CN112934907B - Method for efficiently removing iron from shield mud - Google Patents
Method for efficiently removing iron from shield mud Download PDFInfo
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- CN112934907B CN112934907B CN202110051219.4A CN202110051219A CN112934907B CN 112934907 B CN112934907 B CN 112934907B CN 202110051219 A CN202110051219 A CN 202110051219A CN 112934907 B CN112934907 B CN 112934907B
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 191
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 88
- 238000000034 method Methods 0.000 title claims abstract description 61
- 238000001035 drying Methods 0.000 claims abstract description 37
- 238000002156 mixing Methods 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 10
- 230000002378 acidificating effect Effects 0.000 claims abstract description 9
- 238000001354 calcination Methods 0.000 claims abstract description 9
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 239000003245 coal Substances 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 239000000843 powder Substances 0.000 claims abstract description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 7
- 238000000227 grinding Methods 0.000 claims abstract description 7
- 238000007873 sieving Methods 0.000 claims abstract description 7
- 238000001179 sorption measurement Methods 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 68
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 30
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 235000006408 oxalic acid Nutrition 0.000 claims description 10
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- UMGDCJDMYOKAJW-UHFFFAOYSA-N aminothiocarboxamide Natural products NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- -1 thiourea peroxide Chemical class 0.000 claims description 3
- 238000000643 oven drying Methods 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 239000002918 waste heat Substances 0.000 claims description 2
- 239000010802 sludge Substances 0.000 claims 1
- 238000009412 basement excavation Methods 0.000 abstract description 40
- 239000007787 solid Substances 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 235000013980 iron oxide Nutrition 0.000 abstract 2
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 abstract 1
- 239000002689 soil Substances 0.000 description 18
- 239000002994 raw material Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 239000005995 Aluminium silicate Substances 0.000 description 8
- 235000012211 aluminium silicate Nutrition 0.000 description 8
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 8
- 239000002893 slag Substances 0.000 description 8
- 239000000919 ceramic Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000003760 magnetic stirring Methods 0.000 description 5
- 239000002734 clay mineral Substances 0.000 description 4
- 238000010276 construction Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 229910001172 neodymium magnet Inorganic materials 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 238000003892 spreading Methods 0.000 description 4
- 230000007480 spreading Effects 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- RYYXDZDBXNUPOG-UHFFFAOYSA-N 4,5,6,7-tetrahydro-1,3-benzothiazole-2,6-diamine;dihydrochloride Chemical compound Cl.Cl.C1C(N)CCC2=C1SC(N)=N2 RYYXDZDBXNUPOG-UHFFFAOYSA-N 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- GRWZHXKQBITJKP-UHFFFAOYSA-L dithionite(2-) Chemical compound [O-]S(=O)S([O-])=O GRWZHXKQBITJKP-UHFFFAOYSA-L 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000003746 solid phase reaction Methods 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- LKZCRGABYQYUFX-UHFFFAOYSA-L barium(2+);dithiocyanate Chemical compound [Ba+2].[S-]C#N.[S-]C#N LKZCRGABYQYUFX-UHFFFAOYSA-L 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 229910052598 goethite Inorganic materials 0.000 description 2
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 230000005641 tunneling Effects 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- QJVKUMXDEUEQLH-UHFFFAOYSA-N [B].[Fe].[Nd] Chemical compound [B].[Fe].[Nd] QJVKUMXDEUEQLH-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000009856 non-ferrous metallurgy Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03C—MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03C1/00—Magnetic separation
- B03C1/02—Magnetic separation acting directly on the substance being separated
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B5/00—Operations not covered by a single other subclass or by a single other group in this subclass
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- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a method for efficiently removing iron from shield mud. The method is a method for reducing iron oxides in shield excavation muck (shield muck or shield mud). The method comprises the following steps: drying, grinding and sieving the shield muck or shield mud, uniformly mixing the dry shield muck or shield mud with water, adding an acidic substance, adding a magnet under a stirring state, carrying out adsorption iron removal treatment, taking out the magnet, filtering and separating water, and drying to obtain a solid substance; mixing the solid, the coal powder and the carbonate, heating and calcining to obtain the shield mud after iron removal. The method for removing the iron can reduce the content of the iron oxide in the shield muck to below 1wt%, is a high-efficiency method for removing the iron from the shield mud, is simple to operate, short in treatment time, high in efficiency and low in production cost, and is beneficial to high-quality resource utilization of the shield muck (shield mud).
Description
Technical Field
The invention relates to the field of industrial solid waste resource utilization, in particular to a method for efficiently removing iron from shield mud.
Background
With the rapid development of economy in China, in order to meet the demand of large-capacity rapid traffic for increasing day by day in areas with large population density, underground space is being developed and utilized at an accelerated speed in large domestic cities. The shield method has been widely used in the development of tunnels and underground spaces at home and abroad as a safe and efficient tunnel construction method after more than 200 years of development and technical innovation. By 3 months in 2019, 32 cities are built in China for urban subway rail transit, and the total operation mileage reaches 5151.1km.
The shield muck is slag mud dug out in the tunneling process of the shield tunneling machine. Shield slag rocks and muck exist in large quantities in the construction of subway projects in various cities throughout the country. At present, a small amount of shield muck is spontaneously backfilled and utilized in construction engineering, and most of the rest of the shield muck is not processed and is transported to a muck piling yard for piling. The piling of the shield mud needs a large amount of fields, and the transportation of the muck also needs a large amount of supporting facilities, which brings adverse effects to the society, resources and environment. Research shows that the main component of the shield muck excavated in shield construction is Al 2 O 3 And SiO 2 Containing a small amount of Fe 2 O 3 The results of the phase analysis are shown in FIG. 3. The ceramic is mainly composed of Al 2 O 3 And SiO 2 The main components of the shield mud (shield muck) are similar to those of the ceramic. The shield mud is used for preparing the ceramic instead of the traditional ceramic raw material, so that the problem of treatment difficulty of shield muck and the problem of shortage of the ceramic raw material can be solved. However, the iron content of the shield muck is too high, which affects the whiteness of the ceramic on one hand and the firing and performance of the ceramic on the other hand, so that the high-efficiency iron removal of the shield muck has important social and economic significance.
At present, the iron removal of low-grade raw materials with higher iron content mainly comprises the following aspects: screening out iron in the low-grade raw material by adopting special equipment; oxidizing or reducing iron with an oxidizing agent or a reducing agent, and then removing iron from the raw material. For example, a patent "a gas mixer for a goethite reduction and iron removal process" (CN 209917644U) discloses a gas mixing device for a goethite reduction and iron removal process, which belongs to the field of nonferrous metallurgy equipment. Comprises a main air inlet pipe and a mixed air inlet pipe; the main air inlet pipe and the mixed gas inlet pipe are respectively connected with an inlet of a pipeline mixer, an outlet of the pipeline mixer is communicated with an inlet of a cyclone, and an exhaust pipe is arranged at the top of the cyclone. The mixing uniformity of the gas mixing device can reach more than 99 percent, the main gas and the mixed gas in the bubbles with the diameter less than 1mm can be uniformly distributed, the micro mixing is realized, the contact area of the reaction of the mixed gas and the solution is enlarged, the iron removing device is used for removing iron from low-grade raw materials, the investment is large, the equipment maintenance is difficult, and the occupied area is large; for example, the patent "method for removing iron to white variegated clay mineral by solid phase reaction" (CN 110371994A), discloses a method for removing iron to white variegated clay mineral by solid phase reaction, the method for removing iron to white variegated clay mineral by solid phase reaction is that the naturally produced iron-rich clay mineral powder is mixed with acid, reducing agent and complexing agent, then ball-milled for 1-6 h, then pressed into a sheet with the thickness of 1-3mm by a pair roller treatment, then reacted for 4-12 h under the condition of 80-160 ℃, and then fully washed, separated, dried and crushed to obtain a white nano silicate product, the method uses special equipment to press the raw material into a sheet with the thickness of 1-3mm, the operation is complex, and a large amount of waste water is generated by washing in the operation process; for example, a patent of 'a kaolin iron removal process' (CN 110862093A), discloses a kaolin iron removal process, relating to the field of kaolin production, the method comprises the steps of putting a kaolin filter cake into a sulfuric acid tank, uniformly dispersing, introducing hydrogen peroxide, stirring for 5-10 min, keeping the pH = 1-2 of a solution in the sulfuric acid tank, and then adding barium thiocyanate, wherein the ratio of the barium thiocyanate to the kaolin filter cake is 1: (100-150) standing for 5-10 min to obtain iron-removed ore pulp, filtering to obtain solution without kaolin, and generating more toxic sewage in the treatment process to cause secondary pollution. The document (Yuan Yanying, several iron removal methods for kaolin, and foreign metal ore dressing [ J ]2000,9,19-23) reports that solid dithionite is adopted for iron removal, the obtained kaolin by the method has stable whiteness and reliable quality, a bleaching product is not required to be washed, but the solid dithionite iron removal is expensive and is easy to decompose and oxidize in the presence of oxygen in the presence of moisture, so that the activity of the solid dithionite iron removal is reduced, and a large amount of resources are required to be input in the links of transportation and storage. For the technical method for removing iron from the low-grade raw materials and the equipment thereof reported above, the content of iron oxide in the slag soil can be reduced to below 1wt% after the iron is removed from the slag soil, and the method for processing the low-grade slag soil into the high-grade slag soil raw material has not been reported in documents.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a method for efficiently removing iron from shield mud. In the invention, the shield mud is shield excavation muck or shield excavation mud.
The invention provides a method for reducing the iron content of shield excavation muck, which aims to realize the low-cost and high-efficiency reduction of the iron content of the muck excavated by a shield. According to the method, two or more than two additives of oxalic acid, hydrochloric acid, thiourea peroxide, sulfuric acid, citric acid, coal powder, calcium carbonate and sodium carbonate are introduced, and the iron content in the slag soil of shield excavation is effectively reduced through a series of processes. The method has the advantages of low energy consumption, simple operation, short treatment time, low production cost, good iron and impurity removal effects and contribution to resource utilization of the shield muck.
The purpose of the invention is realized by at least one of the following technical solutions.
The invention aims to provide a method for effectively reducing the iron content in a grade raw material, and the method is used for recycling the shield muck after iron removal.
The invention provides a method for efficiently removing iron from shield mud, which comprises the following steps:
(1) Drying, grinding and sieving shield residual soil or shield mud to obtain shield excavation residual soil A (which can be hermetically stored in a drying chamber for later use); uniformly mixing the shield excavation muck A with water to obtain a mixture B, and then adding an acidic substance to uniformly mix to obtain a mixture C;
(2) Adding a magnet into the mixture C obtained in the step (1) under a stirring state, carrying out adsorption iron removal treatment, taking out the magnet, filtering to obtain a precipitate, and drying to obtain a mixture D; uniformly mixing the mixture D, the coal powder and the carbonate to obtain a mixture E;
(3) And (3) heating the mixture E obtained in the step (2) in an electric furnace to carry out calcination treatment, so as to obtain the shield mud (shield muck with low iron content) after iron removal, wherein the iron oxide content in the shield mud after iron removal is less than 1 wt%.
Further, the drying mode in the step (1) is more than one of drying in the sun, drying by using the waste heat of a factory, microwave drying and oven drying.
Preferably, the drying mode in the step (1) is drying in the sun and drying in an oven.
Further preferably, the drying time in the sun is 0-24h, the drying temperature in an oven is 25-100 ℃, and the drying time in the oven is 0-24h.
Further, the moisture content of the shield excavation muck A in the step (1) is 1-35%.
Further, the size of the sieve holes of the sieve in the step (1) is 120 meshes.
Further, the acidic substance in the step (1) is more than two of oxalic acid solution, hydrochloric acid solution, thiourea peroxide, sulfuric acid solution and citric acid solution; the concentrations of the oxalic acid solution, the hydrochloric acid solution, the sulfuric acid solution and the citric acid solution are all 0.1-1mol/L; the mass of the acidic substance is 0.01-15% of the mass of the mixture B. In the step (1), the valence state of the iron compound in the shield muck is changed by adding an acidic substance.
Preferably, the acidic substances in the step (1) are oxalic acid solution, hydrochloric acid solution and thiourea dioxide.
Further, the solid-liquid ratio of the shield excavation muck A to water in the step (1) is 0.8: 5g/mL.
Preferably, the solid-to-liquid ratio of the shield excavation residue soil A to water in the step (1) is 1g:2mL.
Further, the mass ratio of the magnet in the step (2) to the mixture C is 1-1:1; the magnetic force of the magnet is 1-200MT.
Preferably, the magnet in step (2) is more than one of neodymium iron boron magnets.
Preferably, the stirring state of step (2) is a magnetic stirring state.
Further, the time for the adsorption iron removal treatment in the step (2) is 1min-10h.
Further, the mass of the coal powder in the step (2) is 1-40% of that of the mixture D; the carbonate is more than one of sodium carbonate and calcium carbonate; the mass of the carbonate is 1-40% of that of the mixture D.
Further, the calcining treatment temperature in the step (3) is 150-850 ℃, and the calcining treatment time is 30min-10h.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) The method for efficiently removing the iron from the shield mud provided by the invention does not need large-scale special mechanical equipment, has low cost, ensures the removal of multivalent iron in the shield muck by adopting a two-step iron removal method, has high iron removal efficiency, can effectively reduce the content of the iron in the shield muck, can reduce the content of the oxide of the iron in the shield muck to below 1wt%, and is an efficient iron removal method.
(2) The method for efficiently removing the iron from the shield mud, provided by the invention, is flexible to operate, can reduce the treatment time and treatment steps according to the actual condition, and can increase or decrease the addition of the additive according to the actual condition of the muck so as to ensure the iron removal effect.
(3) The method for efficiently removing the iron from the shield mud has broad-spectrum practicability and can be used for iron removal procedures of other low-grade mineral raw materials with higher iron content.
Drawings
Fig. 1 is a flowchart of a method for efficiently removing iron from shield mud according to an embodiment of the present invention.
FIG. 2 is a flow chart of a method for reducing the iron content of the shield excavation slag provided by the comparative example of the invention.
FIG. 3 is an XRD spectrum of untreated shield excavation residue in an embodiment of the present invention.
Detailed Description
The following examples are presented to further illustrate the practice of the invention, but the practice and protection of the invention is not limited thereto. It is noted that the processes described below, if not specifically described in detail, are all realizable or understandable by those skilled in the art with reference to the prior art. The reagents or apparatus used are not indicated to the manufacturer, and are considered to be conventional products available by commercial purchase.
Example 1
The embodiment provides a method for efficiently removing iron from shield mud, and the preparation process flow is shown in figure 1. The method comprises the following steps:
uniformly spreading shield excavation muck (shield muck) in a storage yard, airing for 24 hours in the sun, drying for 12 hours in an oven at 60 ℃, grinding and sieving to obtain dried shield muck A, and sealing and storing in a drying chamber for later use, wherein the size of a sieved sieve pore is 120 meshes;
accurately weighing 100g of dried shield muck A from a drying chamber, adding 200ml of deionized water, 50ml of 0.1mol/L oxalic acid solution, 40ml of 0.1mol/L hydrochloric acid solution and 5g of thiourea dioxide, and uniformly mixing to obtain a mixture B;
placing the mixture B in a magnetic stirring environment, placing a strong magnet (a neodymium iron boron magnet is selected) into the mixture B under the stirring condition, wherein the mass ratio of the magnet to the mixture C is 1:8, the magnetic force of the strong magnet is 1-200MT, taking out the strong magnet after 30min to obtain a mixture C, filtering the mixture C, and drying to obtain a mixture D;
and mixing the mixture D with 20g of coal powder, 5g of sodium carbonate and 10g of calcium carbonate, calcining for 30min at 400 ℃ in an electric furnace, and naturally cooling to obtain the shield mud subjected to iron removal (namely the shield excavation muck subjected to iron removal).
The iron content of the shield excavation muck before and after treatment is shown in tables 1 and 2. The XRD spectrogram of the shield excavation muck before treatment is shown in figure 3. As can be seen from FIG. 3 and Table 1, the untreated shield excavation muck had Al as a main component 2 O 3 ，SiO 2 And Fe 2 O 3 。
TABLE 1 composition of shield excavation muck before treatment (wt%)
TABLE 2 composition table (wt%) of the residue soil after the iron removal treatment in example 1
As can be seen from the analysis results in tables 1 and 2, the untreated shield excavation muck contained 5.48% (wt%) Fe 2 O 3 After the treatment of the steps, the shield excavation dregs contain Fe 2 O 3 The content of the iron in the shield mud is reduced to 0.8 percent (wt%), and the method for efficiently removing the iron from the shield mud provided by the embodiment 1 can effectively reduce Fe in the shield excavation residue soil 2 O 3 The content of (a).
Example 2
The embodiment provides a method for efficiently removing iron from shield mud, and the preparation process flow is shown in figure 1. The method comprises the following steps:
uniformly spreading the shield excavation muck in the yard, airing the mixture for 24 hours in the sun, drying the mixture for 12 hours in an oven at the temperature of 60 ℃, grinding and sieving the mixture, wherein the size of a sieved sieve pore is 120 meshes to obtain the dried shield muck A, and sealing and storing the dried shield muck A in a drying chamber for later use;
accurately weighing 100g of dried shield muck A from a drying chamber, adding 200ml of deionized water, 50ml of 0.1mol/L oxalic acid solution and 10g of thiourea dioxide, and uniformly mixing to obtain a mixture B;
placing the mixture B in a magnetic stirring environment, placing a strong magnet (neodymium iron boron magnet is selected) into the mixture B under the stirring condition, taking out the strong magnet to obtain a mixture C after the mass ratio of the strong magnet to the mixture C is 1:8 and the magnetic force of the strong magnet is 1-200MT and 30min, and filtering and drying the mixture C to obtain a mixture D;
and mixing the mixture D with 15g of coal powder and 20g of sodium carbonate, calcining the mixture D in a muffle furnace at 500 ℃ for 30min, and naturally cooling the mixture D to obtain the shield mud subjected to iron removal (namely the shield excavation muck subjected to iron removal). The iron content of the treated shield muck is shown in table 3.
TABLE 3 composition table (Wt%) of the residue soil after the iron removal treatment in example 2
As can be seen from tables 1 and 3, the untreated shield excavation muck contained 5.48% (wt%) Fe 2 O 3 After the treatment of the steps, the shield excavation dregs contain Fe 2 O 3 The content of the iron in the shield mud is reduced to 0.9 percent (wt%), and the method for efficiently removing the iron from the shield mud provided by the embodiment 2 can effectively reduce Fe in the shield excavation residue soil 2 O 3 The content of (a).
Comparative example 1
The comparative example provides a method for efficiently removing iron from shield mud, the preparation process flow is shown in figure 2, and the method comprises the following steps:
uniformly spreading the shield excavation muck in the yard, airing the mixture for 24 hours in the sun, drying the mixture for 12 hours in an oven at the temperature of 60 ℃, grinding and sieving the mixture, wherein the size of a sieved sieve pore is 120 meshes to obtain the dried shield muck A, and sealing and storing the dried shield muck A in a drying chamber for later use;
accurately weighing 100g of dried shield muck A from a drying chamber, adding 200ml of deionized water, 50ml of 0.1mol/L citric acid solution and 40ml of 0.1mol/L oxalic acid solution, and uniformly mixing to obtain a mixture B;
placing the mixture B in a magnetic stirring environment, placing a strong magnet (neodymium iron boron magnet is selected) in the mixture B under the stirring condition, taking out the strong magnet to obtain a mixture C after the mass ratio of the strong magnet to the mixture C is 1:8 and the magnetic force of the strong magnet is 1-200MT,30min, and filtering and drying the mixture C to obtain the shield muck after iron removal.
TABLE 4 composition of the shield excavation muck (%) -treated in example 4 with iron removal
As can be seen from the analysis results in tables 1 and 4, the untreated shield excavation muck contained 5.48% (wt%) of Fe 2 O 3 After the steps are carried out, the shield excavation dregs contain Fe 2 O 3 The content of (A) is reduced to 1.8% (wt%), the treatment scheme of the comparative example 1 can also effectively reduce Fe in the shield excavation residue soil 2 O 3 However, when the data in tables 2 and 3 are analyzed, the treatment effect of the comparative example is inferior to that of the example, and after the treatment of examples 1 and 2, the shield excavation residue soil contains Fe 2 O 3 The content of (A) is reduced to below 1 wt%.
Comparative example 2
The comparative example provides a method for efficiently removing iron from shield mud, the preparation process flow is shown in figure 2, and the method comprises the following steps:
uniformly spreading the shield excavation muck in the yard, airing the mixture for 24 hours in the sun, drying the mixture for 12 hours in an oven at the temperature of 60 ℃, grinding and sieving the mixture, wherein the size of a sieved sieve pore is 120 meshes to obtain the dried shield muck A, and sealing and storing the dried shield muck A in a drying chamber for later use;
accurately weighing 100g of dried shield muck A from a drying chamber, adding 200ml of deionized water, 50ml of 0.1mol/L citric acid solution and 40ml of 0.1mol/L oxalic acid solution, and uniformly mixing to obtain a mixture B;
and (2) placing the mixture B in a magnetic stirring environment, placing a strong magnet into the mixture B under the stirring condition, wherein the mass ratio of the strong magnet to the mixture C is 1:8, the magnetic force of the strong magnet is 1-200MT, taking out the strong magnet after 2h to obtain a mixture C, filtering the mixture C, and drying to obtain the shield muck with iron removed.
TABLE 5 composition of the shield excavation muck (%) -treated in example 5 with iron removal
Watch with watch1 and Table 5 show that untreated shield excavation muck contains 5.48% (wt%) Fe 2 O 3 After the steps are carried out, the shield excavation dregs contain Fe 2 O 3 The content of (A) is reduced to 1.1% (wt%), the treatment scheme of the comparative example 2 can also effectively reduce Fe in the shield excavation residue soil 2 O 3 The contents of (b) in the shield excavation residue soil, however, when analyzed in combination with the data in tables 2 and 3, the treatment effect of the comparative example was inferior to that of the example on the premise that the treatment time of the shield excavation residue soil with the strong magnet was longer, and after the treatment of examples 1 and 2, fe in the shield excavation residue soil was present 2 O 3 The content of (A) is reduced to below 1 wt%.
The above examples are only preferred embodiments of the present invention, which are intended to be illustrative and not limiting, and those skilled in the art should understand that they can make various changes, substitutions and alterations without departing from the spirit and scope of the invention.
Claims (8)
1. The method for efficiently removing the iron from the shield mud is characterized by comprising the following steps of:
(1) Drying, grinding and sieving the shield mud to obtain shield mud A; uniformly mixing the shield mud A with water to obtain a mixture B, and then adding an acidic substance to uniformly mix to obtain a mixture C;
(2) Adding a magnet into the mixture C obtained in the step (1) under a stirring state, carrying out adsorption iron removal treatment, taking out the magnet, filtering to obtain a precipitate, and drying to obtain a mixture D; uniformly mixing the mixture D, the coal powder and the carbonate to obtain a mixture E;
(3) Heating the mixture E obtained in the step (2) for calcination treatment to obtain iron-removed shield mud, wherein the iron oxide content in the iron-removed shield mud is less than 1 wt%;
the acidic substance in the step (1) is more than two of oxalic acid solution, hydrochloric acid solution, thiourea peroxide, sulfuric acid solution and citric acid solution; the concentrations of the oxalic acid solution, the hydrochloric acid solution, the sulfuric acid solution and the citric acid solution are all 0.1-1mol/L; the mass of the acidic substance is 0.01-15% of that of the mixture B;
the carbonate in the step (2) is more than one of sodium carbonate and calcium carbonate; the mass of the carbonate is 1-40% of that of the mixture D;
the temperature of the calcination treatment in the step (3) is 150-850 ℃, and the time of the calcination treatment is 30min-10h.
2. The method for removing iron from shield mud according to claim 1, wherein the drying in step (1) is performed by at least one of sun drying, drying by using waste heat from a factory, microwave drying and oven drying.
3. The method for removing iron from shield mud according to claim 1, wherein the moisture content of the shield mud A in the step (1) is 1-35%.
4. The method for removing iron from shield mud with high efficiency according to claim 1, wherein the size of the sieve mesh of the sieve in the step (1) is 120 meshes.
5. The method for removing iron from shield mud according to claim 1, wherein the solid-to-liquid ratio of the shield mud A to water in step (1) is 0.8: 5g/mL.
6. The method for removing iron from shield mud in high efficiency according to claim 1, wherein the mass ratio of the magnet in the step (2) to the mixture C is 1; the magnetic force of the magnet is 1-200MT.
7. The method for removing iron from shield sludge with high efficiency according to claim 1, wherein the time for the adsorption iron removal treatment in the step (2) is 1min-10h.
8. The method for removing iron from shield mud according to any one of claims 1 to 7, wherein the mass of the pulverized coal in the step (2) is 1 to 40 percent of that of the mixture D.
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