.According to atomic absorption spectrochemical analysis,, can obtain Al (OH) from the mud of gained if be expected to handle waste water by ordinary method
3, Fe (OH)
3, Na
2SO
4, Mg (OH)
2Deng material.These compounds can be converted into the most stable material after high-temperature heat treatment.
Usually, in heavy metal-containing waste water, add additive, for example sinking agent such as white lime; Setting accelerator such as poly aluminium chloride (polyaluminum chloride), Tai-Ace S 150 and iron(ic) chloride; And/or stiffening agent such as polyacrylamide, prepare this mud.Because the result of chemical reaction and physical action during above-mentioned processing, mud comprises fine particle and a large amount of moisture content, oxyhydroxide and organism.Therefore, as known from Table 1, when mud was heated to 1000 ℃ or higher temperature, the shaping thing can be because excess shrinkage ftracture or bending.In addition, because the shaping thing is inside and outside uneven, form many spaces therein.Therefore, this mud can not be used as the material of construction that construction work is used.
Terazotiles is a kind of material of construction, generally comprises cement, aggregate, coloured gravel, Dali flag etc.For making terazotiles painted, use coloured gravel.But, the short supply of coloured gravel, the coloured Ceramic Balls of main at present use.
The manufacturing of coloured Ceramic Balls generally is with the ball mill feldspar that fine powder is broken, silica and porcelain stone, mixes with pigment as fixative, and this mixture is configured as the balls of different sizes, and dry back carries out in about 1200 ℃ that sintering obtains.
The terrace finishing material that uses inner facial ornament of coloured Ceramic Balls or outside facial ornament to make generally can adopt two kinds of methods to make it be applied to buildings.First method, feldspar, porcelain stone, silica etc. mix with mineral dye after pulverizing, and are configured as spherical particle, and sintering under high temperature makes coloured Ceramic Balls then, afterwards with ball and mixed with resin, is directly injected to concrete surface and constitutes finishing material.Second method is formed in the coloured Ceramic Balls of shaping and the mixture of cement on the cement flooring, and water grinds then.Yet all there is short defective of buildings life-span in these methods.And waste water that produces during grinding and mud directly are discharged into water exhaust system, and from environmental, these methods are unfavorable.Moreover because the expense of construction personnel increases, building cycle prolongs, and laid down cost improves during with these methods.Therefore, in the popular a kind of method that terazotiles is fixed on building surface of western countries, also often be used in Korea S.
Natural crystal such as feldspar, porcelain stone, silica etc. are pulverized in flakes, mixed with mineral dye, and this mixture is configured as spherical particle, sintering at high temperature can be made coloured Ceramic Balls then.Adopt this method, can be made into versicolor Ceramic Balls.The Ceramic Balls that use is made by natural crystal is made terazotiles, and demanding sintering temperature causes expense to increase.Therefore, use the terazotiles of natural crystal, than other material of construction such as fluoropolymer resin patch block and ceramic patch block costliness.
But, reclaim and use terazotiles and the coloured Ceramic Balls that makes from the mud of heavy metal-containing waste water acquisition, in price competition, all have advantage than the Ceramic Balls of using the natural crystal manufacturing and other material of construction.
Use is made coloured Ceramic Balls from the mud that heavy metal-containing waste water obtains, and when grinding the terazotiles that makes with these Ceramic Balls, the space from Ceramic Balls inside to the surface can occur, makes the of poor quality of Ceramic Balls.Even the space do not occur, also reduced ultimate compression strength and the wearing quality of terazotiles on the surface.
Although use the mud that is obtained by heavy metal wastewater thereby to reclaiming, the method for coloured Ceramic Balls and terazotiles of making has been carried out extensive and deep research, does not obtain satisfied result so far.
If physical properties is identical, light terazotiles is better than heavy terazotiles at aspects such as production, storage, transportation and construction.Yet the natural pebble that uses in terazotiles is compared with the gravel that uses polymer materials to make with the artificial gravel that inorganic materials is made, and its lightweight is second-rate.
For addressing the above problem, the purpose of this invention is to provide the mud and the cenosphere that obtain from heavy metal-containing waste water by mixing, make the method for material of construction such as gravel for building, coloured Ceramic Balls and terazotiles.
Another object of the present invention provides the artificial gravel that has improved the lightweight quality, and the terazotiles that uses this gravel.
By detailed description in conjunction with the accompanying drawings, can more be expressly understood above-mentioned purpose of the present invention and other purpose, feature and other advantage.
Shown in Figure 1 is the synoptic diagram of coloured Ceramic Balls of volume rending;
Fig. 2 is that the mud that obtains from heavy metal-containing waste water is at the x-ray diffraction pattern of 1000 ℃ of roastings after 2 hours;
Fig. 3 is that the mud that obtains from fluoric-containing acid waste water is at the x-ray diffraction pattern of 1000 ℃ of roastings after 2 hours;
Fig. 4 adds the mud that the fluoric acid waste water that contains ferric oxide of 40% (weight) obtains from heavy metal-containing waste water, at the x-ray diffraction pattern of 1000 ℃ of roastings after 2 hours.
Use provided by the invention comprises the following steps: that from the method for the slurry manufacture construction material of waste water water content is the mud from the heavy metal-containing waste water acquisition of 10% (weight), mixes with 20-40% (weight) cenosphere, 10-30 % (weight) stabilizing agent and 10-30% (weight) sintering accelerator; This mixture is configured as the shape of requirement; Dry also this formed body of roasting, described stabilizing agent is selected from iron oxide and contains the fluoric-containing acid wastewater slurry of iron oxide, and described sintering accelerator is selected from feldspar, clay, white clay, kaolin, porcelain stone, flying dust, magnesite, bauxite, cullet, aluminium oxide and useless cast iron products.
By coloured Ceramic Balls that the mud that obtains from heavy metal-containing waste water is made, as long as can satisfy following four conditions, recyclable as concrete and terazotiles. The building gravel has and almost identical the creating conditions and characteristics of coloured Ceramic Balls, therefore only describes coloured Ceramic Balls here, omits the description to artificial gravel.
1) after mud is configured as circular and gravel, when high temperature sintering, should not produce the space in the molding.
2) coloured Ceramic Balls of making should have little adsorption rate and high ultimate compression strength.
3) coloured Ceramic Balls of making should have graceful color and good weathering resistance.
4) should have high ultimate compression strength and hardness by the terazotiles that makes with coloured Ceramic Balls, and good luster performance.
The invention provides use and make the method for coloured Ceramic Balls, building gravel and terazotiles from the mud of heavy metal-containing waste water acquisition.Aspect mud stable, implement the method for the coloured Ceramic Balls of this manufacturing mostly in two ways: by adopting roasting; With the use stablizer.
The ferric oxide that uses among the present invention at high temperature can with reactions such as metal such as calcium, chlorine, chromium, magnesium, zinc, manganese, form stable insoluble black ferrite.When adding ferric oxide or coming the mud of fluoric acid waste water of self-contained a large amount of ferric oxide from the mud that heavy metal-containing waste water obtains, can make coloured Ceramic Balls of black, its black is transparent, and heavy metal ion is water insoluble.
When adding ferric oxide the mud that obtains from heavy metal-containing waste water, the calcium constituent that exists in its amount and the mud and the molar ratio of chromium element total amount are preferably 2: 1.According to the molar ratio meter, when the consumption of ferric oxide during greater than the twice of mud institute containing metal, coloured Ceramic Balls is owing to excessive ferric oxide becomes dark red.On the other hand, if the ferric oxide amount less than the ratio that requires, then forms black, but can not stable existence as the element of calcium and chromium, thereby soluble in water.
The mud that the fluoric-containing acid waste water that produces to handle fluoric acid obtains is as being used for the example of the present invention from the mud that contains the acquisition of ferric oxide waste water.In the factory of a large amount of iron components of use such as electron tube group, semiconductor factory, Steel Plant, glasswork, fertilizer plant, electric bulbs factory, can produce the mud that obtains from fluoric-containing acid waste water when handling waste water.The component that this mud has is listed in the table below 2.
Table 2
The metal component of the mud that obtains from fluoric-containing acid waste water
| Component | Content (weight %) | Component | Content (weight %) |
| ????Si | ????3.21 | ????K | ????0.12 |
| ????Al | ????4.51 | ????Na | ????0.99 |
| ????Fe | ????21.30 | ????Mg | ????0.51 |
| ????Ca | ????23.90 | ||
The mud that is used for fluoric-containing acid waste water of the present invention can produce fluoric acid when heating, produce serious environmental and pollute, and therefore must collect fluoric acid.When from the mud that heavy metal-containing waste water obtains, adding from mud that fluoric-containing acid waste water obtains, add a spot of lime feldspar or white lime together, the calcium oxide in fluoric acid and lime feldspar or the white lime is reacted, be converted into CaF
2, so just can suppress to produce fluoric acid.
For improving the intensity of the coloured Ceramic Balls in the inventive method, the sintering accelerator that should add 10-30% (weight), sintering accelerator are selected from feldspar, clay, white clay, kaolin, porcelain stone, flying dust, magnesite, bauxite, cullet, aluminum oxide and useless cast prod.If sintering quickens dosage less than 10% (weight), the high thermal resistance of coloured Ceramic Balls can be lower, and the shaping thing can be melted at 1100 ℃.On the other hand, if this amount exceeds above-mentioned scope, though high thermal resistance improves the strength degradation of gained black ball.
Making the coloured Ceramic Balls of lightweight, is benchmark with the water-content of 10% (weight), should add the cenosphere (a kind of flying dust suspended substance) of 10-40% (weight).To be collected in flying dust landfill in the particle collector during the coal combustion in the ashpit that the seashore dykes and dams surround the time, the material that is suspended in the water surface is exactly a cenosphere, because contain the space of sealing in this cenosphere, proportion is very little, is 0.3-1.0.Compare with floating dirt, cenosphere is similar with the composition that floats dirt, but proportion is lower, because contain the space of sealing in its particle.
Flood tide or at ebb tide, the cenosphere that swims on the ashpit water surface passes dykes and dams sometimes, pollutes ashpit marine site on every side, as fishing area and laver or algal cultivation district.In this case, cenosphere is difficult to handle.Yet, the good lightweight characteristic that cenosphere possesses owing to the small spaces that contains sealing, useful to many purposes.Therefore, when using the cenosphere of 20-40% (weight), the product of making can gently be changed, and can other character that product keeps not had a negative impact again.
When cenosphere in the product exists with 30% (weight) amount, but the proportion of product reduced, although depend on the proportion of the cenosphere of use.And when using lightweight ore (as ferrite), produce during roasting and shrink, but do not have tangible proportion decline effect.
By some following embodiment, can better understand the present invention, these embodiment are used for explanation, but are not construed as limiting the invention.
Embodiment 1
Determine the mud stability test
To comprise 21.90% (weight) Ca, 28.00% (weight) Fe, 6.16% (weight) Cr, 1.87% (weight) Si, 1.34% (weight) Na, 0.51% (weight) Mg, 0.18% (weight) Al and 0.15% (weight) K from the mud of heavy metal-containing waste water 1000 ℃ of roastings 2 hours.Then, by the crystallization phases of X-ray diffraction (Rigaku provides for X-ray diffraction device, D/Max. II A) detection through the mud of roasting.Detect CaFe with JCPDS (the Joint Committee on Power Diffraction Standards) card that is embedded in the X-ray diffraction device
2O
4Crystallization.Fig. 2 illustrates these results.By among the figure as can be known, with the ferritic form of Ca-, a kind of stable compound exists from the mud of heavy metal-containing waste water.
For determining whether Ca and Cr exist with steady state, get 5 grams and carry out the Cr solubility test through 2 hours sample of 1000 ℃ of roastings, check the existence whether Free Ca is arranged.At first, 5 grams are put into 50 milliliters of 0.1N hydrochloric acid through the material of roasting, heated 30 minutes.Be dissolved in Cr in the hydrochloric acid with atomic absorption spectrochemical analysis, the result has determined to have 100ppm Cr stripping.According to adding through the material of roasting in the ethylene glycol, kept 2 hours in 65 ℃ then, free ca can be dissolved in the principle of ethylene glycol, in 100 milliliters of ethylene glycol, add the material of 5 grams through roasting, kept 2 hours in 65 ℃ then, analyze with atomic absorption spectrum, the stripping quantity of calcium is 300ppm as a result.
Find that mud is only in 1000 ℃ of roastings, Ca can not be converted into the Ca-ferrite fully, and part Fe is with Fe
2O
3Form exists, and the Cr stripping is arranged, so the mud instability.
In addition, if maturing temperature rises to 1100 ℃, the material that contains Cr is a black by green transition.Yet, because the chromium stripping is not only arranged, and in solubility test, find have free ca to be present in the roasting body, do not get off so the mud of visible Steel Plant itself is stable.
Embodiment 2
The relation of loss of test mud weight and Heating temperature
Measure the weight loss of mud that water-content is the heavy metal-containing waste water of 10% (weight) with thermal analyzer (DTA, TGA (5200, Seico supply)).The results are shown in following table 3.
Table 3
| Heating temperature (℃) | ???400 | ???500 | ???600 | ???700 | ???800 | ???900 | ???1000 | ???1100 |
| Weight loss (% weight) | ????15 | ????18 | ????19 | ????20 | ????21 | ????22 | ????23 | ????23 |
Noticed that by last table water and organism are being heated to 400 ℃ of decomposition, the compound of settling form decomposes being higher than under 400 ℃ of temperature, in 800 ℃ of weight loss of almost finishing mud, at last in more than 800 ℃, the solid state reaction of oxide compound takes place.
Embodiment 3
The extra test of stablizer
From the mud of heavy metal-containing waste water, the drying water-content is reduced to 10% (weight) from 50% (weight).With the mud weight is benchmark, in the mud of drying, adds the ferric oxide of 5-50% (weight) with the interval of 5% (weight), mixes then.Afterwards, this mixture is configured as the about 2 centimetres spheroplast of diameter, respectively 1000 ℃ and 1100 ℃ of roastings 2 hours and 4 hours, makes coloured Ceramic Balls then.Coloured Ceramic Balls of various situations is pulverized, so that carry out the heavy metal solubility test, whether test exists the free ca that material of construction is had destruction.
As a result, adding 10%% (weight) ferric oxide in the ball of 1000 ℃ of roastings, free ca does not exist, but has determined to have the heavy metal dissolving in all tests.And at adding 10% (weight) ferric oxide and in 2 hours ball of 1100 ℃ of roastings, not stripping of heavy metal, and do not see that free ca is arranged.Add under the situation of 30% (weight) or more ferric oxide, the color of roasting material begins to redden.When adding 50% (weight) ferric oxide, the color of material becomes dark red fully.
In addition, repeat above-mentioned same step and prepare coloured Ceramic Balls, difference is the mud that adds to come the fluoric acid waste water of self-contained a large amount of ferric oxide, replaces ferric oxide.Add 20% (weight), 30% (weight), 40% (weight) and 50% (weight) mud, and, carry out the heavy metal solubility test in 900 ℃, 100 ℃, 1100 ℃ these mud of roasting 2 hours and 4 hours from fluoric-containing acid waste water.As a result, added the mud from fluoric-containing acid waste water of 40% (weight) and 50% (weight), each comfortable 1100 ℃ of roasting is after 2 hours and 4 hours, not stripping of heavy metal.In addition, add 30% (weight), 40% (weight) and 50% (weight) mud from fluoric-containing acid waste water, then in 1100 ℃ of roastings 2 hours and 4 little after, free ca does not exist.
Notice,,, obtain optimum then in 1100 ℃ of roastings 2 hours when adding the mud of 40% (weight) from fluoric-containing acid waste water.Therefore,, pulverize this material, carry out the X-ray diffraction test for determining the crystallization phases of 2 hours material of 1100 ℃ of roastings.
From the x-ray diffraction pattern of Fig. 3, this figure be contain many oxide compounds from the mud of fluoric-containing acid waste water in 1000 ℃ of roastings after 2 hours, the diffractogram that irradiation obtains can see that main crystallographic component is CaFe
2And Fe
2O
3
Add the mud of 40% (weight) from the mud (containing ferric oxide) of the heavy metal-containing waste water of Steel Plant dischargings from fluoric-containing acid waste water, in 1100 ℃ of roastings 2 hours, afterwards, use the JCPDS card that is embedded in the X-ray diffraction device, determine crystalline phase through the material of roasting.Analytical results is shown in Fig. 4.Among this figure, determine Cr
1.3Fe
0.7O
3With the ferritic position of Ca-among Fig. 2 much at one.Therefore, two kinds of mud mix, and then in 1100 ℃ of roastings 2 hours, obtain CaF, the Fe of crystallized form in the roasting material subsequently
2O
3, Ca-ferrite and Cr
1.3Fe
0.7O
3
Mud, clay and cenosphere from adding in the mud of heavy metal-containing waste water from fluoric-containing acid waste water 1100 ℃ of roastings 2 hours, make coloured Ceramic Balls then, measure the ultimate compression strength and the specific absorption of this ball afterwards.The results are shown in table 4.
Table 4
| Coloured Ceramic Balls manufacture method | Specific absorption (% weight) | Ultimate compression strength (Kgf/cm 2) | Proportion |
| From the mud of heavy metal-containing waste water, be added with the mud of 40% (weight), in 1100 ℃ of roastings 2 hours from fluoric-containing acid waste water | ????8 | ????370 | ?2.7 |
| Mud from heavy metal-containing waste water, be added with mud and 30% (weight) clay of 40% (weight), in 1100 ℃ of roastings 2 hours from fluoric-containing acid waste water | ????5 | ????390 | ?2.8 |
| Mud from heavy metal-containing waste water, be added with 40% (weight) mud, 15% (weight) clay and 15% (weight) cenosphere, in 1100 ℃ of roastings 2 hours from fluoric-containing acid waste water | ????4 | ????380 | ?2.2 |
As seen from the above table, coloured Ceramic Balls has excellent absorption rate and ultimate compression strength.Add 30% (weight) clay and in coloured Ceramic Balls of 2 hours of 1100 ℃ of roastings, its performance is better than not adding coloured Ceramic Balls of clay.
Add under the cenosphere situation, the ultimate compression strength of coloured Ceramic Balls is identical with the coloured Ceramic Balls that only adds clay, but its specific absorption descends, but the lightweight quality obviously improves.
Embodiment 4
The method of the coloured Ceramic Balls of volume rending
Mixing is configured as spherical and rubble shape from mud, 30% (weight) and the ferric oxide of 50% (weight) and the mud of the fluoric-containing acid waste water that comes self-contained a large amount of ferric oxide of heavy metal-containing waste water.The normally used enamel blue of coating pottery on the shaping thing.This shaping thing makes the inner black that is 1100 ℃ and 1000 ℃ of roastings 2 hours, and outside is three-dimensional coloured Ceramic Balls of blueness.
The coloured Ceramic Balls and the cement mixing that make are made terazotiles, afterwards, after the grinding, show that its inside is black, and the outside is blue three-dimensional picture, as shown in Figure 1.
Embodiment 5
The serviceability test of coloured Ceramic Balls
The wearing quality of three kinds of coloured Ceramic Balls under different climate changes that test is made in embodiment 3 soaked coloured Ceramic Balls 10 minutes in water, and remained on-50 ℃ to 60 ℃ scopes until 48 hours with 60 minutes interval, tested the ultimate compression strength of ball subsequently.As a result, the ultimate compression strength of three kinds of coloured Ceramic Balls does not change.
Among the present invention, use and make artificial gravel and coloured Ceramic Balls from the mud of heavy metal-containing waste water, in addition, coloured Ceramic Balls can be used for making the terazotiles that the construction floor material is used.Artificial gravel of the present invention and coloured Ceramic Balls have little specific absorption and high ultimate compression strength and good lightweight character.And, can the same manner make the coloured Ceramic Balls and the terazotiles of volume rending.Therefore, need not use the natural black rock, and reclaim the mud that uses from heavy metal-containing waste water, can reduce the cost of handling waste water, produce economic benefit.Also can reduce environmental pollution.Can make have good physical properties the artificial gravel of black, coloured Ceramic Balls and terazotiles.According to the method for making artificial gravel, use Wingdale to mix from the mud of heavy metal-containing waste water with 10-20% (weight) as glued raw material, roasting under 1300 ℃ of high temperature can be made into the cement clinkers with high-performance then.Then, will burn piece and pulverize, as cement, the performance of this cement is identical with commercially available Portland cement.
Mode with explanation has been described the present invention, and the term that should understand use is descriptive, is not construed as limiting.Can carry out many modifications and change to the present invention according to foregoing.Therefore, be to be understood that below within the appended claims scope mode that can be different with the foregoing description mode.
Claims (3)
1. a method of making material of construction comprises the following steps:
With water-content is that the mud from heavy metal-containing waste water of 10% weight mixes with the sintering accelerator of 20-40% weight cenosphere, 10-30% weight stablizer and 10-30% weight;
Said mixture is configured as the shape of requirement;
Dry and roasting should the shaping thing,
The mud that described stablizer is selected from ferric oxide and is obtained by the fluoric-containing acid waste water that contains ferric oxide, described sintering accelerator is selected from from feldspar, clay, white clay, kaolin, porcelain stone, floats dirt, magnesite, bauxite, cullet, aluminum oxide and useless cast prod.
2. the method for claim 1 is characterized in that described method also is included in before the drying step, with a kind of step of coating solution coating shaping thing.
3. the method for claim 1 is characterized in that described calcination steps carries out under 900-1200 ℃.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR20002529 | 2000-01-20 | ||
| KR1020000002529A KR100346102B1 (en) | 2000-01-20 | 2000-01-20 | A Preparation for the Artificial Gravels and Terazotiles using Sludges of Waste Water |
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| CN1311170A true CN1311170A (en) | 2001-09-05 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101654317B (en) * | 2009-08-31 | 2011-04-06 | 泰兴市固废建材有限公司 | Method for processing iron cement and sludge in building materials |
| CN105130363A (en) * | 2015-08-09 | 2015-12-09 | 肖德意 | Permanent heavy metal waste curing method |
| CN107935284A (en) * | 2017-11-21 | 2018-04-20 | 山东省科学院新材料研究所 | A kind of method of recycling treatment heavy metal wastewater thereby |
| CN113072275A (en) * | 2021-04-01 | 2021-07-06 | 新疆碧水源环境资源股份有限公司 | Novel water treatment process for sludge synergism |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100442924B1 (en) * | 2001-12-03 | 2004-08-02 | 장영옥 | A heavy metal stabilizing agent and a method to stabilize wastes containing heavy metals to use one |
| KR100490731B1 (en) * | 2002-08-02 | 2005-05-23 | 장영민 | A Method for constuction material and civil engineering using waste materials |
| KR100500601B1 (en) * | 2002-09-10 | 2005-07-11 | 주식회사 네이엔 | An Adiabatic Paint |
| KR100562169B1 (en) * | 2003-08-25 | 2006-03-20 | 전북대학교산학협력단 | Manufacturing method of lightweight aggregate using ash from municipal and industrial solid waste incinerators |
| KR100879090B1 (en) * | 2006-12-26 | 2009-01-15 | 한국건설기술연구원 | The greening material for artificial ground and manufacturing method thererof |
| KR101135018B1 (en) * | 2009-08-28 | 2012-04-09 | 정현규 | A Composition of Reinforcement Mortar Having Quick-hardening and Lightweight |
| KR101478422B1 (en) * | 2013-01-03 | 2015-01-02 | 주식회사 넥스트윅 | Composite for humidity control porous board using water treatment sludge and manufacturing method of the humidity control porous board |
| KR101338712B1 (en) | 2013-03-28 | 2013-12-06 | 고광식 | Preparation method of pavement block using wasted water sludge |
| KR101379541B1 (en) * | 2013-10-23 | 2014-03-28 | 고광식 | Preparation method of construct materials using wasted water sludge |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR19990066681A (en) * | 1998-01-07 | 1999-08-16 | 박희섭 | Lightweight artificial corner and its manufacturing method |
| KR19990014546A (en) * | 1998-11-21 | 1999-02-25 | 최성찬 | Manufacturing method of artificial gravel and color ceramics using sludge of heavy metal wastewater |
-
2000
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101654317B (en) * | 2009-08-31 | 2011-04-06 | 泰兴市固废建材有限公司 | Method for processing iron cement and sludge in building materials |
| CN105130363A (en) * | 2015-08-09 | 2015-12-09 | 肖德意 | Permanent heavy metal waste curing method |
| CN107935284A (en) * | 2017-11-21 | 2018-04-20 | 山东省科学院新材料研究所 | A kind of method of recycling treatment heavy metal wastewater thereby |
| CN113072275A (en) * | 2021-04-01 | 2021-07-06 | 新疆碧水源环境资源股份有限公司 | Novel water treatment process for sludge synergism |
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| KR20010073725A (en) | 2001-08-01 |
| KR100346102B1 (en) | 2002-08-13 |
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