CN105294023A - Method for repairing heavy metal-polluted soil by using red mud granular material - Google Patents
Method for repairing heavy metal-polluted soil by using red mud granular material Download PDFInfo
- Publication number
- CN105294023A CN105294023A CN201510796682.6A CN201510796682A CN105294023A CN 105294023 A CN105294023 A CN 105294023A CN 201510796682 A CN201510796682 A CN 201510796682A CN 105294023 A CN105294023 A CN 105294023A
- Authority
- CN
- China
- Prior art keywords
- red mud
- soil
- gelling
- gypsum
- particulate material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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 red mud granular material and an application thereof. A red mud particle soil repairing agent takes red mud powder, gypsum, cement and fly ash as main materials, phosphate is doped as an activation material, thereby, gelling capability of red the mud powder and capability for fixing heavy metal ions in a stable mode can be increased, a series of processes of mixing by adding water, balling, and drying solidification at normal temperature can be carried out, so that the spherical particle soil repairing agent can be obtained by composite moulding of the red mud raw ore powder material. The method realizes preparation of the red mud powder with granulation at normal temperature, the obtained red mud particle soil repairing agent has certain mechanical strength and good heavy metal stable solidification performance, the heavy metal-polluted soil or sludge can be effectively processed, OH radical ions can be slowly released simultaneously, a pH value of the soil after restoration by the repairing agent is basically stabilized below 7.5, problems of fast increase of the pH value of the soil and poor growth condition for plants during a soil restoration process by the red mud powder can be effectively overcome, and the method has high application value and environment benefit.
Description
Technical field
The invention belongs to heavy metal pollution of soil Treatment process field.More specifically, a kind of reparation of the method utilizing red mud particulate material restoration of soil polluted by heavy metal, particularly lead pollution of soil is related to.
Background technology
The soil of China's heavy metal contamination has reached 2,000 ten thousand hm
2, account for 1/6 of total area under cultivation, the farmland of polluting because of Industrial " three Waste " reaches 7,000,000 hm
2, cause annual grain drop in production 10,000,000,000 kg.Dig up mine simultaneously, smelt and also result in the serious heavy metal contamination of the supergene environment such as mining area and surrounding area soil.Southwestern China and middle area, the particularly provinces and regions such as Yunnan, Jiangxi, Hunan, Guizhou and Guangxi, because mining and Metal smelting cause the serious heavy metal contamination in mining area and soil, surrounding area, tract is caused to be unsuitable for cultivating, the ecotope of locality and people's health are constituted a serious threat, hampers agriculture production.
The recovery technique of heavy-metal contaminated soil is mainly divided into two classes: in-situ immobilization and showering.In-situ immobilization mode mainly comprises physical technique, chemical technology and bioremediation technology; Physical technique comprises soil moved in improve the original and is separated with the method for digging, thermal treatment, moves electricity reparation and isolation embedding etc.; Chemical technology comprises that chemistry is fixing, chemical leaching and chemical oxidation/reduction etc.; Bioremediation technology comprises phytoremediation, microorganism remediation and compost etc.Wherein, the tradition of most widely used physical technique excavates landfill recovery technique, because cost is high and take up an area large deficiency, limit its widespread use in soil pollution site remediation, gradually low by cost, under surrounding environment disturbance, in-situ chemical technique for fixing that social acceptable degree is high replace.In-situ chemical fixedly refers to and add a certain class or a few class chemical additive in contaminated soil, change the occurrence patterns of heavy metal in soil by absorption, precipitation or the mechanism such as co-precipitation, ion-exchange, reduce the movability of heavy metal and biological effectiveness thus reduce a kind of recovery technique of heavy metal to environment and harm.The key of fixation in situ technology is to select suitable solidifying agent for the characteristic of contaminated soil, conventional solidifying agent is generally the lower mineral of Financial cost and industrial by-products, as unslaked lime, phosphoric acid salt and mineral thereof, aluminosilicate, iron and manganese oxides, zeolite, mud, compost etc., research finds that these solidifying agent can the heavy metal such as lead, good fortune, copper, zinc, arsenic effectively in fixing soil.
Red mud is the residue produced in aluminum oxide production process, oxide compound containing abundant iron, aluminium and calcium, solubility and the bioavailability of metal can be reduced, continual and steady solidification is played by release OH ion pair heavy metal in soil, promote that the chemical form of Heavy Metals in Contaminated Soils transforms, can be used as the stabilizing and curing agent of heavy-metal contaminated soil.But, substantially or directly utilize red mud powder when current red mud is applied to Pollution abatement and restoration of the ecosystem, because the release of its free alkali is too fast, cause soil pH lift velocity very fast, serious harm is caused to vegetation and soil microorganism.
Therefore, how reducing free alkali release rate, the problem that when how to suppress to administer heavy-metal contaminated soil, soil pH lift velocity is too fast, is that current red mud is applied to heavy-metal contaminated soil improvement reparation aspect problem demanding prompt solution.
Summary of the invention
The technical problem to be solved in the present invention overcomes existingly directly to utilize red mud powder repairing polluted soil; because the release of its free alkali is too fast; P in soil H is caused to rise very soon; the problem that can work the mischief to vegetation and soil microorganism; a kind of soil remediation method adopting granulating red mud stable curing heavy metal ion is provided; the gelling of gypsum, silicate cement, flyash is utilized to prepare red mud granular soil renovation agent, for stable curing heavy metal ion.This particle renovation agent restorative procedure is with low cost, effectively can solve the zooming problem of soil pH, realizes the agricultural land soil in-situ immobilization by heavy metal contamination.
The object of this invention is to provide a kind of red mud particulate material and preparation method thereof.
Another object of the present invention is to provide a kind of method utilizing above-mentioned red mud particulate material restoration of soil polluted by heavy metal or mud.
Above-mentioned purpose of the present invention is achieved through the following technical solutions:
A kind of red mud particulate material, be with useless red mud powder and waste gypsum for main raw material, add the gelling ability that gelling material improves red mud, and add phosphoric acid salt as active material, prepare through the mixing that adds water, balling-up, Air drying, a series of process of solidification; Described gelling material is the mixture of silicate cement and flyash.Described gypsum can be industrial gypsum, also can be industrial residue waste gypsum.
Wherein, preferably, the amount ratio of described silicate cement and flyash is 1 ~ 4:1.
More preferably, the amount ratio of described silicate cement and flyash is 1:1.
Preferably, the red mud of described red mud for producing in alumina producing Bayer process process, its main component is aluminum oxide, ferric oxide and calcium oxide.
Preferably, according to accounting for the gross weight of three than meter, the consumption of red mud, gypsum and gelling material is respectively 80 ~ 90%, 3 ~ 8% and 2 ~ 10%; Described phosphatic consumption accounts for 3 ~ 8% of three's gross weight.Preferably.
More preferably, according to the ratio meter of gross weight accounting for three, the consumption of red mud, gypsum and gelling material is respectively 85%, 5% and 10%, and phosphatic consumption is 2 ~ 5%, and most preferably, phosphatic consumption is 5%.
In addition preferably, the consumption of described water is: according to mass ratio range, water: compound=0.4 ~ 0.6:1, and described compound is the mixture of red mud, gypsum and gelling material.
More preferably, water: compound=0.5:1.
Preferably, described red mud, gypsum and gelling material are powder, and first cross 50 ~ 70 mesh sieves before using.More preferably, 40 ~ 60 mesh sieves are crossed.Most preferably, 60 mesh sieves are crossed.
Preferably, after the first mix and blend 2 ~ 4h of described red mud, gypsum and gelling material, then add water and phosphoric acid salt mixing.
Preferably, the preparation of described red mud particulate material adopts granulating disc.
More preferably, the use rotating speed of granulating disc is 20 ~ 40r/min.
The red mud particulate material of above-mentioned preparation is particulate state, and preferably, its shape is the spherical of particle diameter 1 ~ 5mm.More preferably, shape is the spherical of particle diameter 2 ~ 3mm.
Particularly, the preparation method of above-mentioned red mud particulate material comprises the steps:
S1. batch mixing: red mud, gypsum and gelling material are mixed in proportion, are pulverized, stirs 2 ~ 4h, all powders is mixed; Compound crosses 60 mesh sieves, obtains mixed powder;
S2. granulation: put mixed powder in granulating disc, controls granulation rotating speed 20 ~ 40r/min, sprays into water, then added the phosphoric acid salt of 50 ~ 70 mesh sieves in proportion, by mixed powder granulation balling-up by the water cement ratio of 0.4 ~ 0.6:1;
S3. air-dry: natural air drying 12 ~ 48h;
S4. dry: the green-ball after S3 is air-dry 60 ~ 70 DEG C dries 2 ~ 6h;
S5. naturally cooling, obtains red mud particulate material.
Wherein, preferably, churning time described in step S1 is 3.5h.
Preferably, water cement ratio described in step S2 is 0.5.
Preferably, the particle diameter of ball described in step S2 is 2 ~ 3mm.
Preferably, phosphoric acid salt described in step S2 crosses 60 mesh sieves.
Preferably, the time of natural air drying described in step S3 is 36h.
Preferably, the temperature of drying described in step S4 is 65 DEG C, and the time of described oven dry is 4h.
The application of above-mentioned red mud particulate material in the improvement reparation of heavy-metal contaminated soil or mud is also within protection scope of the present invention.
Preferably, described heavy-metal contaminated soil or mud are Pb
2+, Zn
2+and/or Cu
2+in soil or the mud of heavy-metal pollution.
More preferably, the heavy-metal contaminated soil be suitable for or the standard of mud are: the levels of heavy metal is: Pb
2+≤ 500mg/L, Zn
2+≤ 800mg/L, Cu
2+≤ 650mg/L.
Pb
2+≤ 300mg/L, Zn
2+≤ 500mg/L, Cu
2+≤ 500mg/L preferably can embodiment as one, the method of embody rule, a kind of method utilizing red mud particulate material restoration of soil polluted by heavy metal: according to the amount ratio of 2 ~ 8%, above-mentioned red mud particulate material is mixed into heavy-metal contaminated soil or mud, stablize 5 ~ 10 days under field conditions (factors), namely complete the stable curing to soil and Heavy Metals in Sludge ion.
Preferably, the amount ratio of red mud particulate material is 6%.
The present invention existingly directly utilizes red mud powder repairing polluted soil to overcome, because the release of its free alkali is too fast, soil pH is caused to rise very soon, the problem that can work the mischief to vegetation and soil microorganism, a kind of granular red mud material is prepared through large quantity research and exploration, specifically with useless red mud powder, waste gypsum is main raw material, and the gelling material such as a certain amount of silicate cement of admixture and flyash is as framework material, add activated material phosphoric acid salt again, through adding water mixing, balling-up, nature dry-air blast, drying a series of process composite molding is particulate state renovation agent.This red mud granular soil renovation agent is played by slowly-releasing heavy metal and turns use into continually and steadily, to can be used in the dirty soil of passivation the heavy metal ion such as plumbous zinc, be conducive to promoting that the chemical form of Heavy Metals in Contaminated Soils ion transforms, the more important thing is, effectively can solve soil pH to rise too fast problem, realize the agricultural land soil in-situ immobilization by heavy metal contamination.
The present invention has following beneficial effect:
The present invention utilizes cement and the composite use of flyash can the gelling property of improvement red mud of synergy, and further combined with the phosphatic effect of activated material, achieve the granulating of red mud powder under normal temperature, there is certain physical strength and good stable curing heavy metal ion performance, effectively can process heavy metal, especially lead ion contaminated soil; And the pH of soil is basically stable at less than 7.5 after utilizing red mud particulate material of the present invention reparation, effectively can overcome powdery red mud material rehabilitating soil to there is soil pH and to rise fast, be unfavorable for the problem of plant-growth, industrialized operate continuously can be realized, be conducive to the effective stable curing realizing heavy-metal contaminated soil and Heavy Metals in Sludge ion, in the actual treatment reparation of heavy-metal contaminated soil or mud, there is higher using value.
It is for raw material with useless red mud powder, waste gypsum etc. that the present invention prepares red mud particle, red mud powder, waste gypsum, flyash and cement are cheap material, wide material sources are easy to get, with low cost, and adopt Industry Waste red mud powder as the major ingredient of particle renovation agent, by red mud for the treatment of heavy-metal contaminated soil and mud, not only solve himself and stack the problem of taking up an area, but also solve the problem of heavy-metal contaminated soil, reach the object of the treatment of wastes with processes of wastes against one another, there is higher using value and environmental benefit.
In addition, preparation technology of the present invention is simple, and cost is low, has very high economic worth, is suitable for applying of actual industrial production.
Accompanying drawing explanation
Fig. 1 is the XRD figure of red mud.
Fig. 2 is the preparation flow figure of red mud granular soil renovation agent.
Fig. 3 is the renovation technique schema of red mud particle restoration of soil polluted by heavy metal.
Embodiment
Further illustrate the present invention below in conjunction with Figure of description and specific embodiment, but embodiment does not limit in any form to the present invention.Unless stated otherwise, the present invention adopts reagent, method and apparatus are the art conventional reagent, method and apparatus.Unless stated otherwise, agents useful for same and material are commercial.
Embodiment 1 red mud powder powder material is to the reparation of soil
1, the property analysis of red mud
(1) the image analysis of red mud
The useless red mud that during the present embodiment adopts, electricity throwing Shanxi Aluminum company limited alumina producing Bayer process produces is studied, and as shown in Figure 1, in red mud, essential mineral has calcite (CaCO to the XRD figure of red mud
3), diaspore (AlO (OH)), ca aluminosilicate (CaAl
2o
2si
8), calcium silicate hydrate (Ca
3si
2o
71.5H
2o), lapis calaminaris (Zn
4si
2o
7h
2o) etc.In the middle of these materials, calcite, lapis calaminaris etc. are rhombus crystal face, are main skeletons, can play certain pectisation; And diaspore and silico-calcium Barbiturates mainly play filling effect and pectisation in skeleton.
(2) chemical constitution of red mud
The chemical composition of red mud depends on the material composition of additive in the composition of bauxite, the method for producing aluminum oxide and production process and the composition etc. of newly-generated compound.
Sem energy spectrum analysis (SEM-EDS) and chemical analysis, its chemical constitution is as shown in table 1.
The Chemical Composition of table 1 red mud and content
Can find out from analytical results, red mud itself has certain gelling property, but more weak, and the presetting period is longer.According to the gelation mechanism of red mud, its gelling reaction is as follows:
2 (3CaOSiO
2)+6H
2o → 3CaO2SiO
23H
2o (hydrated calcium silicate gel)+3Ca (OH)
2
2(CaOSiO
2)·4H
2O→3CaO·2SiO
2·3H
2O+Ca(OH)
2
3CaOAl
2o
3+ 6H
2o → 3CaOAl
2o
36H
2o (drated calcium aluminate crystal)
4CaOAl
2o
3fe
2o
3+ 7H
2o → 3CaOAl
2o
36H
2o+CaOFe
2o
3h
2o (hydrated calcium ferrite gel).
2, red mud powder powder material is to the reparation of soil
Cross 60 mesh sieves after being pulverized by red mud, the dosage according to 2%, 4%, 6%, 8%, 10%, 12% adds red mud powder in contaminated soil, then adds the deionized water of 30% by weighting method, stablizes 5 days.Soil sample is gone to clear up mensuration.
Table 2Pb content (850mg/kg)
As can be seen from Table 2, the residual form adding the Lead In Soil of red mud powder increases, and exchangeable species and acid-soluble state reduce.When dosage is 8g/kg, compare with blank, exchangeable species and acid-soluble state lead reduce 49.63%, the plumbous average increase by 46.66% of residual form.Illustrate that red mud effectively can reduce the bioavailability of the lead in soil, alleviate plumbous to animals and plants pollution, improve soil quality.
In addition, as shown in table 3 to the monitored results of changes of pH.
Table 3
Result shows, and soil pH lift velocity is very fast, can cause serious harm to vegetation and soil microorganism.
Embodiment 2 red mud gelling study on the modification
The present invention selects silicate cement and the multiple goods and materials such as gypsum, flyash, to improving the gelling ability of red mud.We screen through large quantifier elimination, and final choice gypsum, cement and flyash are additional material modified as gelling.
1, the gelling property of raw material
As described in Example 1, red mud itself has certain gelling property, but more weak, and the presetting period is longer.Its gelling property is further studied: red mud crosses 60 mesh sieves through air-dry fragmentation, and sealing saves backup.Measuring pH according to cement-water ratio 1:2.5 is 12.36.For measuring the gelling of red mud raw material, being convenient to subsequent granulation experiment, adopting water cement ratio 0.5,0.6, test each sample from gelation time.Related data is in table 4.
The gelling property of table 4 red mud raw material
Red mud itself, containing the material such as more calcium cpd and water calcium aluminate, so have certain cement properties, itself have certain gelling, but gelling is poor.Because red mud has larger retentiveness, up to 700 ~ 1000m3/kg, account for 79% ~ 93% of gross weight.So, water cement ratio 0.5,0.6 time, all do not present mobility.As data in table 2, the red mud presetting period is all greater than 20 hours, and when water cement ratio is 0.6, final setting time is greater than 84 hours.
In addition, when vibrations occur red mud time, the moisture of dry mud absorption can flow out by desorption from red mud, and this reason causes red mud gelling bad, and after gelling, hardness is inadequate.In order to the gelling property that can improve red mud just needs to add certain gelling material in red mud.Meanwhile, utilize waste material red mud in order to as far as possible many, realize the recycling object of red mud, need again reasonably to control admixture total amount while improving gelling.
2, to two kinds of gelling material waste gypsums and cement, adopt water cement ratio condition identical with red mud to measure time of coagulation, the results are shown in following table 5.
The condensation performance of table 5 gelling material
From table 5, the initial set performance of cement and gypsum material is good, can be chosen as interpolation gelling material.
3, additional waste gypsum, cement material affect the gelling property of red mud
By adding waste gypsum and the cement of different amount respectively, after mixing with red mud powder.Stir under water cement ratio 0.5 condition, and make to treat gelling material surfacing by vibrations.Every about measuring its gelling situation half an hour.The sample gelling of different ratio is in table 6 and 7.
Table 6 waste gypsum is to the improvement of red mud gelling property
Table 6 reflects the increase along with gypsum dosage, and initial set and the final setting time of material reduce gradually.When gypsum dosage is 25%, initial set and final set all occur within an hour.But find in experimentation, along with the increase of gypsum dosage, the mobility of material becomes large.Due under larger gypsum dosage, compound is based on the fast gelation of gypsum, and the hydration process of the other materials such as red mud can be hindered.Gypsum dosage is crossed conference and is reduced red mud consumption, and be not inconsistent with experiment original intention, it is more reasonable therefore to control gypsum consumption 5 ~ 10%.
Table 7 cement is to the improvement of red mud gelling property
Compared with table 7 as can be seen from table 6: cement is when dosage is 5% and 10%, and presetting period and final setting time are all less than the compound of admixture gypsum under identical conditions.This illustrates: under little volume condition, when dosage is within 10%, identical addition content Water Under mud sexually revises larger than gypsum to raw material gelling.Because the strong retentiveness of red mud, when addition content is less, most of water is adsorbed by red mud, and the water cement ratio of the cement made reduces further, so, condense under little volume condition faster.
4, additional fly ash material affects the gelling property of red mud
After the same method, the flyash by adding different amount studies its impact on the gelling property of red mud.The sample gelling of different ratio is in table 8.
Table 8 flyash is to the improvement of red mud gelling property
As can be seen from Table 8: flyash is when dosage is 5% and 10%, and presetting period and final setting time are all less than the compound of admixture gypsum under identical conditions, cement.
In sum, cement, gypsum, flyash are all improved effect to red mud gelling property, and the improvement result of flyash is the most remarkable comparatively speaking, and cement takes second place.
The composite impact on red mud gelling property of embodiment 3 gelling material
1, cement and the composite impact on red mud gelling property of flyash
(1) from upper result of study, cement and the improvement result of flyash to red mud gelling property the most remarkable, in order to inquire into better red mud gelling property improving countermeasure further, the present invention is investigated the compounded combination of cement and flyash to the impact of red mud gelling property.
(2) its impact on the gelling property of red mud studied by the cement of different ratio and flyash after the same method, by adding 10%.The sample gelling of different ratio is in table 9.
Table 9 cement and the composite improvement to red mud gelling property of flyash
As can be seen from the contrast of table 9 and table 3, table 4, cement and the composite use of flyash can reach the effect of synergy, significantly can improve the gelling property of red mud, when cement and flyash amount ratio are 1 ~ 4:1, synergy is the most remarkable, the most obvious to the improvement of red mud gelling property, and optimum compound proportion is 1:1.Therefore, following examples of the present invention select cement and flyash according to the composite scheme of 1:1, in conjunction with the use of waste gypsum, prepare red mud particle renovation agent.
2, gypsum, cement and flyash amount ratio are on the impact of red mud gelling property
The gelling measuring the mixing material of different gypsum, cement and flyash amount ratio under water cement ratio 0.5 condition is shown in Table 10.
Table 10 mixing match material is on the impact of the gelling property of red mud
As seen from the above table, do not add flyash, its gelation time is comparatively slow, and after adding flyash, the presetting period improves very fast, but increases not obvious when being increased to 8%, so selected formula 5 is as granulating formula.Determine that various material usage is: 5% cement+5% gypsum+5% flyash+85% red mud.
Embodiment 4 water cement ratio affects the gelling property of red mud
Complete on the basis of experiment, the present embodiment adopts 5% gypsum+10% gelling material (concrete and coal ash of 1:1)+85% red mud proportioning, carries out according to different water cement ratio the research measuring the condensation of materials time,
The results are shown in Table 11.
Table 11 water cement ratio is on the impact of red mud compound gelling property
From experimental result, the universal law of gelling material hydration and hardening is deferred in experiment.Along with the increase of water cement ratio, gelling slows down.The increase of water cement ratio and gelation time are also disproportionate.When water cement ratio is increased to 0.6 from 0.5, the presetting period extends to 1.85h by 0.6h, and fluidity of slurry change is little.In suitable gelation time, select to adopt less water cement ratio, reduce time of coagulation, meet granulation requirement; Therefore best water cement ratio is chosen to be 0.5.
The selection of embodiment 5 red mud particle activated material
1, activated material is on the impact of granulation
Monocalcium phosphate, lime, flyash is selected to test as activated material: on the basis of the materials of 5% cement+5% gypsum+5% flyash+85% red mud, add the activated material lime of said mixture total amount 5%, monocalcium phosphate or flyash, optimize the performance of red mud particle further.Water cement ratio 0.5, becomes mould to measure time of coagulation, the results are shown in Table shown in 12 after mix and blend.
The impact of table 12 red mud time of coagulation
From table 12, after using lime, flyash or monocalcium phosphate to activate further, initial set performance difference is not very large, but final set performance belongs to interpolation, and monocalcium phosphate is better, and consider that the fixed effect of phosphoric acid salt to heavy metal in soil ion is better than lime and flyash, the more important thing is, after using monocalcium phosphate to activate further, significantly can promote the gelling property of particulate material, so select monocalcium phosphate as further activated material.
2, activated material dosage optimization
According to the activator selected, on the basis of the materials of 5% cement+5% gypsum+5% flyash+85% red mud, add the monocalcium phosphate of said mixture total amount 5%, the gelling measuring mixing material in water cement ratio 0.5 condition sees the following form 13.
Table 13 mixing match material is on the impact of the gelling property of red mud
The preparation of embodiment 6 red mud particulate material
1, preparation method
S1. get the raw materials ready: red mud powder, gypsum, cement flour, powdered coal ash are ground and cross 60 mesh sieves;
S2. batch mixing: by weight: 85% red mud+5% cement+5% gypsum+5% flyash, mixing, stirs 4h, all powders is mixed;
S3. granulation: put mixed powder in granulating disc, sprays into water by water cement ratio 0.5, adds the monocalcium phosphate crossing 60 mesh sieves by amount ratio, and control rotating speed 20 ~ 40r/min, making particle diameter is 2 ~ 3mm spherolite;
S4. air-dry: natural air drying 48h under room temperature condition;
S5. dry: the condition of the green-ball after S3 is air-dry 65 DEG C dries 6h;
S6. naturally cooling, obtains red mud granular soil renovation agent.
2, through measuring, the specific surface area of upper prepared red mud granular soil renovation agent is 22.04m
2/ g, Pulverization ratio is 12.60%.
Embodiment 7 simulating pollution soil treatment is applied
1, test container is little plastic cup, the dirty native 100g (CK) of every cup simulation, and add red mud powder (RM) and red mud particle (PL) mixing respectively by design quantity, Setup Experiments repeats for 3 times.
2, test and carry out in the constant temperature culture of 25 DEG C, every other day keep the skin wet to soil with deionized water, make soil moisture keep the water yield to be about 50%.Regular replenishment moisture content, sampled after 5,10,20,30 days respectively, measure the pH value changing conditions for the treatment of group soil, adopt reference material administration of the former European Economic Community to instruct standard three step grading extraction method (BCR method) research of formulating to add the fixed effect of red mud particle to Lead In Soil and zinc.Result is as following table 14 and table 15.
Table 14 is processed the pH value result of variations of soil
As can be seen from Table 14, along with the increase of red mud powder dosage, the pH value of processed soil increases gradually; And along with the prolongation in treatment time, powder alkaline leaching does not delay trend.By contrast, the impact of granular red mud on soil pH is less, and the particle dosage of 6% is in treating processes, and soil pH is basically stable at about 7.5.Less with the initial pH difference of soil sample.Illustrate that red mud granulating of the present invention considerably reduces red mud and leaches the impact of alkalescence on soil.
Table 15 red mud powder and red mud particle are on the impact of soil acid extractable Pb content
As can be seen from Table 15, the exchangeable species and the acid-soluble state that add the Lead In Soil of red mud powder and red mud particulate material have minimizing, wherein, red mud particulate material group is compared with blank, the plumbous decreased average more than 50% of acid-soluble state, illustrate that red mud particle effectively can reduce the bioavailability of the lead in soil, alleviate plumbous to animals and plants pollution, improve soil quality.
The contaminated soil process application of embodiment 8 factory
1, the dirty soil of experiment material takes from Panyu District of Guangzhou City battery production factory; Experimental technique is with example 7.
2, result is as following table 16 and 17.
Table 16 is processed the pH value result of variations table of soil
| Processing mode | Changes of pH |
| 5 days | 10 days | 20 days | 30 days | |
| CK | 6.78 | 6.89 | 7.06 | 6.91 |
| +6％RM | 8.02 | 8.97 | 8.28 | 8.65 |
| +2％PL | 7.12 | 7.10 | 7.32 | 7.14 |
| +6％PL | 7.24 | 7.03 | 7.29 | 7.37 |
| +10％PL | 7.38 | 7.49 | 7.42 | 7.25 |
As can be seen from Table 16, along with the increase of red mud powder dosage, the pH value of processed soil increases gradually; And along with the prolongation in treatment time, powder alkaline leaching does not delay trend.By contrast, the impact of granular red mud on soil pH is less, and 30 day treatment time, soil pH was basically stable at less than 7.5, and the initial pH difference of soil sample is less.Illustrate that granulating red mud can slow releasing hydroxide ion, reduce red mud and leach the impact of alkalescence on soil, the use of phosphoric acid salt activated material further increases red mud particle and overcomes soil pH in the process of red mud powder rehabilitating soil and raise too fast ability.
Table 17 red mud powder and red mud particle are on the impact of soil acid extractable Pb content
As can be seen from Table 17, the residual form adding the Lead In Soil of red mud powder and red mud particulate material increases, and acid-soluble state reduces.Compare with blank, within 20 days, the acid-soluble state lead of red mud powder reduces 40 ~ 50%, red mud particle makes acid-soluble state lead reduce 50 ~ 70%, and red mud particle can continue after 30 days to reduce acid-soluble state lead, illustrate and add the bioavailability that red mud powder and red mud particle effectively can reduce the lead in soil, red mud particle is more effective than red mud powder.
In sum, after red mud particle disposal, in soil, pH can not raise fast, keeps basicly stable, and in soil, the biological effectiveness of metallic lead ion significantly reduces.Therefore, red mud particle can as restoration of soil polluted by heavy metal material, and they can stable soil pH value, the lead in fixing soil, promote that Lead In Soil is from high transport property form to the conversion of low migration form, reduce the plumbous risk being entered crop and human body by food chain.
Claims (10)
1. a red mud particulate material, it is characterized in that, be with useless red mud powder and waste gypsum for main raw material, adds the gelling ability that gelling material improves red mud, and add phosphoric acid salt as active material, prepare through the mixing that adds water, balling-up, Air drying, a series of process of solidification; Described gelling material is the mixture of silicate cement and flyash.
2. red mud particulate material according to claim 1, is characterized in that, according to accounting for the gross weight of three than meter, the consumption of red mud, gypsum and gelling material is respectively 80 ~ 90%, 3 ~ 8% and 2 ~ 10%; Described phosphatic consumption accounts for 3 ~ 8% of three's gross weight.
3. red mud particulate material according to claim 1, it is characterized in that, the amount ratio of described silicate cement and flyash is 1 ~ 4:1.
4. red mud particulate material according to claim 1, it is characterized in that, the red mud of described red mud for producing in alumina producing Bayer process process, its main component is aluminum oxide, ferric oxide and calcium oxide; Described red mud, gypsum and gelling material are powder, and cross 50 ~ 70 mesh sieves; After the first mix and blend 2 ~ 4h of described red mud, gypsum and gelling material, then add water and phosphoric acid salt mixing.
5. red mud particulate material according to claim 1, it is characterized in that, the amount of described water is: according to mass ratio range, water: compound=0.4 ~ 0.6:1, and described compound is the mixture of red mud, gypsum and gelling material.
6. red mud particulate material according to claim 1, it is characterized in that, the shape of described red mud granular soil renovation agent is the particulate state of particle diameter 1 ~ 5mm.
7. the preparation method of the arbitrary described red mud particulate material of claim 1 ~ 6, is characterized in that, comprise the steps:
S1. batch mixing: red mud, gypsum and gelling material are mixed in proportion, are pulverized, stirs 2 ~ 4h, all powders is mixed; Compound crosses 50 ~ 70 mesh sieves, obtains mixed powder;
S2. granulation: spray into water by the water cement ratio of 0.4 ~ 0.6:1, then added the phosphoric acid salt of 50 ~ 70 mesh sieves in proportion, control granulation rotating speed 20 ~ 40r/min, by mixed powder granulation balling-up;
S3. air-dry: natural air drying 12 ~ 48h;
S4. dry: the green-ball after S3 is air-dry 65 DEG C dries 6 ~ 24h;
S5. naturally cooling, obtains red mud granular soil renovation agent.
8. the application of the arbitrary described red mud particulate material of claim 1 ~ 6 in the improvement reparation of heavy-metal contaminated soil or mud.
9. one kind utilizes the method for red mud particulate material restoration of soil polluted by heavy metal, it is characterized in that, according to the amount ratio of 2 ~ 8%, arbitrary for claim 1 ~ 6 described red mud particulate material is mixed into heavy-metal contaminated soil or mud, stablize 5 ~ 10 days under field conditions (factors), namely complete the stable curing to soil and Heavy Metals in Sludge ion.
10. method according to claim 9, it is characterized in that, described heavy-metal contaminated soil or mud are Pb
2+, Zn
2+and/or Cu
2+contaminated soil or mud.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510796682.6A CN105294023B (en) | 2015-11-17 | 2015-11-17 | A kind of method of utilization red mud granular materials restoration of soil polluted by heavy metal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510796682.6A CN105294023B (en) | 2015-11-17 | 2015-11-17 | A kind of method of utilization red mud granular materials restoration of soil polluted by heavy metal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105294023A true CN105294023A (en) | 2016-02-03 |
| CN105294023B CN105294023B (en) | 2017-08-29 |
Family
ID=55191962
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510796682.6A Expired - Fee Related CN105294023B (en) | 2015-11-17 | 2015-11-17 | A kind of method of utilization red mud granular materials restoration of soil polluted by heavy metal |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105294023B (en) |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106433652A (en) * | 2016-10-17 | 2017-02-22 | 安徽理工大学 | Curing agent for remediation of lead-contaminated soil, preparation method of curing agent and application of curing agent |
| CN106587806A (en) * | 2016-11-28 | 2017-04-26 | 山东省交通科学研究院 | Special curing agent for red-mud-based gold tailing roadbeds as well as preparation method and use method of curing agent |
| CN106734162A (en) * | 2016-12-22 | 2017-05-31 | 胡自田 | A kind of inexpensive soil-repairing agent doped with activated sludge and preparation method thereof |
| CN106734130A (en) * | 2016-12-22 | 2017-05-31 | 胡自田 | A kind of improving salinization soil red mud base modified soil renovation agent and preparation method thereof |
| CN106811206A (en) * | 2016-12-22 | 2017-06-09 | 胡自田 | A kind of red mud base modified particles soil remediation material and preparation method thereof |
| CN106833662A (en) * | 2016-12-22 | 2017-06-13 | 胡自田 | It is a kind of to improve red mud base modified soil renovation agent of soil hardening and preparation method thereof |
| CN106904987A (en) * | 2017-02-13 | 2017-06-30 | 北京工业大学 | A kind of method that red mud collaboration calcium iron white residue and waste gypsum prepare foamed ceramics |
| CN108865157A (en) * | 2018-06-14 | 2018-11-23 | 中国恩菲工程技术有限公司 | The reparation medicament and restorative procedure of heavy-metal contaminated soil |
| CN109111927A (en) * | 2018-08-14 | 2019-01-01 | 东南大学 | A kind of heavy metal pollution sandy soil curing agent and its application method |
| CN111214958A (en) * | 2020-01-17 | 2020-06-02 | 中山大学 | Method for extracting soil rare earth nanoparticles |
| CN111285661A (en) * | 2020-02-21 | 2020-06-16 | 广西锰华新能源科技发展有限公司 | Preparation process of manganese slag and red mud baking-free brick |
| CN111875325A (en) * | 2020-08-12 | 2020-11-03 | 太原理工大学 | Curing agent for kaolin polluted by copper ions and sample preparation method |
| CN112779021A (en) * | 2021-02-03 | 2021-05-11 | 中南大学 | Phosphorus-containing heavy metal contaminated soil remediation material and preparation method and application thereof |
| CN113563893A (en) * | 2021-07-26 | 2021-10-29 | 江苏省环境科学研究院 | Soil remediation agent, preparation method and application in reduction of arsenic pollution |
| CN114644929A (en) * | 2020-12-17 | 2022-06-21 | 湖北工业大学 | Novel composite curing agent for heavy metal Cd-polluted soil and use method thereof |
| CN115634917A (en) * | 2022-09-09 | 2023-01-24 | 江苏省环境科学研究院 | Method for restoring dye-contaminated soil |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101143312A (en) * | 2006-09-12 | 2008-03-19 | 中国科学院生态环境研究中心 | Method for manufacturing and regenerating granular red mud absorber used for water process |
| CN102600791A (en) * | 2012-04-01 | 2012-07-25 | 昆明理工大学 | Granular red mud absorbent and preparation method thereof |
| CN103272836A (en) * | 2013-06-09 | 2013-09-04 | 湖南农业大学 | Red mud composite material and repairing method thereof for soil |
| CN103641286A (en) * | 2013-12-09 | 2014-03-19 | 沈阳铝镁设计研究院有限公司 | Sludge stabilizing method |
-
2015
- 2015-11-17 CN CN201510796682.6A patent/CN105294023B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101143312A (en) * | 2006-09-12 | 2008-03-19 | 中国科学院生态环境研究中心 | Method for manufacturing and regenerating granular red mud absorber used for water process |
| CN102600791A (en) * | 2012-04-01 | 2012-07-25 | 昆明理工大学 | Granular red mud absorbent and preparation method thereof |
| CN103272836A (en) * | 2013-06-09 | 2013-09-04 | 湖南农业大学 | Red mud composite material and repairing method thereof for soil |
| CN103641286A (en) * | 2013-12-09 | 2014-03-19 | 沈阳铝镁设计研究院有限公司 | Sludge stabilizing method |
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106433652A (en) * | 2016-10-17 | 2017-02-22 | 安徽理工大学 | Curing agent for remediation of lead-contaminated soil, preparation method of curing agent and application of curing agent |
| CN106587806B (en) * | 2016-11-28 | 2019-03-26 | 山东省交通科学研究院 | Red mud base gold tailings roadbed special curing agent and its preparation method and application method |
| CN106587806A (en) * | 2016-11-28 | 2017-04-26 | 山东省交通科学研究院 | Special curing agent for red-mud-based gold tailing roadbeds as well as preparation method and use method of curing agent |
| CN106734162A (en) * | 2016-12-22 | 2017-05-31 | 胡自田 | A kind of inexpensive soil-repairing agent doped with activated sludge and preparation method thereof |
| CN106734130A (en) * | 2016-12-22 | 2017-05-31 | 胡自田 | A kind of improving salinization soil red mud base modified soil renovation agent and preparation method thereof |
| CN106811206A (en) * | 2016-12-22 | 2017-06-09 | 胡自田 | A kind of red mud base modified particles soil remediation material and preparation method thereof |
| CN106833662A (en) * | 2016-12-22 | 2017-06-13 | 胡自田 | It is a kind of to improve red mud base modified soil renovation agent of soil hardening and preparation method thereof |
| CN106904987B (en) * | 2017-02-13 | 2020-02-04 | 北京工业大学 | Method for preparing foamed ceramic by red mud, calcium, iron and silicon slag and waste gypsum |
| CN106904987A (en) * | 2017-02-13 | 2017-06-30 | 北京工业大学 | A kind of method that red mud collaboration calcium iron white residue and waste gypsum prepare foamed ceramics |
| CN108865157A (en) * | 2018-06-14 | 2018-11-23 | 中国恩菲工程技术有限公司 | The reparation medicament and restorative procedure of heavy-metal contaminated soil |
| CN109111927B (en) * | 2018-08-14 | 2020-07-31 | 东南大学 | Heavy metal polluted sandy soil curing agent and application method thereof |
| CN109111927A (en) * | 2018-08-14 | 2019-01-01 | 东南大学 | A kind of heavy metal pollution sandy soil curing agent and its application method |
| CN111214958A (en) * | 2020-01-17 | 2020-06-02 | 中山大学 | Method for extracting soil rare earth nanoparticles |
| CN111285661B (en) * | 2020-02-21 | 2021-08-27 | 广西锰华新能源科技发展有限公司 | Preparation process of manganese slag and red mud baking-free brick |
| CN111285661A (en) * | 2020-02-21 | 2020-06-16 | 广西锰华新能源科技发展有限公司 | Preparation process of manganese slag and red mud baking-free brick |
| CN111875325A (en) * | 2020-08-12 | 2020-11-03 | 太原理工大学 | Curing agent for kaolin polluted by copper ions and sample preparation method |
| CN114644929A (en) * | 2020-12-17 | 2022-06-21 | 湖北工业大学 | Novel composite curing agent for heavy metal Cd-polluted soil and use method thereof |
| CN112779021A (en) * | 2021-02-03 | 2021-05-11 | 中南大学 | Phosphorus-containing heavy metal contaminated soil remediation material and preparation method and application thereof |
| CN112779021B (en) * | 2021-02-03 | 2021-10-15 | 中南大学 | Phosphorus-containing heavy metal contaminated soil remediation material and preparation method and application thereof |
| CN113563893A (en) * | 2021-07-26 | 2021-10-29 | 江苏省环境科学研究院 | Soil remediation agent, preparation method and application in reduction of arsenic pollution |
| CN115634917A (en) * | 2022-09-09 | 2023-01-24 | 江苏省环境科学研究院 | Method for restoring dye-contaminated soil |
| CN115634917B (en) * | 2022-09-09 | 2023-11-14 | 江苏省环境科学研究院 | Restoration method for dye-contaminated soil |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105294023B (en) | 2017-08-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105294023A (en) | Method for repairing heavy metal-polluted soil by using red mud granular material | |
| CN105316001A (en) | Red mud particle soil repairing adhesives and preparation method thereof | |
| CN107789787B (en) | Stabilizing agent for repairing arsenic-containing waste residue and using method | |
| Jiang et al. | Solidification/stabilization of soil heavy metals by alkaline industrial wastes: A critical review | |
| CN104560046A (en) | Contaminated soil passivator and preparation method and application thereof | |
| CN104004524A (en) | Environmental-friendly heavy metal stabilizer and application method thereof | |
| CN104418560A (en) | Curing agent for treating heavy metal pollution and heavy metal curing method | |
| CN103740373A (en) | Stabilizing agent for heavy metal contaminated soil and preparation method and application thereof | |
| CN106336869A (en) | Passivating agent used for arsenic polluted soil restoration, arsenic polluted soil restoration method, and application of passivating agent | |
| CN110627391B (en) | High-activity anhydrous phosphogypsum cementing material and preparation method thereof | |
| JP5599061B2 (en) | Neutral solidifying material additive, neutral solidifying material and method for suppressing elution of heavy metals | |
| CN106978184B (en) | Curing agent for composite heavy metal polluted soil and preparation and application methods thereof | |
| CN113337293B (en) | Anti-freezing solidification stabilizing agent for antimony-polluted soil and preparation method and application thereof | |
| CN106467745A (en) | It is suitable for the steel slag and desulfurized gypsum base soil-solidified-agent of As polluted soil | |
| CN104861983A (en) | Farmland soil conditioner and preparation method thereof | |
| CN109796982A (en) | A kind of soil remediation stabilizer and its preparation method and application prepared by high iron tailings | |
| Al-Kindi | Evaluation the solidification/stabilization of heavy metals by Portland cement | |
| CN108774531A (en) | A kind of renovation agent and preparation method thereof for administering alkaline cadmium pollution soil | |
| CN107010911B (en) | Curing agent suitable for strong-acid compound heavy metal polluted soil and preparation and use methods thereof | |
| CN104973843A (en) | Soil remediation chemical and remediation method thereof | |
| CN108611098A (en) | Handle the heavy metal deactivator and preparation method thereof of heavy-metal contaminated soil | |
| CN107021714A (en) | A kind of curing agent and methods for making and using same for heavy metal polluted soil | |
| KR20190048515A (en) | Adsorbent for removal of arsenic containing mine drainage sludge, method for preparing the same, and arsenic removal method using the same | |
| CN107699251A (en) | The fluorite cream base passivator and preparation method of a kind of heavy metal pollution agricultural land soil | |
| CN107398473A (en) | A kind of preparation and application of broad spectrum type heavy-metal contaminated soil stabilization agent |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170829 Termination date: 20181117 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |