CN101259314A - Method for curing heavy metal and its special-purpose base soil polymer - Google Patents
Method for curing heavy metal and its special-purpose base soil polymer Download PDFInfo
- Publication number
- CN101259314A CN101259314A CNA2008100239214A CN200810023921A CN101259314A CN 101259314 A CN101259314 A CN 101259314A CN A2008100239214 A CNA2008100239214 A CN A2008100239214A CN 200810023921 A CN200810023921 A CN 200810023921A CN 101259314 A CN101259314 A CN 101259314A
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- heavy metal
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- base soil
- nitrate
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- 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
The invention discloses a fly ash-based geopolymer, which is prepared by reaction after the raw materials are mixed, the raw materials with the following weight percentages comprises 40.0-80.0 percent of fly ash and 20.0-60.0 percent of alkali-activator which consists of sodium hydroxide and water glass. The fly ash-based geopolymer prepared by the invention can be finally hardened into solid at room temperature after being added into proper quantity of water and stirred, and also has better solidification effect to added heavy metals like copper, lead, nickel, zinc, cadmium and so on. The solidification rate is all above 99.9 percent. The geopolymer is also characterized by excellent physical and mechanical performance and durability, and is a novel solidification technology for the heavy metals.
Description
Technical field
The invention belongs to environmental protection technical field, relate to and a kind ofly be used to use industrial residue to carry out the technology of heavy metals immobilization.
Background technology
The a large amount of bazardous waste of the annual generation of China.China also is in reduced levels to the harmless treatment of solid waste, generally with hazardous waste stacking temporarily, landfill or discharging, heavy metals such as a large amount of lead that contain in these solid waste, copper, cadmium, nickel can leach gradually, enter underground water and soil, the whole ecological environment is polluted and destroys.Therefore, do not become the environmental problem that China needs to be resolved hurrily with the harmful solid waste science safe disposal through strictness is innoxious.Disposal heavy metal refuse method preferably is to be cured processing, to reach innoxious purpose.The curing technology last decade is developed rapidly, is used to handle dangers such as electroplating mud, chromium slag, and main curing technology has: cement solidification, lime curing etc.There are a lot of problems in the cement solidification technology in application process, such as: the precipitated product of formation can become solvable under low ph environment; Organic existence has interference effect to cement hydration process, and it is difficult that solidification process becomes; The existence of dissolubility salt reduces firming body intensity, causes fluffy and destruction; Sulfate in the refuse and hydrated cementitious product react, and cause firming body to expand and break; Firming body is subjected to acid medium easily and corrodes.The discharging of a large amount of harmful wastes and the severe durable New Building Materials of pollution reality an urgent demand are handled effective curing of heavy metal with realization.
Soil polyalcohol is a kind of high performance alkali excitation material, the inorganic material that is generated under the effect of alkali-activator by the silica-aluminum materials of low calcium.The reaction mechanism and the ordinary cement of soil polyalcohol have essential distinction, do not have the such hydration reaction of ordinary cement.Defectives such as it has overcome portland cement durability deficiency, it is big to shrink, environment compatibility difference, have endurance qualities such as good antiacid erosion, alkali resistant erosion, resisting erosion of sulfate, freeze thawing resistance circulation, heat endurance, also have advantages such as alkali-aggregate reaction, constriction coefficient and infiltration coefficient are little do not take place.Though alkali slag cement also has endurance quality preferably, shrinkage and fragility are still very big, and setting time is very short, and extremely difficult control and adjustment have greatly limited applying of alkali slag cement.Because use the silica-aluminum materials of low calcium, make soil polyalcohol both have the excellent durability energy of alkali slag cement, avoided the fast hard defective of alkali slag cement again.Therefore, soil polyalcohol has unique physical and mechanical property and endurance quality, have aspect the heavy metals immobilization processing cement and alkali slag cement the superiority that can not compare, have broad application prospects.
At present, China's development of electric power industry is rapid, has caused the sharp increase of flyash discharge capacity, and annual emissions is more than 1.6 hundred million tons.Contain a large amount of Al in the flyash
2O
3And SiO
2, can be used as the high-quality raw material of fly ash base soil polyalcohol.The fly ash base soil polyalcohol has utilized industrial residue-flyash, consumes the energy seldom, does not produce CO2 emission substantially, is " green " Binder Materials.
Summary of the invention
Problem at existing in the present technology the objective of the invention is to: propose the inorganic material that the fly ash base soil polyalcohol of heavy metal is handled in a kind of effective curing.The alkali-activator that the present invention uses industrial residue-flyash, NaOH and waterglass to form prepares the fly ash base soil polyalcohol, and is used for the curing processing of heavy metal.
The present invention is a kind of fly ash base soil polyalcohol, by the raw material of following mass percent, mixes afterreaction and makes.
Flyash 40.0～80.0%
The alkali-activator 20.0～60.0% that NaOH and waterglass are formed
Fully stir after adding an amount of water in the fly ash base soil polyalcohol of the present invention's preparation, at room temperature finally can harden into solid.
The fly ash base soil polyalcohol of the present invention preparation has solidification effect preferably to heavy metals such as the copper that adds, lead, nickel, zinc, cadmiums, and curing degree is all more than 99.9%.Soil polyalcohol also has good physical and mechanical property and endurance quality, is a kind of novel heavy metal curing technology.
The specific embodiment
Below the present invention is described in further detail by specific embodiment:
Embodiment 1:
Flyash 48.5%
The alkali-activator 51.5% that NaOH and waterglass are formed
Get 588 parts of said mixtures, add 566 parts of medium sands, add 1150 parts of particle diameters rubble and 45 parts of water at 5～31.5mm, stir, make fly ash base soil polyalcohol concrete, the initial slump of concrete is 200mm, and the rapid hardening phenomenon does not appear in concrete.Concrete pours in the die trial, after sclerosis under 20 ± 3 ℃ of environment, put into then temperature 20 ± 3 ℃, humidity greater than 90% environment under, maintenance to 28 day length of time.Record the concrete following physical and mechanical property of fly ash base soil polyalcohol with reference to DL/T 5150-2001 " concrete for hydraulic structure testing regulations ": 28 days compression strength intensity is 25.6MPa, and tensile strength is 2.15MPa, and tension bullet mould is 2.62 * 10
4MPa, limit stretch value are 138 * 10
-6Fly ash base soil polyalcohol concrete has similar mechanical behavior with normal concrete.
Embodiment 2:
Get 588 parts in mixture among the embodiment 1, add 566 parts of medium sands, add 1150 parts of particle diameters rubble and 45 parts of water, stir, make fly ash base soil polyalcohol concrete at 5～31.5mm.Record the concrete following endurance quality of fly ash base soil polyalcohol with reference to DL/T 5150-2001 " concrete for hydraulic structure testing regulations " and JTJ 270-98 " marine traffic engineering concrete test rules ": after 100 circulations of fast freeze-thaw, mass loss rate is 4.4%, and relative dynamic elastic modulus is 69.0%; 28 days carbonation depth of flash carbonization is 14.0mm; Chloride diffusion coefficient is 1.79 * 10
-12m
2/ s.The endurance quality that fly ash base soil polyalcohol concrete is more more superior than normal concrete.
Embodiment 3:
Get 540 parts in mixture among the embodiment 1, add 1350 parts of iso standard sand, add 24 parts of water, stir, make fly ash base soil polyalcohol mortar, after sclerosis under 20 ± 3 ℃ of environment, put into then temperature 20 ± 3 ℃, humidity greater than 90% environment under, maintenance to 14 day, the test specimen of half is put into 20 ℃ of clear water, the test specimen of half immerses in the 3000mg/L metabisulfite solution and soaked 112 days, measures the expansion rate of mortar weekly, and fly ash base soil polyalcohol mortar is subjected to not producing any volumetric expansion after sodium sulphate corrodes.This explanation, the fly ash base soil polyalcohol has good sulphate-corrosion resistance energy.
Embodiment 4:
Get 540 parts in mixture among the embodiment 1, add 1350 parts of iso standard sand, add 24 parts of water, stir, make fly ash base soil polyalcohol mortar specimen.After the mortar moulding, put into maintenance under 20 ℃ of room temperatures, the surface coverage preservative film prevents water evaporates, after the form removal, puts into the drying shrinkage chamber, and test is just long, and the drying shrinkage room temperature is controlled at 20 ℃ ± 2 ℃, and humidity is controlled at 60% ± 5%.Just long test finishes, and continues to be placed on the drying shrinkage chamber, to stipulating testing length in the length of time, shrinkage from mold dimensions.The contract with dry rate of fly ash base soil polyalcohol mortar all significantly less than the conventional cement mortar with water-solid ratio, reached 0.0488% when the 28 day length of time, be 56.6% of conventional cement mortar.
Embodiment 5:
Flyash 72.1%
The alkali-activator 27.9% that NaOH and waterglass are formed
Get 416 parts of said mixtures, 115 parts in water, 3.5 parts of copper nitrates add clean slurry mixer together, machine and stir 3 minutes, stir, and in the plastics water tumbler of packing into, and cover with preservative film and to tighten, and avoid water evaporates.Put into the standard curing room maintenance, carry out after 1 month, put into baking oven under 105 ℃, dried 24 hours, break into pieces with iron hammer, sieve removes particle greater than 5mm, according to " hazardous waste judging standard---leach toxicity and differentiate " (GB5085.3-1996) standard carry out leaching toxicity test.The leaching percentage that records copper ion is 0.048%, and curing degree is 99.952%.Copper ion concentration in the leachate is 0.17mg/L, significantly is lower than the maximum permissible concentration of 50mg/L of regulation in " the hazardous waste judging standard---leaching toxicity is differentiated " (GB 5085.3-1996), and therefore prepared firming body does not possess leaching toxicity.
Embodiment 6:
Get 416 parts in mixture among the embodiment 5,115 parts in water, 1.9 parts of plumbi nitras add clean slurry mixer together, machine and stir 3 minutes, stir, and in the plastics water tumbler of packing into, and cover with preservative film and to tighten, and avoid water evaporates.Put into the standard curing room maintenance, carry out after 1 month, put into baking oven under 105 ℃, dried 24 hours, break into pieces with iron hammer, sieve removes particle greater than 5mm, according to " hazardous waste judging standard---leach toxicity and differentiate " (GB5085.3-1996) standard carry out leaching toxicity test.The leaching percentage that records lead ion is 0.008%, and curing degree is 99.992%.Plumbum ion concentration in the leachate is 0.03mg/L, significantly is lower than the maximum permissible concentration of 3mg/L of regulation in " the hazardous waste judging standard---leaching toxicity is differentiated " (GB 5085.3-1996), and therefore prepared firming body does not possess leaching toxicity.
Embodiment 7:
Get 333 parts in mixture among the embodiment 5,92 parts in water, 4.8 parts of nickel nitrates add clean slurry mixer together, machine and stir 3 minutes, stir, and in the plastics water tumbler of packing into, and cover with preservative film and to tighten, and avoid water evaporates.Put into the standard curing room maintenance, carry out after 1 month, put into baking oven under 105 ℃, dried 24 hours, break into pieces with iron hammer, sieve removes particle greater than 5mm, according to " hazardous waste judging standard---leach toxicity and differentiate " (GB5085.3-1996) standard carry out leaching toxicity test.The leaching percentage that records nickel ion is 0.002%, and curing degree is 99.998%.Nickel ion concentration in the leachate is 0.008mg/L, significantly is lower than the maximum permissible concentration of 10mg/L of regulation in " the hazardous waste judging standard---leaching toxicity is differentiated " (GB 5085.3-1996), and therefore prepared firming body does not possess leaching toxicity.
Embodiment 8:
Get 333 parts in mixture among the embodiment 5,92 parts in water, 9.6 parts of nickel nitrates add clean slurry mixer together, machine and stir 3 minutes, stir, and in the plastics water tumbler of packing into, and cover with preservative film and to tighten, and avoid water evaporates.Put into the standard curing room maintenance, carry out after 1 month, put into baking oven under 105 ℃, dried 24 hours, break into pieces with iron hammer, sieve removes particle greater than 5mm, according to " hazardous waste judging standard---leach toxicity and differentiate " (GB5085.3-1996) standard carry out leaching toxicity test.The leaching percentage that records nickel ion is 0.004%, and curing degree is 99.996%.Nickel ion concentration in the leachate is 0.013mg/L, significantly is lower than the maximum permissible concentration of 10mg/L of regulation in " the hazardous waste judging standard---leaching toxicity is differentiated " (GB 5085.3-1996), and therefore prepared firming body does not possess leaching toxicity.
The fly ash base soil polyalcohol has good physical and mechanical property and endurance quality, heavy metal had good solidification effect, therefore, the fly ash base soil polyalcohol is a kind of novel curing technology, can solidify effectively to handle the industrial waste that contains poisonous metal.The fly ash base soil polyalcohol is used for harmful waste as a kind of novel curing technology solidifies processing, can realize the dual purpose of " with the waste disposal refuse ", will help reducing environmental pollution, improve the ecological environment greatly, have the important social meaning.
Though the present invention with preferred embodiment openly as above; but they are not to be used for limiting the present invention; anyly have the knack of this skill person; without departing from the spirit and scope of the invention; from when can doing various variations or retouching, so being as the criterion of should being defined with the application's claim protection domain of protection scope of the present invention.
Claims (5)
1, a kind of method of curing heavy metal is characterized in that:
Get 333～416 parts of special-purpose base soil polymers, 92～115 parts in water, 1.9～9.6 parts in heavy metal nitrate stirs, and puts into the standard curing room maintenance after the covering about one month.
2, the method for curing heavy metal according to claim 1 is characterized in that:
Get 333～416 parts of soil polyalcohol composite cement specials, 92～115 parts in water, 1.9～9.6 parts in heavy metal nitrate, add clean slurry mixer together, machine and stirred 2.7～3.3 minutes, stir, pack in the plastics water tumbler, and cover with preservative film and to tighten, avoid water evaporates, put into standard curing room maintenance one month.
3, the method for curing heavy metal according to claim 1 and 2 is characterized in that: described heavy metal nitrate is one of copper nitrate, plumbi nitras, zinc nitrate, nickel nitrate, cadmium nitrate.
4, a kind of method special-purpose base soil polymer according to the described curing heavy metal of claim 1, it is to be made by the raw material of following mass percent:
Flyash 40.0～80.0%
The alkali-activator 20.0～60.0% that NaOH and waterglass are formed.
5, fly ash base soil polyalcohol according to claim 4 is characterized in that:
Flyash 48.5～72.1%
The alkali-activator 27.9～51.5% that NaOH and waterglass are formed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100239214A CN101259314A (en) | 2008-04-22 | 2008-04-22 | Method for curing heavy metal and its special-purpose base soil polymer |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100239214A CN101259314A (en) | 2008-04-22 | 2008-04-22 | Method for curing heavy metal and its special-purpose base soil polymer |
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| CN101259314A true CN101259314A (en) | 2008-09-10 |
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|---|---|---|---|
| CNA2008100239214A Pending CN101259314A (en) | 2008-04-22 | 2008-04-22 | Method for curing heavy metal and its special-purpose base soil polymer |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102989741A (en) * | 2012-11-20 | 2013-03-27 | 盐城工学院 | Preparation method of heavy metal solid waste curing agent |
| CN103269993A (en) * | 2010-12-20 | 2013-08-28 | 路易斯安那理工大学研究基金会,路易斯安那理工大学基金会分公司 | Geopolymer mortar and method |
| CN103834410A (en) * | 2013-12-27 | 2014-06-04 | 云南省环境科学研究院(中国昆明高原湖泊国际研究中心) | Heavy metal immobilizing agent and method for immobilization and stabilization of soil heavy metals by using heavy metal immobilizing agent |
| CN105802635A (en) * | 2016-04-25 | 2016-07-27 | 浙江丰瑜生态科技有限公司 | Soil heavy metal passivator |
| CN107335165A (en) * | 2017-07-31 | 2017-11-10 | 武汉钢铁有限公司 | Chromium slag integration removing toxic substances curing based on metallurgical solid waste |
| CN107473426A (en) * | 2017-10-11 | 2017-12-15 | 大连青松智慧生态科技有限公司 | A kind of method for reclaiming heavy metal-polluted dye liquor |
| CN108641723A (en) * | 2018-06-14 | 2018-10-12 | 国电新能源技术研究院有限公司 | A kind of high-alkali coal ash for manufacturing for soil conditioner method |
| CN110964531A (en) * | 2018-09-26 | 2020-04-07 | 广东清大同科环保技术有限公司 | Desulfurization gypsum granular soil and preparation method thereof |
| CN111346903A (en) * | 2020-03-24 | 2020-06-30 | 陕西地建土地工程技术研究院有限责任公司 | Method for solidifying and stabilizing heavy metal contaminated soil by taking fly ash as raw material |
| CN112194391A (en) * | 2020-09-16 | 2021-01-08 | 中能化江苏地质矿产设计研究院有限公司 | High-efficiency curing material for heavy metal polluted bottom mud prepared based on coal-based solid waste |
| CN113337293A (en) * | 2021-06-23 | 2021-09-03 | 哈尔滨工业大学 | Anti-freezing solidification stabilizing agent for antimony-polluted soil and preparation method and application thereof |
-
2008
- 2008-04-22 CN CNA2008100239214A patent/CN101259314A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103269993A (en) * | 2010-12-20 | 2013-08-28 | 路易斯安那理工大学研究基金会,路易斯安那理工大学基金会分公司 | Geopolymer mortar and method |
| CN102989741A (en) * | 2012-11-20 | 2013-03-27 | 盐城工学院 | Preparation method of heavy metal solid waste curing agent |
| CN103834410A (en) * | 2013-12-27 | 2014-06-04 | 云南省环境科学研究院(中国昆明高原湖泊国际研究中心) | Heavy metal immobilizing agent and method for immobilization and stabilization of soil heavy metals by using heavy metal immobilizing agent |
| CN105802635A (en) * | 2016-04-25 | 2016-07-27 | 浙江丰瑜生态科技有限公司 | Soil heavy metal passivator |
| CN107335165A (en) * | 2017-07-31 | 2017-11-10 | 武汉钢铁有限公司 | Chromium slag integration removing toxic substances curing based on metallurgical solid waste |
| CN107473426A (en) * | 2017-10-11 | 2017-12-15 | 大连青松智慧生态科技有限公司 | A kind of method for reclaiming heavy metal-polluted dye liquor |
| CN108641723A (en) * | 2018-06-14 | 2018-10-12 | 国电新能源技术研究院有限公司 | A kind of high-alkali coal ash for manufacturing for soil conditioner method |
| CN110964531A (en) * | 2018-09-26 | 2020-04-07 | 广东清大同科环保技术有限公司 | Desulfurization gypsum granular soil and preparation method thereof |
| CN110964531B (en) * | 2018-09-26 | 2021-11-02 | 广东清大同科环保技术有限公司 | Desulfurization gypsum granular soil and preparation method thereof |
| CN111346903A (en) * | 2020-03-24 | 2020-06-30 | 陕西地建土地工程技术研究院有限责任公司 | Method for solidifying and stabilizing heavy metal contaminated soil by taking fly ash as raw material |
| CN112194391A (en) * | 2020-09-16 | 2021-01-08 | 中能化江苏地质矿产设计研究院有限公司 | High-efficiency curing material for heavy metal polluted bottom mud prepared based on coal-based solid waste |
| CN113337293A (en) * | 2021-06-23 | 2021-09-03 | 哈尔滨工业大学 | Anti-freezing solidification stabilizing agent for antimony-polluted soil and preparation method and application thereof |
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Open date: 20080910 |