CN105294023B - A kind of method of utilization red mud granular materials restoration of soil polluted by heavy metal - Google Patents
A kind of method of utilization red mud granular materials restoration of soil polluted by heavy metal Download PDFInfo
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- CN105294023B CN105294023B CN201510796682.6A CN201510796682A CN105294023B CN 105294023 B CN105294023 B CN 105294023B CN 201510796682 A CN201510796682 A CN 201510796682A CN 105294023 B CN105294023 B CN 105294023B
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Abstract
The invention discloses a kind of red mud granular materials and its application.The red mud granular soil renovation agent is using red mud powder, gypsum, cement, flyash as primary raw material, and phosphate is mixed as activated material, improve the gelling ability of red mud powder and the ability of stable fixed heavy metal ion, by a series of processes of dry solidification under add water mixing, balling-up, normal temperature so that red mud original ore powder pulverulent material composite molding obtains spheric granules soil-repairing agent.The present invention is realized to be prepared under the granulating normal temperature of red mud powder; obtained red mud granular soil renovation agent has certain mechanical strength and good heavy metal stable curing performance; the soil or sludge of heavy metal pollution can effectively be handled; it can slowly discharge OH radical ions simultaneously; less than 7.5 are basically stable at using the pH of soil after the renovation agent reparation; cause soil pH rise too fast during red mud powder rehabilitating soil effectively being overcome; the problem of being unfavorable for plant growth, with higher application value and environmental benefit.
Description
Technical field
The invention belongs to heavy metal pollution of soil Treatment process field.Red mud granular material is utilized more particularly, to one kind
Expect the reparation of the method, particularly lead-contaminated soil of restoration of soil polluted by heavy metal.
Background technology
The soil of China's heavy metal pollution is up to 20,000,000 hm2, the 1/6 of total area under cultivation is accounted for, because of Industrial " three Waste " pollution
Farmland up to 7,000,000 hm2, cause the annual kg of grain drop in production 10,000,000,000.Mining simultaneously, smelting also result in mining area and surrounding area
The serious heavy metal pollution of the supergene environments such as soil.Southwestern China and middle part, particularly Yunnan, Jiangxi, Hunan, Guizhou and
The provinces and regions such as Guangxi, because mining and metal smelt cause the serious heavy metal pollution in mining area and surrounding area soil, cause sheet
Soil is unsuitable for cultivating, and local ecological environment is constituted a serious threat with people's health, agricultural production is hampered.
The recovery technique of heavy-metal contaminated soil is broadly divided into two classes:In-situ immobilization and showering.In-situ immobilization mode
Mainly include physical technique, chemical technology and bioremediation technology；Physical technique includes soil moved in improve the original and method of digging, heat treatment are separated,
Dynamic electricity is repaired and isolation is embedded etc.；Chemical technology includes chemical fixation, chemical leaching and chemical oxidation/reduction etc.；It is biological prosthetic
Technology includes phytoremediation, microorganism remediation and compost etc..Wherein, the tradition of most widely used physical technique is excavated landfill and repaired
Technology, because cost is high and takes up an area big deficiency, limits its extensive use in soil pollution site remediation, gradually by into
This is low, surrounding environment is disturbed under, the high in-situ chemical technique for fixing of social acceptable degree replaced.In-situ chemical, which is fixed, to be referred to
Be that a certain class or a few class chemical addition agents are added into contaminated soil, pass through absorption, precipitation or the machine such as co-precipitation, ion exchange
Manage to change occurrence patterns of the heavy metal in soil, reduce the mobility and biological effectiveness of heavy metal to reduce heavy metal
A kind of recovery technique endangered environment and human body.The key of fixation in situ technology is to close for the characteristic selection of contaminated soil
Suitable curing agent, conventional curing agent is generally the relatively low mineral and industrial by-products of financial cost, such as quick lime, phosphate and
Its mineral, aluminosilicate, iron and manganese oxides, zeolite, sludge, compost etc., research find that these curing agent can effectively fix soil
The heavy metals such as lead, good fortune, copper, zinc, arsenic in earth.
Red mud is the residue produced in aluminum oxide production process, and the oxide containing abundant iron, aluminium and calcium can reduce gold
The solubility and bioavilability of category, continual and steady solidification is played by discharging OH ion pair heavy metal in soil, is promoted dirty
Contaminate heavy metal in soil chemical form conversion, can as heavy-metal contaminated soil stabilizing and curing agent.But, current red mud should
Substantially red mud powder is utilized during for pollution control and restoration of the ecosystem or directly, because its free alkali discharges too fast, causes soil
The pH rates of climb quickly, serious harm are caused to vegetation and edaphon.
Therefore, free alkali rate of release how is reduced, raising speed on soil pH when how to suppress to administer heavy-metal contaminated soil
The problem of spending fast, is that current red mud is applied to urgent problem to be solved in terms of heavy-metal contaminated soil improvement reparation.
The content of the invention
The technical problem to be solved in the present invention is to overcome existing direct utilization red mud powder repairing polluted soil, because it is free
Alkali release is too fast, causes P in soil H to rise quickly, and the problem of being caused harm to vegetation and edaphon uses there is provided one kind
Granulate red mud stable curing heavy metal ion soil remediation method, using gypsum, portland cement, flyash gelling
Red mud granular soil renovation agent is prepared, for stable curing heavy metal ion.The particle renovation agent restorative procedure is with low cost, energy
The problem of effectively solving soil pH rapid increase, realizes the agricultural land soil in-situ immobilization by heavy metal pollution.
It is an object of the invention to provide a kind of red mud granular materials and preparation method thereof.
Another object of the present invention is to provide one kind and utilizes above-mentioned red mud granular materials restoration of soil polluted by heavy metal or sludge
Method.
Above-mentioned purpose of the present invention is achieved through the following technical solutions：
A kind of red mud granular materials, is that, using useless red mud powder and waste gypsum as primary raw material, addition binder materials improves red mud
Gelling ability, and add phosphate as active material, by the mixing that adds water, balling-up, air drying, solidify a series of processes
Prepare；The binder materials is the mixture of portland cement and flyash.The gypsum can be industrial gypsum, also may be used
To be industrial residue waste gypsum.
Wherein it is preferred to, the amount ratio of the portland cement and flyash is 1~4：1.
It is highly preferred that the amount ratio of the portland cement and flyash is 1：1.
Preferably, the red mud is the red mud produced by during alumina producing Bayer process, and its main component is oxidation
Aluminium, iron oxide and calcium oxide.
Preferably, according to accounting for the gross weight of three than counting, the consumption of red mud, gypsum and binder materials is respectively 80~
90%th, 3~8% and 2~10%；The phosphatic consumption accounts for the 3~8% of three's gross weight.Preferably.
It is highly preferred that according to the ratio meter for the gross weight for accounting for three, the consumption of red mud, gypsum and binder materials is respectively
85%th, 5% and 10%, phosphatic consumption is 2~5%, most preferably, and phosphatic consumption is 5%.
Additionally preferably, the consumption of the water is：According to weight ratio meter, water：Compound=0.4~0.6：1, the mixing
Expect for the mixture of red mud, gypsum and binder materials.
It is highly preferred that water：Compound=0.5：1.
Preferably, the red mud, gypsum and binder materials are powder, and 50~70 mesh sieves are first crossed before use.More preferably
Ground, crosses 40~60 mesh sieves.Most preferably, 60 mesh sieves are crossed.
Preferably, the red mud, gypsum and binder materials are first mixed after 2~4h, are added water and phosphate mixing.
Preferably, the preparation of described red mud granular materials uses granulating disc.
It is highly preferred that the use rotating speed of granulating disc is 20~40r/min.
The red mud granular materials of above-mentioned preparation is graininess, it is preferable that it is shaped as the spherical of 1~5mm of particle diameter.More preferably
Ground, is shaped as the spherical of 2~3mm of particle diameter.
Specifically, the preparation method of above-mentioned red mud granular materials comprises the following steps：
S1. batch mixing：Red mud, gypsum and binder materials are mixed in proportion, crushed, 2~4h is stirred, all powders are mixed
Uniformly；Compound crosses 60 mesh sieves, obtains mixed powder；
S2. granulate：Mixed powder is put in granulating disc, control granulation 20~40r/min of rotating speed, by 0.4~0.6：1
The ratio of mud spray into water, then added the phosphate of 50~70 mesh sieves in proportion, mixed powder granulated into balling-up；
S3. air-dry：12~48h of natural air drying；
S4. dry：60~70 DEG C of 2~6h of drying of green-ball after S3 is air-dried；
S5. natural cooling, obtains red mud granular materials.
Wherein it is preferred to, mixing time described in step S1 is 3.5h.
Preferably, the ratio of mud described in step S2 is 0.5.
Preferably, the particle diameter of ball described in step S2 is 2~3mm.
Preferably, phosphate described in step S2 crosses 60 mesh sieves.
Preferably, the time of natural air drying described in step S3 is 36h.
Preferably, the temperature dried described in step S4 is 65 DEG C, and the time of the drying is 4h.
Application of the above-mentioned red mud granular materials in terms of the improvement reparation of heavy-metal contaminated soil or sludge is also in the present invention
Protection domain within.
Preferably, the heavy-metal contaminated soil or sludge are Pb2+、Zn2+And/or Cu2+The soil polluted etc. heavy metal ion
Earth or sludge.
It is highly preferred that applicable heavy-metal contaminated soil or the standard of sludge are：The levels of heavy metal are：Pb2+≤
500mg/L, Zn2+≤ 800mg/L, Cu2+≤650mg/L。
Pb2+≤ 300mg/L, Zn2+≤ 500mg/L, Cu2+≤ 500mg/L as it is a kind of it is preferred can embodiment, specifically
The method of application, a kind of method of utilization red mud granular materials restoration of soil polluted by heavy metal：, will according to 2~8% amount ratio
Above-mentioned red mud granular materials is mixed into heavy-metal contaminated soil or sludge, stablizes under field conditions (factors) 5~10 days, that is, completes to soil
And the stable curing of Heavy Metals in Sludge ion.
Preferably, the amount ratio of red mud granular materials is 6%.
The present invention, because its free alkali discharges too fast, leads to overcome existing direct utilization red mud powder repairing polluted soil
Soil pH is caused to rise quickly, the problem of being caused harm to vegetation and edaphon is prepared by numerous studies and exploration
A kind of red mud material of granulating, specifically using useless red mud powder, waste gypsum as primary raw material, and fills a certain amount of silicate cement
The binder materials such as mud and flyash is as framework material, then adds activated material phosphate, by mixing, balling-up, the nature of adding water
Dry-air blast, a series of process composite moldings of drying are graininess renovation agent.The red mud granular soil renovation agent is by being sustained to a huge sum of money
Category plays continual and steadyization effect, available for heavy metal ion such as lead zinc in the dirty soil of passivation, may advantageously facilitate weight in contaminated soil
The chemical form conversion of metal ion, it is often more important that, the problem of soil pH rises too fast can be effectively solved, is realized by heavy metal
The agricultural land soil in-situ immobilization of pollution.
The invention has the advantages that：
The present invention is capable of the gelling property of the improvement red mud of Synergistic using cement and flyash compounding use, goes forward side by side one
Step combine the phosphatic effect of activated material, realize the granulating of red mud powder under normal temperature, with certain mechanical strength with
Good stable curing heavy metal ion performance, can effectively handle heavy metal, especially lead ion contaminated soil；And utilize
The pH of soil is basically stable at less than 7.5 after the red mud granular materials reparation of the present invention, can effectively overcome powdery red mud material to repair
The problem of earth backing earth has soil pH rapid increase, is unfavorable for plant growth, can realize industrialized continuous operation, be conducive to
Effective stable curing of heavy-metal contaminated soil and Heavy Metals in Sludge ion is realized, in the reality of heavy-metal contaminated soil or sludge
Border processing has higher application value in repairing.
The present invention prepare red mud particle be with useless red mud powder, waste gypsum etc. for raw material, red mud powder, waste gypsum, flyash and
Cement is cheap material, and wide material sources are easy to get, with low cost, and is used as particle renovation agent using Industry Waste red mud powder
Major ingredient, red mud is used to handle heavy-metal contaminated soil and sludge, its own is not only solved and stacks the problem of taking up an area, but also
The problem of solving heavy-metal contaminated soil, reaches the purpose of the treatment of wastes with processes of wastes against one another, with higher application value and environmental benefit.
In addition, the preparation technology of the present invention is simple, cost is low, with very high economic value, suitable for actual industrial production
Popularization and application.
Brief description of the drawings
Fig. 1 is the XRD of red mud.
Fig. 2 is the preparation flow figure of red mud granular soil renovation agent.
Fig. 3 is the renovation technique flow chart of red mud particle restoration of soil polluted by heavy metal.
Embodiment
The present invention is further illustrated below in conjunction with Figure of description and specific embodiment, but embodiment is not to the present invention
Limit in any form.Unless stated otherwise, the reagent of the invention used, method and apparatus routinely try for the art
Agent, method and apparatus.Unless stated otherwise, agents useful for same and material are purchased in market.
Reparation of the red mud dusty material of embodiment 1 to soil
1st, the property analysis of red mud
(1) the image analysis of red mud
Useless red mud produced by electricity throws Shanxi Aluminum Co., Ltd alumina producing Bayer process during the present embodiment is used is carried out
Research, as shown in Figure 1, essential mineral has calcite (CaCO to the XRD of red mud in red mud3), diaspore (AlO (OH)), silicon
Calcium aluminate (CaAl2O2Si8), afwillite (Ca3Si2O7·1.5H2O), smithsonite (Zn4Si2O7·H2O) etc..In these things
Calcite, smithsonite etc. are rhombus crystal face among matter, are main skeletons, can play certain gelatification；And diaspore and
Silico-calcium Barbiturates mainly plays filling effect and gelatification in skeleton.
(2) chemical composition of red mud
The chemical composition of red mud depends on additive in the composition of bauxite, the method and production process that produce aluminum oxide
Material composition, and the newly-generated composition of compound etc..
Sem energy spectrum analysis (SEM-EDS) and chemical analysis, its chemical composition are as shown in table 1.
The chemical analysis and content of the red mud of table 1
It can be seen that from analysis result, red mud has certain gelling property in itself, but weaker, and the presetting period is longer.According to
The gelation mechanism of red mud, its gelling reaction is as follows：
2(3CaOSiO2)+6H2O→3CaO·2SiO2·3H2O (hydrated calcium silicate gel)+3Ca (OH)2
2(CaOSiO2)·4H2O→3CaO·2SiO2·3H2O+Ca(OH)2
3CaO·Al2O3+6H2O→3CaO·Al2O3·6H2O (drated calcium aluminate crystal)
4CaO·Al2O3·Fe2O3+7H2O→3CaOAl2O3·6H2O+CaO·Fe2O3·H2O (hydrated calcium ferrite gel).
2nd, reparation of the red mud dusty material to soil
60 mesh sieves are crossed after red mud is crushed, according to 2%, 4%, 6%, 8%, 10%, 12% dosage to contaminated soil
Middle addition red mud powder, then with the deionized water of gravimetric method addition 30%, stablizes 5 days.Soil sample is gone to clear up measure.
The Pb contents (850mg/kg) of table 2
From table 2 it can be seen that the residual form for adding lead in the soil of red mud powder increases, exchangeable species and sour solvent subtract
It is few.When dosage is 8g/kg, compared with blank, exchangeable species and sour solvent lead reduce 49.63%, and residual form lead is averaged
Increase by 46.66%.Illustrate that red mud can effectively reduce the bioavailability of the lead in soil, mitigate lead and animals and plants are polluted,
Improve soil quality.
In addition, the monitored results to changes of pH are as shown in table 3.
Table 3
As a result show, the soil pH rate of climb quickly, can cause serious harm to vegetation and edaphon.
The red mud of embodiment 2 gelling study on the modification
Present invention selection a variety of goods and materials such as portland cement and gypsum, flyash, to improve the gelling ability of red mud.I
By it is substantial amounts of research screening, final choice gypsum, cement and flyash as be gelled it is additional material modified.
1st, the gelling property of raw material
As described in Example 1, red mud has certain gelling property in itself, but weaker, and the presetting period is longer.It is gelled
Performance is further studied：Red mud crushed 60 mesh sieves through air-drying, and sealing preserve is standby.According to cement-water ratio 1：2.5 determine
PH is 12.36.To determine the gelling of red mud raw material, it is easy to subsequent granulation to test, using the ratio of mud 0.5,0.6, tests each examination
Sample from gelling time.Related data is shown in Table 4.
The gelling property of the red mud raw material of table 4
Red mud contains the material such as more calcium compound and water calcium aluminate in itself, so with certain cement properties, sheet
Body has certain gelling, but gelling is poor.Because red mud has larger retentiveness, up to 700~1000m3/
Kg, accounts for the 79%~93% of gross weight.So, mobility is not showed at the ratio of mud 0.5,0.6.Such as number in table 2
According to the red mud presetting period is all higher than 20 hours, and when the ratio of mud is 0.6, final setting time is more than 84 hours.
In addition, when red mud shakes, the moisture of dry mud absorption can be desorbed outflow from red mud, and this reason is led
Cause red mud gelling bad, and hardness is inadequate after gelling.It is accomplished by adding into red mud in order to improve the gelling property of red mud
Plus certain binder materials.Meanwhile, for as far as possible many utilization waste material red muds, the recycling purpose of red mud is realized, is improving glue
Additive total amount need to reasonably be controlled again while solidifying property.
2nd, to two kinds of binder materials waste gypsums and cement, setting time, knot are determined using ratio of mud condition identical with red mud
Fruit see the table below 5.
The condensation performance of the binder materials of table 5
From table 5, the pre-hardening performance of cement and gypsum material is good, can select as addition binder materials.
3rd, additional waste gypsum, cement material influence on the gelling property of red mud
By adding different amounts of waste gypsum and cement respectively, after being well mixed with red mud powder.In the condition of the ratio of mud 0.5
Under stir, and by vibrations make to treat binder materials surfacing.Its gelling situation is determined every about half an hour.Different ratio
Sample gelling be shown in Table 6 and 7.
Improvement of the waste gypsum of table 6 to red mud gelling property
Table 6 reflects that, with the increase of gypsum dosage, the initial set of material and final setting time are gradually decreased.When gypsum is added
Measure for 25% when, initial set and final set occur within an hour.But found in experimentation, with the increasing of gypsum dosage
Greatly, the mobility of material becomes big.Because under larger gypsum dosage, compound is based on the fast gelation of gypsum, red mud etc.
The hydration process of other materials can be hindered.Gypsum dosage crosses conference and reduces red mud consumption, is not inconsistent with experiment original intention, therefore
The control of gypsum consumption is relatively more reasonable 5~10%.
Improvement of the cement of table 7 to red mud gelling property
Compared by table 6 with table 7 and can be seen that：Cement is when dosage is 5% and 10%, and presetting period and final setting time are equal
Less than the compound that gypsum is filled under identical conditions.This explanation：Under the conditions of small volume, dosage is identical when within 10%
Cement sexually revises bigger than gypsum to raw material gelling under the conditions of addition content.Because the strong retentiveness of red mud, less in addition content
In the case of, most of water is adsorbed by red mud, and the ratio of mud of the cement made further reduces, so, condensed under the conditions of small volume
Faster.
4th, additional fly ash material influences on the gelling property of red mud
After the same method, the influence of its gelling property to red mud is studied by adding different amounts of flyash.No
Sample gelling with proportioning is shown in Table 8.
Improvement of the flyash of table 8 to 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 respectively less than together
Gypsum, the compound of cement are filled under the conditions of one.
In summary, cement, gypsum, flyash have improvement result to red mud gelling property, comparatively flyash
Improvement result is most notable, and cement takes second place.
The binder materials of embodiment 3 compounds the influence to red mud gelling property
1st, cement and flyash compound the influence to red mud gelling property
(1) from upper result of study, cement and flyash are most notable to the improvement result of red mud gelling property, in order to enter
One step inquires into more preferable red mud gelling property improving countermeasure, and the present invention is investigated the compounded combination of cement and flyash to red mud
The influence of gelling property.
(2) after the same method, it is studied to red mud by the cement and flyash for the different ratio for adding 10%
The influence of gelling property.The sample gelling of different ratio is shown in Table 9.
The cement of table 9 and flyash compound the improvement to red mud gelling property
From table 9 and table 3, table 4 contrast as can be seen that cement and flyash compounding use can reach the work of Synergistic
With the gelling property of red mud can be significantly improved, when cement and flyash amount ratio are 1~4：Synergistic is most notable when 1, right
The improvement of red mud gelling property is the most obvious, and optimum compound proportion is 1：1.Therefore, following examples selection cement of the present invention
With flyash according to 1：The scheme of 1 compounding, with reference to the use of waste gypsum, prepares red mud particle renovation agent.
2nd, the influence of gypsum, cement and flyash amount ratio to red mud gelling property
The gelling that the mixing material of different gypsum, cement and flyash amount ratio is determined under the conditions of the ratio of mud 0.5 is shown in
Shown in table 10.
Influence of the mixing match material of table 10 to the gelling property of red mud
As seen from the above table, flyash is not added with, its gelling time is slower, the presetting period improves quickly after addition flyash, but
Increase is not obvious when increasing to 8%, so selected formula 5 is used as granulating formula.Determine that various material usages are：5% cement+
The red mud of+5% flyash of 5% gypsum+85%.
The ratio of mud of embodiment 4 influences on the gelling property of red mud
On the basis of experiment has been completed, the present embodiment uses the binder materials (1 of 5% gypsum+10%：1 cement+fine coal
Ash)+85% red mud proportioning, the research of condensation of materials time is measured according to the different ratio of muds,
It the results are shown in Table 11.
Influence of the ratio of mud of table 11 to red mud compound gelling property
From experimental result, the universal law of binder materials hydration and hardening is deferred in experiment.With the increase of the ratio of mud, glue
It is solidifying to slow down.The increase of the ratio of mud and gelling time are simultaneously disproportionate.When the ratio of mud increases to 0.6 from 0.5, the presetting period by
0.6h extends to 1.85h, and fluidity of slurry change is little.In suitable gelling time, selection uses the less ratio of mud,
Setting time is reduced, granulation is met and requires；Therefore the optimal ratio of mud is chosen to be 0.5.
The selection of the red mud particle activated material of embodiment 5
1st, influence of the activated material to granulation
Selection calcium dihydrogen phosphate, lime, flyash are made activated material and tested：In the powder of+5% gypsum of 5% cement+5%
On the basis of the materials of the red mud of coal ash+85%, the activated material lime of addition said mixture total amount 5%, calcium dihydrogen phosphate or
The performance of flyash, further optimization red mud particle.The ratio of mud 0.5, determines setting time into mould after mixing, the results are shown in Table
Shown in 12.
The influence of the red mud setting time of table 12
From table 12, after lime, flyash or calcium dihydrogen phosphate further activation, pre-hardening performance difference is not
It is very big, but final set performance category addition calcium dihydrogen phosphate is preferably, and heavy metal in soil ion is consolidated in view of phosphate
Determine effect and be better than lime and flyash, it is often more important that, after further being activated using calcium dihydrogen phosphate, particle can be substantially improved
The gelling property of material, so selection calcium dihydrogen phosphate is used as further activated material.
2nd, activated material dosage optimization
According to the activator of selection, on the basis of the materials of the red mud of+5% flyash of+5% gypsum of 5% cement+85%,
The calcium dihydrogen phosphate of said mixture total amount 5% is added, the gelling for determining mixing material in the condition of the ratio of mud 0.5 see the table below
13。
Influence of the mixing match material of table 13 to the gelling property of red mud
The preparation of the red mud granular materials of embodiment 6
1st, preparation method
S1. get the raw materials ready：Red mud powder, gypsum, cement flour, powdered coal ash are ground and 60 mesh sieves are crossed；
S2. batch mixing：By weight：The flyash of+5% gypsum of+5% cement of 85% red mud+5%, mixing stirs 4h, makes institute
There is powder to be well mixed；
S3. granulate：Mixed powder is put in granulating disc, water is sprayed into by the ratio of mud 0.5,60 are crossed by amount ratio addition
The calcium dihydrogen phosphate of mesh sieve, controls 20~40r/min of rotating speed, and particle diameter is made for 2~3mm spherolites；
S4. air-dry：Natural air drying 48h under room temperature condition；
S5. dry：The condition of 65 DEG C of green-ball after S3 is air-dried dries 6h；
S6. natural cooling, obtains red mud granular soil renovation agent.
2nd, by determining, the specific surface area of upper prepared red mud granular soil renovation agent is 22.04m2/ g, pulverization rate is
12.60%.
The simulating pollution soil treatment application of embodiment 7
1st, experiment container is small plastic cup, and per cup, simulation dirt soil 100g (CK), adds red mud powder respectively by design quantity
(RM) and red mud particle (PL) mix, 3 repetitions of Setup Experiments.
2nd, experiment is carried out in 25 DEG C incubated, is every other day kept the skin wet with deionized water to soil, is made soil
Earth water tariff collection water is 50% or so.Regular replenishment moisture content, samples 5, after 10,20,30 days, determines a treatment group soil respectively
The pH value situation of change of earth, the step grading extraction method (BCR of standard three for instructing to formulate is affixed one's name to using former European Economic Community's reference material
Method) addition red mud particle is studied to lead in soil and the fixed effect of zinc.As a result such as table 14 below and table 15.
Table 14 is processed the pH value result of variations of soil
As can be seen from Table 14, with the increase of red mud powder dosage, the pH value of processed soil gradually increases；And with
The extension of processing time, powder alkaline leaching does not delay trend.By contrast, influence of the red mud of granulating to soil pH
Smaller, 6% particle dosage is in processing procedure, and soil pH is basically stable at 7.5 or so.With the initial pH of soil sample difference compared with
It is small.Illustrate that the red mud granulating of the present invention considerably reduces red mud and leaches influence of the alkalescence to soil.
The influence of the red mud powder of table 15 and red mud particle to soil acid extractable Pb contents
As can be seen from Table 15, the exchangeable species and sour solvent of lead in the soil of red mud powder and red mud granular materials are added
All it is reduced, wherein, red mud granular materials group compares with blank, and sour solvent lead averagely reduces more than 50%, illustrates red mud
Grain can effectively reduce the bioavailability of the lead in soil, mitigate lead and animals and plants are polluted, improve soil quality.
The contaminated soil processing application of 8 factories of embodiment
1st, the dirty soil of experiment material is derived from Panyu District of Guangzhou City battery production factory；Experimental method is with example 7.
2nd, result such as table 16 below 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, with the increase of red mud powder dosage, the pH value of processed soil gradually increases；And with
The extension of processing time, powder alkaline leaching does not delay trend.By contrast, influence of the red mud of granulating to soil pH
Smaller, in 30 day processing time, soil pH was basically stable at less than 7.5, and the initial pH of soil sample differs smaller.Illustrate granulating
Red mud can slowly discharge hydroxide ion, reduce red mud and leach influence of the alkalescence to soil, the use of phosphate activated material
Further increase soil pH during red mud particle overcomes red mud powder rehabilitating soil and raise too fast ability.
The influence of the red mud powder of table 17 and red mud particle to soil acid extractable Pb contents
As can be seen from Table 17, the residual form for adding lead in the soil of red mud powder and red mud particulate material increases, sour solvent
Reduce.Compared with blank, 20 days red mud powder sour solvent lead reduces 40~50%, red mud particle make sour solvent lead reduce 50~
70%, and red mud particle can continue reduction sour solvent lead after 30 days, illustrate that adding red mud powder and red mud particle can effectively subtract
The bioavailability of lead in few soil, red mud particle is more more effective than red mud powder.
In summary, after red mud particle disposal, pH will not be raised quickly in soil, keep basicly stable, in soil
The biological effectiveness of metal lead ion is significantly reduced.Therefore, red mud particle can be as restoration of soil polluted by heavy metal material, it
Can be with stable soil pH value, the lead in fixing soil promotes in soil lead from high migration form to low migration form
Conversion, reduction lead enters the risk of crop and human body by food chain.
Claims (7)
1. a kind of red mud granular materials, it is characterised in that be, using useless red mud powder and waste gypsum as primary raw material, to add binder materials
The gelling ability of red mud is improved, and adds phosphate as active material, by the mixing that adds water, balling-up, air drying, solidification one
Serial procedures are prepared；The binder materials is the mixture of portland cement and flyash；Wherein, according to accounting for the total of three
Weight ratio meter, the consumption of red mud, gypsum and binder materials is respectively 80~90%, 3~8% and 2~10%；The phosphatic use
Amount accounts for the 3~8% of three's gross weight；The amount ratio of the portland cement and flyash is 1~4：1；The amount of the water is：Press
According to weight ratio meter, water：Compound=0.4~0.6：1, the compound is the mixture of red mud, gypsum and binder materials.
2. red mud granular materials according to claim 1, it is characterised in that the red mud is alumina producing Bayer process process
In produced by red mud, its main component be aluminum oxide, iron oxide and calcium oxide；The red mud, gypsum and binder materials are
Powder, and cross 50~70 mesh sieves；The red mud, gypsum and binder materials are first mixed after 2~4h, are added water mixed with phosphate
Close.
3. red mud granular materials according to claim 1, it is characterised in that the red mud particle is shaped as 1~5mm of particle diameter
Graininess.
4. the preparation method of any red mud granular materials of claims 1 to 3, it is characterised in that comprise the following steps：
S1. batch mixing：Red mud, gypsum and binder materials are mixed in proportion, crushed, 2~4h is stirred, makes all powder mixing equal
It is even；Compound crosses 50~70 mesh sieves, obtains mixed powder；
S2. granulate：By 0.4~0.6：1 ratio of mud sprays into water, then adds the phosphate of 50~70 mesh sieves in proportion, controls
20~40r/min of rotating speed is granulated, mixed powder is granulated into balling-up；
S3. air-dry：12~48h of natural air drying；
S4. dry：65 DEG C of 6~24h of drying of green-ball after S3 is air-dried；
S5. natural cooling, obtains red mud granular soil renovation agent.
5. any red mud granular materials of claims 1 to 3 is in terms of the improvement reparation of heavy-metal contaminated soil or sludge
Using.
6. a kind of method of utilization red mud granular materials restoration of soil polluted by heavy metal, it is characterised in that according to 2~8% consumption
Than any red mud granular materials of claims 1 to 3 being mixed into heavy-metal contaminated soil or sludge, under field conditions (factors) surely
It is fixed 5~10 days, that is, complete the stable curing to soil and Heavy Metals in Sludge ion.
7. method according to claim 6, it is characterised in that the heavy-metal contaminated soil or sludge are Pb2+、Zn2+And/or
Cu2+Contaminated soil or sludge.
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| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
| CN111214958B (en) * | 2020-01-17 | 2022-07-19 | 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 |
| 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 |
| 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 |
| CN113563893B (en) * | 2021-07-26 | 2022-06-17 | 江苏省环境科学研究院 | Soil remediation agent, preparation method and application in reduction of arsenic pollution |
| CN115634917B (en) * | 2022-09-09 | 2023-11-14 | 江苏省环境科学研究院 | Restoration method for dye-contaminated soil |
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| CN102600791A (en) * | 2012-04-01 | 2012-07-25 | 昆明理工大学 | Granular red mud absorbent and preparation method thereof |
| CN103272836B (en) * | 2013-06-09 | 2015-04-29 | 湖南农业大学 | Red mud composite material and repairing method thereof for soil |
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