CN102061177A - Heavy metal zinc polluted soil curing agent taking industrial waste carbide slag as raw material - Google Patents
Heavy metal zinc polluted soil curing agent taking industrial waste carbide slag as raw material Download PDFInfo
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- CN102061177A CN102061177A CN2010105333633A CN201010533363A CN102061177A CN 102061177 A CN102061177 A CN 102061177A CN 2010105333633 A CN2010105333633 A CN 2010105333633A CN 201010533363 A CN201010533363 A CN 201010533363A CN 102061177 A CN102061177 A CN 102061177A
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Abstract
The invention discloses a heavy metal zinc polluted soil curing agent taking industrial waste carbide slag as a raw material, which comprises the following components in percentage by mass: 70 to 80 percent of common silicate cement and 20 to 30 percent of industrial waste carbide slag. The cement is a common curing agent for the treatment of heavy metal polluted soil, and the effect of improving the strength of cured soil can be achieved by adding cement powder or cement paste into the polluted soil and fully stirring. When the cement is separately used in a project, the mixing ratio is relatively high and is about 12 to 18 percent. Even so, the strength, durability and curing quality of the cured soil are still difficult to ensure. Aiming at the phenomena, the invention provides a heavy metal zinc polluted soil curing formula taking the industrial waste carbide slag as the raw material. The formula consists of cement, carbide slag and bentonite. By promoting the hydration reaction of the cement and enhancing the Zn<2+> coating capability of crystal, the purposes of reducing the consumption of the cement and improving the curing effect are fulfilled.
Description
Technical field:
The present invention relates to heavy metal polluted soil and administer technical field, particularly relate to a kind of hardener formula that heavy metal zinc pollutes soil of administering.
Background technology:
In recent years, along with the development in China city, the outer suburbs is moved by the city in the factory site of many chemical industry, electronic enterprise, because the technology imperfection of most business processes " three dirts " discharge, causing former site foundation soil to be subjected to heavy metal contamination becomes industrial pollution soil.Contaminated foundation soil physico mechanical characteristic all can change, and causes that bearing capacity of foundation soil reduces, and causes buildings unstability or destruction, causes a series of accidents resulting from poor quality of projects; On the other hand, the pollutant component in the industrial pollution place can move to surrounding enviroment, harm local resident's health and ecotope.Therefore, adopting which kind of technology governance industrial pollution place, make its demand that satisfies second development and utilization, is an important topic that faces in China's modern city process of construction.
The chemosetting method is to administer heavy-metal contaminated soil utilization method the most widely at present.So-called chemosetting is handled and is meant with chemical process and makes the process of its stabilization with the harmful waste blending and be included in the closely knit inertia base material, and the used inert material of chemosetting is called solidifying agent.
The tradition solidify material has cement, lime, flyash, and wherein cement plays a major role.Cement solidification heavy metal mechanism: the moisture generation hydration reaction in cement and the contaminated soil generates gel, the objectionable impurities particulate is contained, and progressively sclerosis forms solidified cement body.The structure of this cured body mainly is hydrated reaction product C-S-H (many microporositys of a kind of amorphous glue material of cement, has very high surface-area, can adsorb a large amount of positively charged ions by physics mode), bag has advanced contaminant particle in the aquation xln, make the objectionable impurities of polluting in the soil be closed in cured body inside, thereby reach purpose innoxious, stabilization.Facts have proved that adopting cement solidification to handle is had certain effect by the soil of various heavy-metal pollutions, some heavy metal ion also can be wrapped in the lattice of cement matrix, thereby prevents the leaching of heavy metal ion effectively.But need higher cement mixing content in the engineering, use cement to improve cost undoubtedly merely, it is also undesirable to facts have proved that native endurance quality is polluted in simple use cement solidification.Except cement also has traditional solidifying agent such as flyash, lime, studies show that unconfined compression strength is low after polluting soil and using these two kinds of material cured, heavy metal ion leaches the concentration height, does not reach engineering and requirement on environmental protection.In sum, traditional solidifying agent exists cost height, solidified earth poor durability, is difficult to effectively wrap up heavy metal ion in the contaminated site, can not effectively improve the rheobasic shortcoming of contaminated land.
Carbide slag is the waste residue that produces when producing important industrial chemicals acetylene with calcium carbide, and main component is Ca (OH)
2, also contain CaCO
3, SiO
2, metals such as sulfide, magnesium and iron inorganics and a small amount of organism such as oxide compound, oxyhydroxide.According to national development and reform council statistics, state's endosymbiosis electrogenesis stone was 5,300,000 tons in 2003, produced 1.2 tons of carbide slags by consuming calcium carbide per ton, and the carbide slag that the whole nation produces is above 6,000,000 tons.The water content of carbide slag slurries is big, alkalescence is high, and flow is big, is the major polluting sources of sewage network; And the main component of dried carbide slag is a calcium oxide, is the high alkalinity material, and the pH value reaches more than 12.Discharging and store electricity rock ballast often take a large amount of arable lands, and the serious calcification in the soil of long-term storage, second ploughing be difficulty very.If the miscarriage meeting causes local ecotope and has a strong impact on.How with the carbide slag comprehensive recycling, to turn waste into wealth be the extremely urgent problem of enterprise.
Summary of the invention:
For solving existing heavy metal polluted soil solidifying agent; especially heavy metal zinc pollutes the existing cost height of native solidifying agent, solidified earth poor durability and the not good shortcoming of solidification effect; the invention provides a kind of heavy metal zinc that is raw material with the useless carbide slag of industry and pollute native solidifying agent; the present invention not only can reduce the solidifying agent cost; strengthen the solidification effect that pollutes soil; more carbide slag can be turned waste into wealth, play the effect of comprehensive utilization and protection environment.
The following technical scheme of the present invention:
A kind of heavy metal zinc that is raw material with the useless carbide slag of industry pollutes native solidifying agent, comprising: the useless carbide slag of ordinary Portland cement and industry, its mass percent is: 70%-80%: 20%-30%, wherein carbide slag is a quality under the complete drying state.
Beneficial effect:
For heavy metal zinc polluted soil, the chemosetting method was a kind of suitable in-situ treatment scheme, it is advantageous that the utilization solidifying agent changes soil physico-chemical property, fixing poisonous Zn
2+, reduce toxic substance to deep layer and underground water migration.Wherein most crucial is to mix solidifying agent kind and quality.At the lower soft clay ground of water ratio, mixing than being about 12%-18% of cement needs a large amount of cement in the construction process, and the price of cement material is higher simultaneously, accounts for the major part of treatment cost; And in the soft clay area of high-moisture percentage more, cement mixed ratio is bigger, is difficult to guarantee regulation effect simultaneously.The solidifying agent that adopts this patent to propose can effectively remedy the deficiency of traditional solidifying agent.According to present test-results, the useless carbide slag (complete drying state) of industry can replace the cement usage quantity of 20%-30%, thereby save cost 20%-30%, and adopt the solidified earth of this patent solidifying agent to have more high strength, better weather resistance and lower Zn
2+Leachability.
Description of drawings:
Fig. 1 is the unconfined compression strength comparison diagram that different ingredients solidifies zinc pollution soil.
Fig. 2 is that different ingredients solidifies zinc pollution soil drying and watering cycle accumulative total mass loss rate comparison diagram.
Fig. 3 is that different ingredients solidifies Zn in the zinc pollution soil
2+Leach the concentration comparison diagram.
Embodiment:
Embodiment 1
A kind of heavy metal zinc that is raw material with the useless carbide slag of industry pollutes native solidifying agent, comprise: the useless carbide slag of ordinary Portland cement and industry, its mass percent is: 70%-80%: 20%-30%, in the present embodiment, ordinary Portland cement with the mass percent of the useless carbide slag of industry is: 70%: 30%, 80%: 20% or 72%: 28%, described ordinary Portland cement can be the P.O.32.5 ordinary Portland cement, and carbide slag is the complete drying state.
A kind of heavy metal zinc that is raw material with the useless carbide slag of industry pollutes native solidifying agent, described solidifying agent is made up of ordinary Portland cement, the useless carbide slag of industry and sodium bentonite, wherein, ordinary Portland cement with the mass percent of the useless carbide slag of industry is: 70%-80%: 20%-30%, the incorporation of sodium bentonite is not more than ordinary Portland cement and 15% of the useless carbide slag incorporation sum of industry, in the present embodiment, ordinary Portland cement with the mass percent of the useless carbide slag of industry is: 70%: 30%, 80%: 20% or 75%: 25%; The incorporation of sodium bentonite is ordinary Portland cement and 15%, 12%, 0.1% or 7% of the useless carbide slag incorporation sum of industry.
The present invention is according to above-mentioned prescription, with its mixing solidifying agent that gets product.The use volume of solidifying agent is 15% or 18% (heavy metal zinc behind solidifying agent quality/complete drying pollutes the soil property amount).Table 1 and table 2 have provided the basic physics-chem characteristic and the chemical ingredients of carbide slag respectively.
Because one of the raw material that solidifying agent of the present invention adopts carbide slag is an alkaline matter, provides the higher pH environment for polluting native solidification process, make the aquation coagulation reaction of cement accelerate, pollute the Zn in the soil simultaneously
2+Under alkaline condition, generate the oxyhydroxide and the carbonate that are insoluble in water, Zn
2+Be fixed in the lattice of cement matrix, thereby prevent Zn effectively
2+Leach the harm environment.The a small amount of sodium bentonite that mixes can effectively improve the endurance quality of polluting solidified earth, strengthens Zn
2+The curing stabilising effect.
The basic physics-chem characteristic of table 1 carbide slag
Table 2 carbide slag chemical composition analysis
The present invention will be further described below in conjunction with laboratory test results:
The resettlement of zinc-plated workshop, Lianyungang is got former factory site soil and is tested, and the Main physical chemical index of original position soil sees Table 3, and chemical analysis results shows the Zn of serious regional soil of pollution
2+Content (Zn
2+Quality accounts for the per-cent of the pollution soil total mass of complete drying) be 0.5%.
Detect the water ratio that pollutes soil, utilize NJ-160 type cement paste stirrer marginal not waterside to stir the pollution soil sample that contaminated soil was configured in 5 minutes water ratio 60% (pollute the water in soil quality and account for the per-cent that the soil property amount is polluted in oven dry fully), put it in the holding barrel and sealing, make water ratio even.The pollution soil sample for preparing is mixed 15% (solidifying agent accounts for the mass percent of the pollution soil of complete drying) solidifying agent, adopt the homotype agitator to stir 5 minutes.Be the effect of contrast solidifying agent of the present invention and traditional plain cement solidifying agent, solidifying agent adopts three kinds of prescriptions: prescription A: plain cement; Prescription B:70% cement+30% carbide slag; Prescription C:70% cement+20% carbide slag+10% sodium bentonite.The back taking-up solidified earth that stirs is inserted the mould of 5cm (diameter) * 10cm (highly), and manual jolt ramming is wipeed off, make sample, cover film, leave standstill 24h after, the demoulding, the curing room of putting into 24 ℃ and 100% humidity maintenance 7 days, 28 days, 56 days and 90 days respectively.For more novel solidifying agent and traditional plain cement prescription pollute native intensity, weather resistance and control Zn improving
2+The effect of dissolving out capability is carried out unconfined compressive strenght test, cyclic wetting and drying test and TCLP leaching experiment in the different length of times to each group sample.
Experimental result shows: the solidifying agent that adopts prescription B, C is to the raising effect of contaminated site intensity more obviously (the unconfined compressive strenght test result is with reference to Fig. 1); Adopt the weather resistance of the solidified earth of prescription B, C also be better than the filling a prescription solidified earth (the cyclic wetting and drying test result is with reference to Fig. 2) of A; TCLP leaching test-results shows that the solidifying agent of fill a prescription B, C is solidifying Zn
2+Effect on the A outstanding more (pouring rate test-results is with reference to Fig. 3) that fills a prescription.
The Main physical index of table 3 soil sample
| The soil sample title | Water ratio (%) | Proportion | Plastic limit (%) | Liquid limit (%) | The pH value |
| Weak soil | 45? | 2.72? | 25.8? | 55.1? | 8.20? |
1. unconfined compressive strenght test
Unconfined compressive strenght test uses YSH-2 type limestone soil not have the confining pressure instrument according to " highway earthwork test rule " (JTG E40-2007), and compression speed is 1mm/min.The curing age of sample was respectively 28 days, 56 days and 90 days, and each is organized sample and all gets 3 parallel samples and carry out unconfined compressive strenght test, with its mean value as unconfined compression strength, data preparation drafting pattern 1.Fig. 1 interpretation of result as can be known, in each length of time of test determination, the intensity of the curing zinc pollution soil of prescription B, C exceeds 20%-33% and 15%-27% than the solidified earth intensity of prescription A respectively, the effect that prescription B, C improve intensity is more obvious.
2. cyclic wetting and drying test
Cyclic wetting and drying test is carried out according to Japanese standard [Public Works Research Institute:Final Report ofCooperative Research, 1997, pp.77-82].During curing age to 28 day, 3 groups of solidified earth are respectively got 2 parallel samples (test-results is averaged), carry out cyclic wetting and drying test (the cyclic wetting and drying test method sees Table 4).
Table 4 cyclic wetting and drying test method
Drying and watering cycle is carried out ten grades altogether, all measures the quality m that different ingredients solidifies soil sample when every grade of cyclic wetting and drying test finishes
n, in conjunction with sample initial mass m
0, the calculated mass rate of loss
Analyze accumulative total mass loss rate ∑ w
n=w
1+ w
2+ ... w
nThe mass loss rate data logging of sample sees Table 5, and the mass accumulation rate of loss contrasts as shown in Figure 2.
Each formulation cured zinc pollution soil cyclic wetting and drying test accumulative total mass loss rate of table 5
Adopting accumulative total mass loss rate after ten drying and watering cycles of solidified earth of prescription A as can be known according to Fig. 2 is respectively 1.5 times and 2.5 times of solidified earth that adopt prescription B and prescription C, and the visible endurance quality of the solidified earth of prescription B and prescription C that adopts is better than the solidified earth that adopts A to fill a prescription.
3.TCLP leaching test
Zn in the different ingredients curing heavy metal zinc pollution soil
2+Leach toxicity leaching test TCLP (U.S.Environmental Protection Agency.TechnicalAssistance Document for Complying with the TC Rule and Implementing the ToxicityCharacteristic Leaching Procedure (TCLP) [R] .U.S.A of the test of concentration according to the recommendation of U.S. Environmental Protection Administration, Washington DC, www.epa.gov, 1994) method is measured, and adopts the Zn in the atom light absorption method detection leachate
2+Concentration.The curing soil sample curing age that TCLP leaching test is adopted is 7d and 28d, all adopts two parallel samples, and the result gets its mean value, and test-results is seen Fig. 3.
Test-results as shown in Figure 3, the result shows detected Zn from prescription A sample leachate
2+Concentration is 1.2 times that measure numerical value the identical length of time from B, C prescription sample leachate.As seen B, the prescription C Zn to zinc pollution soil fills a prescription
2+Solidification effect is better than prescription A.
Claims (2)
1. one kind is that the heavy metal zinc of raw material pollutes native solidifying agent with the useless carbide slag of industry, it is characterized in that comprise: the useless carbide slag of ordinary Portland cement and industry, its mass percent is: 70%-80% ﹕ 20%-30%.
2. the heavy metal zinc that is raw material with the useless carbide slag of industry according to claim 1 pollutes native solidifying agent, it is characterized in that, described solidifying agent is made up of ordinary Portland cement, the useless carbide slag of industry and sodium bentonite, wherein, ordinary Portland cement with the mass percent of the useless carbide slag of industry is: 70%-80% ﹕ 20%-30%, the incorporation of sodium bentonite are not more than ordinary Portland cement and 15% of the useless carbide slag incorporation sum of industry.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102992724A (en) * | 2012-12-03 | 2013-03-27 | 东南大学 | Curing agent for expansible heavy metal polluted clay as well as preparation method and using method of 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 |
| CN104327858A (en) * | 2014-09-22 | 2015-02-04 | 广西大学 | Soil heavy metal compound stabilizer and method using soil heavy metal compound stabilizer for passivation of soil heavy metals |
| CN112321225A (en) * | 2020-10-20 | 2021-02-05 | 上海市政工程设计研究总院（集团）有限公司 | Curing agent for curing soft soil and widening roadbed |
| CN112875832A (en) * | 2021-03-17 | 2021-06-01 | 辽宁工程技术大学 | Preparation method of alkaline slow-release material |
| CN113185980A (en) * | 2021-04-09 | 2021-07-30 | 太原理工大学 | Lead-polluted soil curing agent combining red mud, carbide slag and phosphogypsum and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101275394A (en) * | 2008-04-28 | 2008-10-01 | 北京航空航天大学 | Curing method for saline soil |
-
2010
- 2010-11-05 CN CN2010105333633A patent/CN102061177A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101275394A (en) * | 2008-04-28 | 2008-10-01 | 北京航空航天大学 | Curing method for saline soil |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102992724A (en) * | 2012-12-03 | 2013-03-27 | 东南大学 | Curing agent for expansible heavy metal polluted clay as well as preparation method and using method of curing agent |
| CN102992724B (en) * | 2012-12-03 | 2014-07-09 | 东南大学 | Curing agent for expansible heavy metal polluted clay as well as preparation method and using method of 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 |
| CN104327858A (en) * | 2014-09-22 | 2015-02-04 | 广西大学 | Soil heavy metal compound stabilizer and method using soil heavy metal compound stabilizer for passivation of soil heavy metals |
| CN104327858B (en) * | 2014-09-22 | 2017-09-29 | 广西大学 | A kind of soil heavy metal combined stabilizer and its passivating method to heavy metal-polluted soil |
| CN112321225A (en) * | 2020-10-20 | 2021-02-05 | 上海市政工程设计研究总院（集团）有限公司 | Curing agent for curing soft soil and widening roadbed |
| CN112875832A (en) * | 2021-03-17 | 2021-06-01 | 辽宁工程技术大学 | Preparation method of alkaline slow-release material |
| CN112875832B (en) * | 2021-03-17 | 2022-08-23 | 辽宁工程技术大学 | Preparation method of alkaline slow-release material |
| CN113185980A (en) * | 2021-04-09 | 2021-07-30 | 太原理工大学 | Lead-polluted soil curing agent combining red mud, carbide slag and phosphogypsum and preparation method thereof |
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Application publication date: 20110518 |