CN101200890A - Soil hardening material - Google Patents

Soil hardening material Download PDF

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Publication number
CN101200890A
CN101200890A CNA2006101728685A CN200610172868A CN101200890A CN 101200890 A CN101200890 A CN 101200890A CN A2006101728685 A CNA2006101728685 A CN A2006101728685A CN 200610172868 A CN200610172868 A CN 200610172868A CN 101200890 A CN101200890 A CN 101200890A
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soil
scope
quality
magnesia
curing material
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CN101200890B (en
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新松智
阿野宪一
伊藤博美
福光邦夫
粟田敬二
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Ube Chemical Industries Co Ltd
Ube Material Industries Ltd
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K17/00Soil-conditioning materials or soil-stabilising materials
    • C09K17/02Soil-conditioning materials or soil-stabilising materials containing inorganic compounds only
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01FCOMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F5/00Compounds of magnesium
    • C01F5/02Magnesia
    • C01F5/04Magnesia by oxidation of metallic magnesium
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K17/00Soil-conditioning materials or soil-stabilising materials
    • C09K17/02Soil-conditioning materials or soil-stabilising materials containing inorganic compounds only
    • C09K17/06Calcium compounds, e.g. lime
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K17/00Soil-conditioning materials or soil-stabilising materials
    • C09K17/02Soil-conditioning materials or soil-stabilising materials containing inorganic compounds only
    • C09K17/08Aluminium compounds, e.g. aluminium hydroxide

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Soil Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Geology (AREA)
  • Soil Conditioners And Soil-Stabilizing Materials (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

To provide a magnesium oxide-containing soil solidifier having a high soil solidifying capacity. The soil solidifier comprises 20 to 60 mass% magnesium oxide, 1 to 50 mass% sulfate of magnesium, calcium and/or aluminum, 0.1 to 10 mass% phosphate, and 10 to 60 mass% calcium carbonate.

Description

Soil curing material
Technical field
The present invention relates to soil curing material, relate in particular to soil curing material useful in the curing of weak soil earth.
Background technology
As one of magnesian purposes, be purposes as the curing materials of weak soil earth.Magnesia is compared with same calcium oxide as soil curing material, is weakly alkaline, therefore has few this advantage of load to environment.Yet magnesia exists curing reaction speed slow, and the ability to cure of soil is compared poor slightly such problem with calcium oxide.Therefore, promote material to study in magnesia, adding sulfate etc. as the reaction of soil solidification to improve the soil solidification ability.
In patent documentation 1, disclose the magnesian soil curing material that contains of sulfate as reaction promoter.In this patent documentation,, calcium sulfate, magnesium sulfate have been enumerated as the example of sulfate.
In patent documentation 2, disclose and used phosphate, sulfate, carbonate, organic acid any is above as containing of reaction promoter of magnesian soil curing material.In this patent documentation, as phosphatic ion, can enumerate calcium superphosphate, double superhosphate, fused phosphate, sintering phosphate fertilizer, example as sulfate, hard burnt plaster, dihydrate gypsum, potassium sulfate, aluminum sulfate, ammonium sulfate, potassium alum, soda alum can be enumerated,, sodium carbonate, sodium acid carbonate can be enumerated as the example of carbonate, as the organic acid example, can enumerate citric acid, tartaric acid, lactic acid, oxalic acid.
Patent documentation 1: the spy opens the 2003-193050 communique
Patent documentation 2: the spy opens the 2003-193462 communique
Summary of the invention
It is weakly alkaline that magnesia is compared with calcium oxide, and the magnesian amount of adding if consideration curing processing back to the load of environment, then preferably is used for soil solidification is less.
Therefore, the objective of the invention is to develop and a kind ofly compare with containing magnesian soil curing material at present, the soil curing material that the ability to cure of soil is high by adding a small amount of as far as possible magnesia, just can obtain high soil solidification effect.
The inventor studies comprising containing of magnesia and sulfate magnesian soil curing material, found that phosphate and calcium carbonate by adding ormal weight again, can further improve the ability to cure of soil.
The present invention is a kind of soil curing material that contains sulfate, 0.1~10 quality % phosphate and 10~60 quality % calcium carbonate of 20~60 quality % magnesia, 1~50 quality % magnesium, calcium and/or aluminium.
Optimal way of the present invention is as described below.
(1) in the scope that with respect to 100 mass parts magnesia is 1~90 mass parts, further contains calcium oxide and/or light dolomite (De ロ イ マ イ ト).
(2) contain the sulfate of magnesium, calcium and/or aluminium in magnesia 1/50~1 quality scope doubly.
(3) contain phosphate in magnesia 1/100~1/10 quality scope doubly.
(4) contain calcium carbonate in magnesia 1/3~3 quality scope doubly.
(5) magnesian mean square magnesite crystallite particle diameter is in the scope of 10~50nm, and the BET specific area is at 5~20m 2In the scope of/g, average grain diameter is in the scope of 1~5 μ m, and the proportion of particles that particle diameter surpasses 10 μ m is no more than 10 volume %, and apparent density is at 0.3~0.8g/cm in addition 3Scope in.
Soil curing material of the present invention is compared with containing magnesian soil curing material at present, and the ability to cure of soil also is improved.Therefore, the soil curing material of the application of the invention can reduce the magnesian amount of adding in weak soil earth, therefore can reduce the load to environment.
Description of drawings
[Fig. 1] in embodiment 1 handled with the soil solidification of comparative example 1, the relation of the cone index of soil was handled in the amount of the basic matterial that adds in soil and curing.
[Fig. 2] in embodiment 2 handled with the soil solidification of comparative example 2, the relation of the cone index of soil was handled in the amount of the basic matterial that adds in soil and curing.
[Fig. 3] in embodiment 3 handled with the soil solidification of comparative example 3, the relation of the cone index of soil was handled in the amount of the basic matterial that adds in soil and curing.
[Fig. 4] in embodiment 4 handled with the soil solidification of comparative example 4, the relation of the cone index of soil was handled in the amount of the basic matterial that adds in soil and curing.
The specific embodiment
Soil curing material of the present invention is must composition for four kinds with sulfate, phosphate and the calcium carbonate that is selected from one or two or more kinds metal in magnesia, magnesium, calcium and the aluminium.
Magnesian content must composition with respect to all amount, in the scope of 20~60 quality %, preferably in the scope of 25~60 quality %.If magnesian content lacks than above-mentioned scope, then the ability to cure of soil reduces.
The sulfate of magnesium, calcium and aluminium, phosphate and calcium carbonate play the effect as magnesian reaction promoter.In addition, the sulfate of magnesium, calcium and aluminium is faintly acid, therefore also has to suppress to solidify the effect that processing back soil pH rises.Because it is calcium carbonate is compared with magnesia and had alkalescent, therefore few to the load that solidifies the soil after handling.
The content of sulfate must composition with respect to all amount, in the scope of 1~50 quality %, preferably in the scope of 10~30 quality %.In addition, the content of sulfate is preferably in magnesian 1/50~1 quality scope doubly, more preferably in 1/10~3/4 quality scope doubly.
Phosphatic content must composition with respect to all amount, in the scope of 0.1~10 quality %, preferably in the scope of 0.5~5 quality %.In addition, phosphatic content is preferably in magnesian 1/100~1/10 quality scope doubly, more preferably in 1/50~1/20 quality scope doubly.
The content of calcium carbonate must composition with respect to all amount, in the scope of 10~60 quality %, preferably in the scope of 20~60 quality %.In addition, the content of calcium carbonate is preferably in magnesian 1/3~3 quality scope doubly, more preferably in 1/3~2 quality scope doubly.
If it is the content of sulfate, phosphate and calcium carbonate is less than above-mentioned scope, then insufficient as the effect of reaction promoter.
The magnesia that uses in the soil curing material of the present invention is light calcined magnesia preferably.Particularly preferred magnesian mean square magnesite crystallite particle diameter is in the scope of 10~50nm, and the BET specific area is at 5~20m 2In the scope of/g, average grain diameter is in the scope of 1~5 μ m, and the proportion of particles that particle diameter surpasses 10 μ m is no more than 10 volume %, and apparent density is at 0.3~0.8g/cm in addition 3Scope in.
Magnesian mean square magnesite crystallite particle diameter is in the scope of 10~50nm, preferably in the scope of 20~40nm.Mean square magnesite crystallite particle diameter is the average grain diameter that forms the crystallite of magnesium oxide particle.Mean square magnesite crystallite particle diameter is one of reactive index of expression magnesia.If mean square magnesite crystallite particle diameter is in above-mentioned scope, then magnesian reactivity improves, and the expression of soil solidification is accelerated.
Magnesian BET specific area is at 5~20m 2In the scope of/g, preferably at 10~20m 2In the scope of/g.The BET specific area is one of reactive index of expression magnesia.If the BET specific area is in above-mentioned scope, then magnesian reactivity improves, and the expression of soil solidification is accelerated.
Magnesian average grain diameter is in the scope of 1~5 μ m.Average grain diameter is one of index of expression magnesia dispersiveness and operability.If average grain diameter is in above-mentioned scope, then magnesia disperses in solidifying object soil easily, and operability is improved in addition.
The proportion of particles that magnesian particle diameter surpasses 10 μ m is no more than 10 volume %.Magnesian size distribution is one of dispersed index of expression.If particle diameter surpasses the proportion of particles of 10 μ m in above-mentioned scope, then magnesia disperses in solidifying object soil easily, and operability is improved in addition.
Magnesian apparent density is at 0.3~0.8g/cm 3Scope in, preferably at 0.5~0.8g/cm 3Scope in.Apparent density is one of index of expression magnesia dispersiveness and operability.If apparent density is in above-mentioned scope, then magnesia disperses in solidifying object soil easily, and operability is improved in addition.
Above-mentioned magnesia can by will alkali such as calcium hydroxide add the magnesium hydroxide particle that generates in the seawater under 650~900 ℃ the temperature, preferably under 680~900 ℃ temperature, carry out sintering and prepare.In the magnesium hydroxide particle that is obtained by seawater, owing to sneaked into the sulfate radical in the seawater, therefore in this magnesium hydroxide particle magnesia that sintering obtains in the said temperature scope, the amount in the scope of 0.5~2.5 quality % contains sulfate radical usually.Sintering time is different according to essential factors such as sintering temperature and magnesium hydroxide particle sizes, normally 10~120 minutes.
The sulfate of the magnesium that uses in the soil curing material of the present invention, calcium and aluminium can be anhydrous salt, also can be moisture salt.Sulfate preferably contains the above sulfuric acid composition (SO of 35 quality % 4 2-).As the example of sulfate, can enumerate the known sulfate as soil curing material such as anhydrous magnesium sulfate, magnesium sulfate 7 water salt, dead plaster (hard burnt plaster), calcium sulfate 0.5 water salt (semi-hydrated gypsum), calcium sulfate 2 water salt, anhydrous slufuric acid aluminium, aluminum sulfate 18 water salt.Sulfate can a kind uses separately, also can be with coupling more than 2 kinds.As sulfate, preferably use the sulfate of magnesium and calcium.
In the phosphate that in soil curing material of the present invention, uses, contain orthophosphates, condensed phosphate and composition thereof.As phosphatic example, can enumerate sodium phosphate, sodium pyrophosphate, sodium phosphate trimer, calgon, calcium superphosphate, double superhosphate, fusing phosphate fertilizer, sintering phosphate fertilizer.Phosphate can a kind uses separately, also can be with coupling more than 2 kinds.As phosphate, preferably use calgon.
In soil curing material of the present invention, calcium carbonate can use common Powdered or granular calcium carbonate.The granularity of calcium carbonate is being preferably under 100 mesh sieves more than the 50 quality %, more preferably more than the 80 quality %.
In soil curing material of the present invention,, can also add calcium oxide and/or light dolomite [burnt dolomite (compound carbonate of magnesium and the calcium) magnesia that obtains and the compound of calcium oxide] in order to quicken the soil solidification effect and to express soil solidification.It is alkaline that calcium oxide is compared with magnesia with light dolomite, handles the load of back to environment if therefore consider to solidify, and the addition of calcium oxide and/or light dolomite is with respect to 100 mass parts magnesia, preferably in the scope of 1~90 mass parts.Especially add in soil curing material under the situation of calcium oxide and/or light dolomite, the total content of the basic matterial in the soil curing material (magnesia, calcium oxide and light dolomite) is preferably in the scope of 25~80 quality %.
Soil curing material of the present invention can prepare by for example above-mentioned each composition being used known mixing arrangements such as mixer to mix.
Soil curing material of the present invention can also add in the weak soil earth that solidifies object with the state of powder, also can add under the state with the suspension that disperses in water.The addition of the relative weak soil earth of soil curing material changes to some extent according to the softness and the moisture content of soil, therefore can not decide without exception, usually, with respect to 1m 3Soil is in the scope of 20~150kg.
Embodiment
Use following material preparation soil curing material.
(1) magnesia A
In seawater, add the calcium hydroxide suspension of 15 quality % concentration, make that the calcium amount is 0.9 with respect to magnesium amount in the seawater with molar ratio computing, thereby generate magnesium hydroxide particle, obtain magnesium magma.Concentrate the magnesium magma that obtains, make that solid component concentration is 35 quality %.After washing concentrated magnesia magma with industry, filter, drying, thus obtain magnesium hydroxide.The average grain diameter of the magnesium hydroxide that obtains is 3.3 μ m.This magnesium hydroxide in rotary-type klining freezing of a furnace, 700 ℃ sintering temperatures 30 minutes, is obtained magnesia.
The magnesian periclase crystallite particle diameter that obtains is 31nm, and the BET specific area is 15.8m 2/ g, average grain diameter 3.3 μ m, the proportion of particles that particle diameter surpasses 10 μ m is 7 volume %, apparent density is 0.66g/cm 3, purity is 95.88 quality %, the content of sulfate radical is 1.82 quality %.In addition, magnesian mean square magnesite crystallite particle diameter, average grain diameter, particle diameter are measured by the following method above proportion of particles and the apparent density of 10 μ m.
[mean square magnesite crystallite particle diameter]
Using the X-ray diffraction device, is that 40kV, tube current are the X-ray diffraction pattern of measuring magnesian periclase crystallite (200) face under the condition of 20mA at tube voltage, tries to achieve mean square magnesite crystallite particle diameter.For standard specimen, use silicon.
[average grain diameter, particle diameter surpass the proportion of particles of 10 μ m]
Magnesia is dropped in the ion exchange water, after carrying out 30 seconds ultrasonic wave dispersion treatment, use laser diffraction formula particle size distribution device (SK レ-ザ-LMS-30, (strain) セ イ シ Application enterprise system) to measure size distribution, try to achieve the proportion of particles that average grain diameter and particle diameter surpass 10 μ m.
[apparent density]
At capacity is 50cm 3Graduated cylinder in, slowly add magnesia on a small quantity until reaching graduated cylinder 50cm repeatedly 3Graticule after, magnesian quality in the weighing graduated cylinder calculates apparent density by following formula.
Apparent density (g/cm 3)=magnesian quality (g)/50 (cm 3)
(2) magnesia B
Periclase crystallite particle diameter is 58nm, and the BET specific area is 12.9m 2/ g, average grain diameter 15.8 μ m, the proportion of particles that particle diameter surpasses 10 μ m is 67 volume %, apparent density is 0.68g/cm 3, purity is 96.94 quality %, the content of sulfate radical be 0.03 quality % in homemade light calcined magnesia
(3) magnesium sulfate 7 water salt
(4) calcium sulfate (hard burnt plaster)
(5) calgon
(6) calcium carbonate (the マ テ リ ア of space portion Le ズ Co., Ltd. system)
Particle diameter: 90 quality % are by 100 mesh sieves
(7) calcium oxide
(the マ テ リ ア of space portion Le ズ Co., Ltd. system)
Particle diameter: 95 quality % are by 200 mesh sieves
[embodiment 1~4, comparative example 1~4]
Mass ratio shown in above-mentioned raw materials according to the form below 1 and the table 2 is mixed the preparation soil curing material.In table 1 and table 2, alkali component content (quality %) is the weight percent of basic matterial (magnesia, calcium oxide) contained in the soil curing material.
Table 1
Figure A20061017286800081
Table 2
Figure A20061017286800091
[curing of soil is handled]
At 1m 3Weak soil earth (Northeast ロ-system, moisture content: 133 quality %, moistening density: 1.331g/cm 3, dry density: 0.797g/cm 3, pH:6.5) in, respectively with the 30kg/cm shown in following table 3 and the table 4 3, 70kg/cm 3, 100kg/cm 3Ratio add the above-mentioned soil curing material that obtains and mix and preparation is solidified and handled soil.In table 3 and table 4, the amount (kg/cm of the basic matterial that in soil, adds 3) be the amount of contained basic matterial in the soil curing material that in soil, adds (magnesia and calcium oxide).The intensity of this curing processing soil and the evaluation result of pH are shown in table 3 and the table 4.The intensity of soil is estimated according to circular cone (cone) index.Cone index and pH measure according to following method.
[assay method of cone index]
, place it in the closed container for the examination body according to JGS-0716 (the cone index test method of compacted soil) preparation, (20 ℃, 80%RH) preservation was down measured cone index (kN/m after aging 14 days in thermostatic constant wet chamber 2).Cone index is high more, and the intensity of expression soil is high more.
[assay method of pH]
To solidify processing soil is placed in the closed container, (20 ℃ of thermostatic constant wet chamber, 80%RH) preserve down, after aging 14 days, by method according to JGS-0211 " the pH test method of native suspension ", 10g is added in the 50g pure water by the sample that non-seasoning obtains, stir after 1 hour, left standstill 1 hour, and measured the pH of this water.
Table 3
Figure A20061017286800101
Table 4
Figure A20061017286800111
In Fig. 1, be illustrated in the soil solidification processing of embodiment 1 and comparative example 1 amount of the basic matterial that in soil, adds and the relation of solidifying the cone index of handling soil.In Fig. 2, be illustrated in the soil solidification processing of embodiment 2 and comparative example 2 amount of the basic matterial that in soil, adds and the relation of solidifying the cone index of handling soil.In Fig. 3, be illustrated in the soil solidification processing of embodiment 3 and comparative example 3 amount of the basic matterial that in soil, adds and the relation of solidifying the cone index of handling soil.In Fig. 4, be illustrated in the soil solidification processing of embodiment 4 and comparative example 4 amount of the basic matterial that in soil, adds and the relation of solidifying the cone index of handling soil.
Shown in the chart of Fig. 1~Fig. 4, the discovery interpolation contains phosphate to be compared with the curing processing soil of the soil curing material (comparative example 1~4) of calcium carbonate with adding not phosphorous hydrochlorate with the curing processing soil of the soil curing material (embodiment 1~4) of calcium carbonate, and existence demonstrates the tendency of high value with respect to the cone index of the amount of the basic matterial that adds in soil.

Claims (6)

1. soil curing material, it contains sulfate, 0.1~10 quality % phosphate and 10~60 quality % calcium carbonate of 20~60 quality % magnesia, 1~50 quality % magnesium, calcium and/or aluminium.
2. soil curing material as claimed in claim 1 wherein, further contains calcium oxide and/or light dolomite in the scope that with respect to 100 mass parts magnesia is 1~90 mass parts.
3. soil curing material as claimed in claim 1 wherein contains the sulfate of magnesium, calcium and/or aluminium in magnesia 1/50~1 quality scope doubly.
4. soil curing material as claimed in claim 1 wherein contains phosphate in magnesia 1/100~1/10 quality scope doubly.
5. soil curing material as claimed in claim 1 wherein contains calcium carbonate in magnesia 1/3~3 quality scope doubly.
6. soil curing material as claimed in claim 1, wherein magnesian mean square magnesite crystallite particle diameter is in the scope of 10~50nm, and the BET specific area is at 5~20m 2In the scope of/g, average grain diameter is in the scope of 1~5 μ m, and the proportion of particles that particle diameter surpasses 10 μ m is no more than 10 volume %, and apparent density is at 0.3~0.8g/cm in addition 3Scope in.
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