Technical field
[0001]
The present invention, the fluidity reducing agent of the solid-liquid mixture, and a method for producing a low flow mixture.
BACKGROUND
[0002]
Conventionally, in the civil engineering seawall construction, etc. of the river, the excavated soil degraded the embankment portion, when replacing the modified soil or good earth, therefore the construction process requiring significant materials and amount of work, the intensity as a method of simplifying the replacement of reinforced improved soil, a method of utilizing finely minced waste paper it has been proposed (see Patent documents 1, 2 and 3).
CITATION
Patent Document
[0003]
Patent Document 1: JP 2007-197902 Patent Publication
Patent Document 2: JP 2008-106088 Patent Publication
Patent Document 3: JP 2001-121193 JP
Summary of the Invention
Problems that the Invention is to Solve
[0004]
　However, in the conventional use of a finely subdivided paper technique, it is difficult to realize the improved soil with a strength capability to be practiced in civil engineering, from excavated soil obtained in a construction site, practically sufficient reinforcing modified soil having a strength, for a short enforcement period, if it is possible to obtain, it is considered to be greater effectiveness.
[0005]
　The present inventors focused on the point excavated soil degraded is solid-liquid mixture containing water solid components of the soil, if it is possible to reduce by simple operation in a short time the fluidity of the solid-liquid mixture, It was thought to be able to overcome the difficulties of the above in the civil engineering. Further, the present inventors have found that when reducing the fluidity of the solid-liquid mixture, were considered volume reduction, from the viewpoint of cost, it is necessary to suppress the increase volume.
[0006]
　The present invention was made in view of the above problems, irrespective of the chemical composition of the solid-liquid mixture, by simple operation in a short time, while suppressing an increase volume, decrease the fluidity of the solid-liquid mixture it can be, and to provide liquidity lowering agents and methods of solid-liquid mixtures.
Means for Solving the Problems
[0007]
　The present inventor has found that by trapping by entering the solid and liquid phases of the solid-liquid mixture into the gap formed by entanglement of fibers, specifically, a specific granules having fibers entangled structure, by using a fluidity reducing agent of the solid-liquid mixture, it can solve the above problems, and have completed the present invention.
[0008]
　A first aspect of the invention includes granules having fibers entangled structure, the granules have an average particle diameter is not less 300μm or less, the specific surface area by BET method of 0.25 m 2 / g or more 100 m 2 / g or less, a fluidity reducing agent of the solid-liquid mixture.
[0009]
　A second aspect of the present invention comprises a particulate material having fibers entangled structure, the granules, (1-bulk density / true density) porosity calculated by × 100 is 50% or more, BET specific surface area is 0.25 m 2 / g or more 100 m 2 or less / g, a flowability-lowering agent of the solid-liquid mixture.
[0010]
　A third aspect of the present invention, a mixture of a solid-liquid mixture and the fluidity reducing agent includes obtaining low flow mixture is a method for producing a low flow mixture. One embodiment of the third aspect of the present invention, a solid-liquid mixture, comprising mixing a fluidity reducing agent of the solid-liquid mixture in a vessel to obtain a low flow mixture of low flow mixture a manufacturing method,
　the fluidity dropping agents include particulates having fibers entangled structure, the granules have an average particle diameter of the specific surface area due to 300μm or less and the BET method 0.25m2 / g or more 100m2 / g or less, or (1-bulk density / true density) porosity calculated by × 100 is the specific surface area by 50% or more and the BET method is less 0.25M2 / g or more 100 m @ 2 / g,
　said container the relative mounting target volume of low flow mixture, the solid-liquid mixture is mixed in an amount of less than 50 volume% 100 volume%, and the volume of the amount of the solid-liquid mixture and the fluidity reducing agent to the total to said container It said a method exceeding mounting target volume of low flow mixture.
[0011]
　A fourth aspect of the present invention includes moving equipped with a low flow mixture obtained by the above method to the mobile, is a method for transporting low flow mixture.
[0012]
　A fifth aspect of the present invention, by capturing by entering the solid and liquid phases of the solid-liquid mixture into the gap formed by entanglement of fibers, by a method of improving the degree of fluidity decrease in the solid-liquid mixture is there.
[0013]
　Sixth aspect of the present invention, by capturing by entering the solid and liquid phases of the solid-liquid mixture into the gap formed by entanglement of fibers, the chemical composition of the solid-liquid mixture to be fluidity dropping a method to increase flexibility.
[0014]
　Seventh aspect of the present invention inhibit by capturing by entering the solid and liquid phases of the solid-liquid mixture into the gap formed by entanglement of fibers, the volume increase of the solid-liquid mixture after fluidity dropping method it is.
Effect of the invention
[0015]
　According to the present invention, irrespective of the chemical composition of the solid-liquid mixture, by simple operation in a short time, while suppressing an increase volume, it is possible to reduce the fluidity of the solid-liquid mixture. Further, according to the present invention allows the above, it is possible to provide liquidity lowering agents and methods of solid-liquid mixtures.
BRIEF DESCRIPTION OF THE DRAWINGS
[0016]
[1] Figure 1 is a photograph showing a fluidity lowering agent according to the present invention.
FIG. 2 is a photograph showing a state in which the soil particles to the formed voids by entanglement of the fibers in the fluidity reducing agent are trapped according to the present invention.
[3] FIGS. 3 (a) and 3 (b) is a graph showing the results of thermogravimetric-differential analysis of fluidity lowering agent according to the present invention.
[4] FIG. 4 is a graph showing the results of X-ray diffraction analysis for the ignition ash fluidity lowering agent according to the present invention.
DESCRIPTION OF THE INVENTION
[0017]
[Fluidity reducing agent of the solid-liquid mixture]
　One aspect of the fluidity reducing agent according to the present invention is a particulate material having fibers entangled structure, the granules have an average particle diameter of at 300μm or less, BET specific surface area according to law 0.25 m 2 / g or more 100 m 2 at / g or less, the fluidity reducing agent of the solid-liquid mixture. Another aspect of the fluidity reducing agent according to the present invention is a particulate material having fibers entangled structure, the granules, porosity is calculated by (1-bulk density / true density) × 100 There is 50% or more, the specific surface area by BET method of 0.25 m 2 / g or more 100 m 2 or less / g, a flowability-lowering agent of the solid-liquid mixture. In this alternative embodiment, the average particle diameter of the granules, may be 300μm or less. In the present specification, the average particle diameter refers to the average value of the particle diameter of the granules was measured under a light microscope.
[0018]
　As the fiber is not particularly limited, for example, those containing a hydrophilic polymer. When the fibers contains a hydrophilic polymer, when the liquid phase in a solid-liquid mixture comprising water, improved affinity for the fibers and the liquid phase becomes the liquid phase tends to be trapped in the fluidity reducing agent , more likely to increase the degree of fluidity decrease of the solid-liquid mixture. The hydrophilic polymer is not particularly limited, for example, cellulose, polyvinyl alcohol, polyalkylene glycols (e.g., polyethylene glycol, polypropylene glycol, etc.), include polyacrylic acid or the like, biodegradable or neutral pH range ( for example, a pH8 longitudinal), from the viewpoint of excellent low environmental load resistance, cellulose.
[0019]
　If the fiber contains a hydrophilic polymer, the content of the hydrophilic polymer in the fluidity reducing agent according to the present invention is preferably 40 wt% or more, more preferably 45 wt% or more, it is even more preferred is 47 wt% or more. When the content is 40 wt% or more, when the liquid phase in a solid-liquid mixture comprising water, improved affinity for the fibers and the liquid phase, the liquid phase is trapped in fluidity reducing agent easy it, is likely to further increase than the degree of fluidity decrease of the solid-liquid mixture. The upper limit of the content, but may be 100% by weight, considering the extent such liquidity reduction of the solid-liquid mixture, preferably 80 wt% or less, more preferably 60 wt% or less, 57 wt% or less is more preferred.
[0020]
　Fluidity-lowering agent according to the present invention, unless impair the object of the present invention, as an optional ingredient, calcium carbonate (CaCO 3 ), kaolin (Al 4 Si 4 O 10 (OH) 8 ), talc (Mg 3 Si 4 O 10 (OH) 2 ) may be used together with inorganic fillers such.
[0021]
　The solid-liquid mixture is not particularly limited, for example, mud. The content of the liquid phase in the solid-liquid mixture is not particularly limited, typically 20 to 90 wt%, more typically 30 to 75 wt%, more typically from 40-60% by weight, in particular typically 45 to 55% by weight. Mud is cone index qc is 400 (kN / m 2 may be less than), in particular 350 (kN / m 2 ) or less, 300 (kN / m 2 ) or less, 250 (kN / m 2 ) or less , 200 (kN / m 2 ) or less, 175 (kN / m 2 ) or less, 0.99 (kN / m 2 ) or less, 125 (kN / m 2 ) or less, 100 (kN / m 2 ) or less, 75 (kN / m 2 ) or less, 60 (kN / m 2 may be at) or less. The lower limit of the cone index qc mud is not particularly limited, 10 (kN / m 2 may be about).
[0022]
　Method for producing a fluidity lowering agent according to the present invention is not particularly limited, for example, a method comprising grinding a piece of material by milling. The material piece, for example, include those capable of forming fibers by pulverization by the mill, more specifically, shredder scrap, include paper waste paper or the like. By this method, granules having fibers entangled structure.
[0023]
　Hereinafter, in accordance with the following properties listed fluidity lowering agent according to the present invention will be described the fluidity reducing agent.
(1) the instantaneous resistance
(2) working simplicity
(3) general purpose
(4) low volume increase rate
[0024]
(1) the moment of
　the conventional approach is the approach solidified due to the chemical reaction of hydration, etc. around the cement solidifying material, reaction time, i.e. requires "curing period". On the other hand, the fluidity reducing agent according to the present invention, a physical liquid absorption is primarily mechanism, it does not require reaction times. As a result, such high water ratios sludge, it is possible to shorten the time to reach the completion of processing from the occurrence of a high solid-liquid mixture flowable (completion of low flow mixture).
[0025]
　Granules constituting the fluidity reducing agent according to the present invention has a fiber entangled structure, as shown in the Examples, the structure exhibits a flocculent. The cotton-like structure will have many voids with a communicability, the flowable reducing agent is added to the high solid-liquid mixture of liquid content ratio, such as sludge, fine particles constituting the water or sludge to the gap from entering in time, the internal pressure is less likely to work. As a result, the air meets the air gap, the replacement of water and fine particles occurs rapidly. In this way, water or fine particles, the air meets the communication of voids in the cotton-like structure of the flowable reducing agent turned into tiny air (bubbles), with these air physically constrained communicability void It is.
[0026]
　Solid-liquid mixture, such as high water ratio had a liquid sludge, in this way, it is constrained freedom of movement by the fiber structure, the addition and stirring of the flowable lowering agent (the fluidity reducing agent after dispersion) of the solid-liquid mixture, the plastic is brought immediately. Incidentally, the subject of the fibers constituting the fluidity reducing agent is a hydrophilic polymer such as cellulose, if the liquid phase of the solid-liquid mixture comprising water, since the hydrophilic polymer having many hydrophilic groups in the molecular side chains acts electrical attraction between the fibers constituting the water molecule and voids contribute to out to continue difficulty of water entering the communicability gap (binding).
[0027]
　Further, the granulate constituting the fluidity-lowering agent, in one embodiment, an average particle size of less and a minimum 300 [mu] m. This was added to the flowable reducing agent to the solid-liquid mixture, which contributes to the dispersion of the height of the flowable reducing agent in performing the stirring, together with the physical constraints mechanism, at the moment of It has contributed. From the viewpoint of the dispersibility, the average particle diameter is preferably 250μm or less, more preferably 200μm or less. The lower limit of the average particle diameter is not particularly limited, typically 3μm or more and more typically 50μm or more.
[0028]
　On the other hand, a BET specific surface area of particulate material constituting the fluidity-lowering agent, 0.25 m 2 / g or more 100 m 2 at / g or less. Fiber itself constituting the fluidity reducing agent also has the fine voids, (BET specific surface area: approximately 500m silica gel used in the hygroscopic material or the like 2 / g) and activated carbon used for the adsorption or the like (specific surface area by the BET method: about 1000 m 2 / g) as compared to, small BET specific surface area. Silica gel or activated carbon to have a gap (pore) countless angstrom order in the material, the granules, the particle constituent fibers themselves, not have much pores of angstrom order it means that. The adsorption performance of the gas, while the pores is greatly influenced, in the case of liquid-absorbing, particularly a short time, when considering the modest effect of the pores, the measurement of the specific surface area of the flowable lowering agent the value is to support the liquid absorbing principle moments of the physical restraint mechanism as a main principle according communicability voids by entanglement of fibers constituting the fluidity reducing agent.
[0029]
　BET specific surface area of the particle constituting the fluidity reducing agent, from the viewpoint of liquid absorbing performance due to the fluidity reducing agent, preferably 0.25 m 2 / g or more 100 m 2 / g or less, more preferably 0 .5M 2 / g or more 10 m 2 / g or less, still more preferably 0.75 m 2 / g or more 5 m 2 / g or less, particularly more preferably 1 m 2 / g or more 2m 2 or less / g.
[0030]
(2) working simplicity
　fluidity lowering agent according to the present invention, the liquid absorbing due to physical constraints, such as described above, since it is led to plastic to solid-liquid mixture having a liquid, the work required for the processing , i.e., only stirred and added to the solid-liquid mixture of the flowable lowering agent. Thus, the addition or more drugs, the order of addition with a plurality of drug addition, without requiring the amount of complex procedures and work-Considerations such balance and the like, the work is made simple, which can be anyone.
[0031]
　Also, in the case of physical restraint mechanism, it is not necessary to examine the chemical composition of the solid-liquid mixture is an improvement target advance, because it can see the effect immediately by the addition and stirring, for such liquid content ratio of time to measure also, it is not necessary to investigate before working, it is possible to sample the solid-liquid mixture in situ, was added and stirring portionwise the flowable lowering agents, to determine easily the addition ratio which exhibits plasticity of interest .
[0032]
(3) versatility
　fluidity lowering agent according to the present invention, the liquid absorbing due to physical constraints, such as described above, since it is led to plastic to solid-liquid mixture having a liquid, solid-liquid is an improvement target chemical composition of the mixture can be used regardless of the. For example, the solid phase of the solid-liquid mixture, be an inorganic substance or an organic substance. The liquid phase of the solid-liquid mixture, in water may be an organic solvent may be a solution. For the solution, e.g., concentration of solutes or ions such as electrolyte, any kind, and the like.
[0033]
(4) low volume increase
　granules constituting the fluidity reducing agent according to the present invention, as described above, having a void. This gap, the flowable lowering agent communicability voids by entanglement of fibers constituting the fine voids having the fiber itself, is inter-particle voids. Granules constituting the fluidity reducing agent according to the present invention, in one embodiment, (1-bulk density / true density) porosity calculated by × 100 is 50% or more. The porosity, from the viewpoint of liquid absorbing performance due to the fluidity reducing agent, preferably 60% or more, more preferably 70% or more, even more preferably 80% or more, particularly preferably 85% or more. The upper limit of the porosity, from the viewpoint of the strength of the flowable reducing agent, preferably 95% or less, more preferably 93% is less, still more preferably 91%, particularly preferably at most 89%.
[0034]
　In the present specification, the bulk density, fluidity reducing agent, filled in a container of a volume, in particular without applying a load from above, and the internal volume of the granules that constitute the fluidizing lowering agent filled it is those calculated by the weight.
[0035]
　Here, in Example 2, for example, corn moisture content 48% by weight of the mud, which is one of the quality class to be defined in the "Construction Sludge treated soil available technical standards," "fourth type processing soil" has index 200 kN / m 2 when improving or more, 1 m 3 has been shown that it is necessary to add fluidity lowering agents 25kg per. True density of 1.9 g / cm of granules constituting the fluidity reducing agent used in Example 2 3 volumes of considering that the particulate matter constitutes an added fluidity reducing agent in Example 2 is, 25 × 1000 / (1.9 × 100 × 100 × 100) ≒ 0.013 m 3 is. That is, the volume increase rate by component fibers or the like after addition of fluidity reducing agent in Example 2 can be calculated as about 1%. The volume increase rate is solidified methods involving hydrate formation due to hydration reaction of cement solidifying material such as, in comparison with the plasticized approach high polymer system that expands by incorporating water into the molecule, the volume rate of increase is very small.
[0036]
　Moreover, the physical constraints of the communication of the gap formed by the entanglement of the fibers constituting the granules, while having a certain water retention, water that has been constrained by Serudoron is by physical outreach by compression or the like, extruding It is possible. Thus, for example, while improving the handling property in carrying out such construction sludge, by achieving physical dehydration such as compression, since it becomes possible to easily perform volume reduction and weight of the sludge, high temperature firing compared to the conventional volume reduction method and lightweight methods in the furnace or the like, it is possible to achieve a volume reduction and weight reduction at low cost.
[0037]
(5) low environmental impact of
　the fibers constituting the fluidity reducing agent according to the present invention is a case containing cellulose, explaining the low environmental load resistance. Cellulose, which is decomposed by the cellulase, to be degraded by fungi or the like present in the soil, over the flowable lowering agent time added to the environment, go back to the original soil. Moreover, the biodegradability, the addition of enzymes such as cellulase, makes it possible to solve physically constrained water and fine particles and the like from the restraint by the flowable lowering agents. Further, pH of the flowable reducing agent is a neutral zone (pH 8 before and after), pH of the soil after the addition of the flowable lowering agent from staying in the neutral region, a small impact on the agricultural and surrounding vegetation.
[0038]
[Method for low flow Mixture
　according to the present invention, a method of manufacturing low-fluidizable mixture includes obtaining a low flow mixture by mixing a fluidity reducing agent according to the solid-liquid mixture and the present invention. Mixing method is not particularly limited, and may be a known method. The amount of the fluidity reducing agent to be mixed with the solid-liquid mixture is not particularly limited, from the viewpoint of the degree or the like of the fluidity deterioration of the solid-liquid mixture, to solid-liquid mixture 100 parts by weight, for example, 1.5 parts by weight or more, preferably 3 parts by weight or more, more preferably 4.5 parts by weight or more, even more preferably 9 parts by weight or more. The upper limit of the amount is not particularly limited, from such a point that tends to suppress the increase in volume, with respect to the solid-liquid mixture 100 parts by weight, for example, 50 parts by weight or less, preferably not more than 30 parts by weight, more preferably 20 parts by weight or less, still more preferably not more than 15 parts by weight.
[0039]
　As described above, according to the fluidity lowering agent used in the present invention, the volume increase of about mixing hardly occurs. Therefore, according to the present invention, in the manufacturing method of the low flow mixture for mounting the target volume of the low flow mixture to the vessel, the solid-liquid mixture is mixed in an amount of less than 50 volume% 100 volume%, and it is preferable that the volume total of the solid-liquid mixture and the amount of the fluidity reducing agent exceeds mounting target volume of low flow mixture to the vessel.
[0040]
　The amount of the solid-liquid mixture is preferably 60 volume% or more of the mounting target volume, more preferably 70 volume% or more, 80 vol% or more, 85 vol% or more, 90 vol% or more, 95% by volume or more and 97 volume% or more. The amount of the solid-liquid mixture, consideration of slight volume increase after mixing, 99.9 volume% or less with respect to mounting the target volume, 99.5% by volume or less, 99% by volume or less, 95% by volume or less it may be 90 volume% or less. Note that the mounting target volume of low flow mixture to the vessel, may be a variable value set to each use, or determined constant in terms of safety for each container, or of each container it may be a fixed value such as the maximum volume.
[0041]
　Further, since the volume increase after mixing is suppressed, the volume total of the amount of the solid-liquid mixture and fluidity reducing agent, to mount the target volume of the low flow mixture to the vessel, there in 101% by volume or more at best, preferably 102% by volume or more, 103% by volume or more, 108% by volume or more, 110% by volume or more and 115% by volume or more. On the other hand, the volume sum of above, for example, may be less than 200% by volume with respect to mounting the target volume of the low flow mixture to the vessel, in particular 190% by volume or less, 175 volume% or less, 150 volume% or less, 140 volume% or less, 130 volume% or less, may be 120% by volume or less. The amount described above is preferable in view of efficiency of the manufacturing process of the low flow mixture with one vessel, the present invention, the solid-liquid mixture and the volume total of the amount of the fluidity reducing agent is mounted target volume 101 may be an amount of volume percent.
[0042]
　The mixing can be done in the space of the closed space or a constant volume of the vessel. Even if the mixing in the present invention in the space of the closed space or constant volume, tends to prevent vessel damage caused by the significant increase in volume. The mixing in space of the closed space or constant volume, as compared to mixing in the release space, generally difficult or sufficient mixing to poor operability, a confirmation that the mixing is sufficiently performed difficult there are problems or, instantaneous property in the present invention, the working simplicity, since use of the fluidity lowering agent is excellent in versatility, it is also possible to solve the problems described above. From the same viewpoint, the mixing may be performed using a container on granule truck. Incidentally, the space enclosed spaces or constant volume only needs to be closed or volume kept constant during mixing encompasses space reversibly release or a variable volume container capable. It is also possible to use a container having a release space in the present invention.
[0043]
　Cone Index qc aspect of low flow resulting mixture with the mud in the method of the present invention is not particularly limited, 50 (kN / m than the cone index qc mud 2 is preferably high) m 2 ) or more, 100 (kN / m 2 ) or more, 125 (kN / m 2 ) or more, 140 (kN / m 2 ) or more, 175 (kN / m 2 ) or more, 200 (kN / m 2 ) or more, 250 (kN / m 2 ) or more, 300 (kN / m 2 ) or more, 400 (kN / m 2 ) or more, 500 (kN / m 2 ) or more, 600 (kN / m 2 ) or more , 700 (kN / m 2 ) or more, 800 (kN / m 2 ) or more, 900 (kN / m 2 ) or more, 1000 (kN / m 2 may be higher) or more.
[0044]
　Low flow mixture prepared in the manner described above, it is or if additional stabilizing treatment (e.g., calcination treatment and additives such as solidifying agent) may be used after being subjected (eg reforming mud, construction, etc. ), and it may be discarded.
[0045]
[Method of transporting low flow Mixture
　according to the present invention, the transport method of low flow mixture, according to the present invention, a moving mobile body low flow mixture obtained by the production method of low flow mixture including. The mobile, for example, powdered or granular truck, a dump truck and the like. Low flow mixture that is conveyed, may be used for construction work in the destination, it may be discarded.
[0046]
[Solid-liquid method to improve the degree of fluidity decrease of the mixture]
　Another aspect of the present invention, by capturing by entering the solid and liquid phases of the solid-liquid mixture into the gap formed by entanglement of fibers, the a method for improving the degree of fluidity decrease of the solid-liquid mixture. In this method, for example, it can be used fluidity lowering agent according to the present invention. Granules constituting the fluidity lowering agent has a space formed by the entanglement of the fibers, this gap, because the solid and liquid phases of the solid-liquid mixture is captured by invasion.
[0047]
[Chemical methods to improve the degree of freedom in the composition of the solid-liquid mixture to be flowable reduction]
　Another aspect of the present invention, intrusion of the solid and liquid phases of the solid-liquid mixture into the gap formed by entanglement of fiber by trapping by a method for improving the flexibility of the chemical composition of the solid-liquid mixture to be fluidity dropping. In this method, for example, it can be used fluidity lowering agent according to the present invention. As described above, the fluidity reducing agent according to the present invention can be used regardless of the chemical composition of the solid-liquid mixture, improve the degree of freedom in the chemical composition of the solid-liquid mixture to be fluidity dropping it can be.
[0048]
[A method of suppressing the increase in volume of the solid-liquid mixture after illiquidity]
　Another aspect of the present invention, by capturing by entering the solid and liquid phases of the solid-liquid mixture into the gap formed by entanglement of fiber a method of suppressing the increase in volume of the solid-liquid mixture after fluidity dropping. In this method, for example, it can be used fluidity lowering agent according to the present invention. As described above, the fluidity reducing agent according to the present invention, it is possible to suppress the volume increase of the solid-liquid mixture after fluidity dropping.
Example
[0049]
　Hereinafter, a more detailed explanation of the present invention by showing Examples, the scope of the present invention is not limited to these examples.
[0050]
Example 1: Preparation of flowable reducing agent]
　shredder scrap (specific surface area 0.23m by BET method 2 was ground by mill / g), average particle size 200 [mu] m, specific surface area by the BET method: 1.6 m 2 / g It was obtained consisting of granules fluidity reducing agent. Observation of the granules with an optical microscope, have fibers entangled structure, the structure had exhibited flocculent (Figure 1). Measurement of the specific density of the granules made by Shimadzu Corporation dry density meter, 1.9 g / cm 3 was. The bulk density of the granules is 0.25 g / cm 3 was. Therefore, porosity of the granules was (1-0.25 / 1.9) × 100 ≒ 87%.
[0051]
[Examples 2-5 and Comparative Example 1: fluidity reducing agent and mud mixed for]
　a fluidity lowering agent water content 48% by weight of mud and obtained in Example 1, were mixed in a weight shown in Table 1 . For soil after mixing, in compliance with JIS A 1228, it was measured cone index. The results are shown in Table 1. In Table 1, the ratio refers to a ratio by weight of the flowable lowering agent for the mud.
[0052]
[Table 1]

[0053]
　As is apparent from Table 1, with respect to water content of 48% by weight of the mud by mixing 1.6 wt% or more of the flowable lowering agent, quality is defined in the "Construction Sludge treated soil available technical standards" Category cone index 200 kN / m with it is one "fourth type treated soil" in 2 range of more is satisfied, it was possible to reduce the fluidity of the mud.
[0054]
　A state after mixing 10 wt% of the flowable reducing agent to water content of 60% by weight of the mud are shown in FIG. As shown in FIG. 2, the soil of the fine particles had been trapped in the gap flocculent structure in the entangled fibers in the fluidity reducing agent. Since photography, moisture was evaporated by drying.
[0055]
[Example 6, Comparative Example 2, and Reference Example 1: degradation test with cellulase]
　to decomposition test with cellulase used was the following samples.
Example 6: Example 1 obtained in fluidity reducing agent
Comparative Example 2: shredder scrap used to obtain a fluidity reducing agent in Example 1
Reference Example 1: Cellulose Microcrystalline (Merck)
[0056]
　Cellulase agent (trade name: Cellulase SS, Nagase ChemteX Corporation) was diluted to a concentration of 1/50 with a 0.1M acetate buffer (pH 5.5), to prepare enzyme diluent. The sample 25mg was added to the enzyme dilution 0.5 ml, followed by stirring. At that time, according to the visual, both samples were observed to hardly dissolved. It was then incubated at 40 ℃ 24 hours. The reaction time of 0 hours and 24 hours kept by centrifugation (7,000 × g, 5 minutes), the supernatant was recovered. The reaction supernatant was boiled for 5 minutes and stopped. The amount of glucose contained in the supernatant was measured by the glucose test Wako CII (manufactured by Wako Pure Chemical Industries, Ltd.). The results are shown in Table 2.
[0057]
[Table 2]

[0058]
　As is apparent from Table 2, the fluidity reducing agent according to the present invention, as compared to the shredder scrap of Comparative Example 2, can be efficiently decomposed by cellulase, it was confirmed that excellent biodegradability.
[0059]
Example 7: pH measurement]
　After the sample 10g was obtained by mixing the mud and the fluidity reducing agent in Example 3 was collected in a glass container, stirring was carried out thereto Pure water was added to 25 ml, It was allowed to stand for 1 hour. Soil suspension after standing, after gentle agitation, the pH was measured with a glass electrode method. It is to be noted that the test method, Japan soil fertilizer Society of supervision "soil environment analysis" Chapter V soil chemistry 1. pH pH (H of (glass electrode method) 2 with reference to O).
[0060]
Example 8: Physical properties analysis of fluidity reducing agent]
1. Analysis contents
　The following analysis was performed on the fluidity reducing agent obtained in Example 1.
(1) loss on ignition (hereinafter, also referred to as
ig-Loss.) (2) thermogravimetric-differential analysis (hereinafter, referred to as
TG-DTA.) (3) X-ray diffraction analysis of the ignition ash (hereinafter XRD both Say.)
[0061]
2. Analytical Methods
(1) ig-Loss
　magnetic crucible to the fluidity reducing agent about 8g weighed accurately to 1/100 g, was heated at about 2 hours placed in an electric furnace up to 1,000 ° C., and held for 1 hour. Then removed magnetic crucible gradually cooled in the furnace to around 100 ° C. from the furnace and placed in a desiccator. Allowed to cool to room temperature, it was quickly weighed. Because the flowable lowering agent that is expected loss is large, the measurement was performed three times. The ignition loss was calculated by the following equation.
Ignition loss = (before heating weight - weight after heating) / before heating Weight
[0062]
(2)
　TG-DTA TG-DTA is a situation where the material by heating causes a chemical change (. Including combustion) is a method of examining a way of examining fever endothermic behavior and weight change. Liquidity lowering agents obtained in Example 1, using a Rigaku Thermo Plus EVO2 differential示熱balance TG8121, it was measured TG-DTA. Incidentally, measurement conditions, sample weight 15 mg, measurement temperature range 20 ~ 950 ° C., was heating rate 20 ° C. / min.
[0063]
(3) XRD XRD
　is an analytical method for performing qualitative and quantitative use substances that individual substances has a unique crystal structure. The ash generated by ig-Loss above (1) was pulverized in an agate mortar, the ash generated in an agate mortar grinding, the ash generated in an agate mortar grinding, was ground in an agate mortar, packed into XRD measurement holder It was. The analysis, using the Rigaku smart lab. Measurement conditions, goniometer: MultiFlex + goniometer, X-rays: CuKa, 40 kV / 30 mA, scan mode: continuous mode, scan speed: 2.0 ° / min, scanning range: was 2θ = 5 ~ 65 °.
[0064]
3. Analysis Results
(1) ig-Loss
　results are shown in Table 3.
[0065]
[table 3]

[0066]
(2) TG-DTA
　showing the results in FIGS. 3 (a) and 3 (b). In the figure, "TEMP" and displayed line indicates the heating temperature, the displayed line weight change as "TG" (TG curve) indicates, "DTA" and displayed lines exothermic endothermic (DTA curve) It is shown. Incidentally, FIG. 3 (b) is obtained by changing the drawing scale of the DTA curve in FIG. 3 (a).
[0067]
(3) XRD
　The results are shown in FIG.
[0068]
4. Discussion
(1) ig-Loss
　3 times measurements have little variation, ig-Loss was about 74%. Organic components by the strong heat in combustion or lost, believed filler and other inorganic contaminants remained as ash. The details will be discussed in the next TG-DTA and XRD.
[0069]
[Table 4]

[0070]
(2) TG-DTA
　there is gradual endothermic peak at room temperature ~ 100 ° C., the TG curve at the same temperature is lowered slightly (and weight loss), the water adsorbed on the fluidity reducing agent is evaporated It is shown that. Reading from the measured value, the weight ratio of the adsorbed water fluidity lowering agent had was about 3%.
[0071]
　Then, a large exothermic peak was observed in DTA curve when heated to 250 ~ 350 ° C., it is understood that the weight loss decreases larger TG curve at the same temperature. This cellulose is burned, decomposed into water vapor and carbon dioxide means that are released into the atmosphere (heat generation amount is too large, the heating control becomes ineffective, "TEMP" and displayed line is also increased doing.). Weight loss at this time was about 49%.
[0072]
　When the combustion of the cellulose is finished, it appeared little gentle exothermic peak 350 ~ 570 ° C.. Heating at this temperature, the inferred from would fluidity lowering agent contains substances, lignin, ink carbon, or the possibility of unburned carbon remaining during combustion in the 300 ~ 350 ° C.. Wood fibers, in addition to cellulose, but contains a large amount of hemicellulose and lignin, lignin from being removed as much as possible in the papermaking process to become discolored has viscosity, the content is very small. Therefore, considered that the combustion of unburned carbon and / or printed carbon of the cellulose. Weight loss at this point was about 7% from the measured value.
[0073]
　Appeared gentle endothermic peak at 700 ℃ ~ 800 ℃, it is reduced even weight at the same temperature. This is what captures the phenomenon carbonate force calcium fillers contained in the fluidity reducing agent is decarboxylation. Reduction of the decarboxylation was about 12%.
[0074]
　Incidentally, a variety of purposes in the papermaking process, fillers are used. Generally as filler employed, calcium carbonate (CaCO 3 ), kaolin (Al 4 Si 4 O 10 (OH) 8 ), talc (Mg 3 Si 4 O 10 (OH) 2 ), and the like. Possibility that also contains filler other than calcium carbonate to the fluidity reducing agent is high. Thermal decomposition of calcium carbonate (Scheme: CaCO 3 + [Delta] H → CaO + CO 2 , [Delta] H is the amount of heat) is at 700 ° C. or more, the weight loss (theoretical 44%) often, depending clearly detectable (literature, thermal decomposition of calcium carbonate, reports and that occurs from around 600 ° C., there is also data that occurs at 900 ° C. vicinity, in the present measurement conditions is 700 ~ 800 ℃.). Meanwhile, since the thermal decomposition of kaolin and talc (these dehydration of crystal water) temperature is broadly in 350 ~ 650 ° C., and the weight loss is small 10 to 14% since overlapping the combustion reaction of the cellulose, the TG-DTA is difficult to detect.
[0075]
　In summary, as shown in Table 5.
[Table 5]

[0076]
　Weight Loss sum obtained by TG-DTA (heating to 950 ° C.) is 72.12%, substantially coincides with 73.72 percent loss on ignition (heating to 1000 ° C.) of (1). The content of cellulose contained in the flowable lowering agent, was approximately 48-56%.
[0077]
　Note that the flowable lowering agent, JIS P 8251: weight loss at a defined ashing temperature 575 ° C. to 2002 was 61.84% (however, also includes decrease amount of adsorbed water on the value .).
[0078]
(3) XRD
　The XRD patterns shown in Figure 4, the ash, calcium oxide (CaO), gehlenite (Ca 2 Al (AlSi) O 7 ), magnetite (iron oxide Fe 2 0 3 ), calcium hydroxide (Ca ( OH) 2 ) it seems to have been included. Extrapolating from the height of the detected peak, the amount contained in the ash is calcium oxide> gehlenite >> magnetite> calcium hydroxide.
[0079]
　Calcium oxide is a calcium carbonate filler was produced by decarboxylation from ignition material contained most in the ash. Incidentally, trace detected calcium hydroxide are those calcium oxide in the sample has reacted with moisture in the air during the measurement. Then, it was included gehlenite of clay-based filler such as kaolin appears to have generated by dehydration and recrystallization. The main component of the ash content in this two, it can be seen that due to the filler.
[0080]
　In addition, although there is a small amount, magnetite can also be seen. This stapler, wear of the pulverization blade, may be due to ink components and the like.

The scope of the claims
[Requested item 1]
A granulate having fibers entangled structure, the granules have an average particle diameter of at 300μm or less, the specific surface area by BET method of 0.25 m 2 / g or more 100 m 2 or less / g, the solid-liquid mixture of liquidity-lowering agent.
[Requested item 2]
　A granulate having fibers entangled structure, the particulate matter is a (1-bulk density / true density) porosity calculated by × 100 is 50% or more, a BET specific surface area of 0.25m 2 / g or more 100 m 2 at / g or less, the fluidity reducing agent of the solid-liquid mixture.
[Requested item 3]
　Fluidity lowering agent according to claim 2 average particle diameter of 300μm or less.
[Requested item 4]
　Fluidity lowering agent according to any one of claims 1 to 3, wherein the fiber contains a hydrophilic polymer.
[Requested item 5]
　Fluidity lowering agent according to claim 4 wherein the hydrophilic polymer is cellulose.
[Requested item 6]
　Fluidity lowering agent according to claim 4 or 5 content of the hydrophilic polymer is 40 wt% or more in the fluidity reducing agent.
[Requested item 7]
　Fluidity lowering agent according to any one of claims 1 to 6, wherein the solid-liquid mixture is mud.
[Requested item 8]
　By mixing a fluidity reducing agent according to the solid-liquid mixture with any one of claims 1 to 6, comprising obtaining a low flow mixture, method for producing a low flow mixture.
[Requested item 9]
　Wherein said solid-liquid mixture and with said flowable reducing agent are mixed in a vessel to obtain a low flow mixture,
　with respect to mounting the target volume of the low flow mixture into the container, the solid-liquid mixture 50 is mixed in an amount of less than volume% to 100 volume%, and claims volume total amount of the solid-liquid mixture and the fluidity reducing agent exceeds mounting target volume of the low flow mixture into said container 8 the method according to.
[Requested item 10]
　The mixing method according to claim 9 carried out in the space of the closed space or a constant volume of said container.
[Requested item 11]
　The mixing method according to claim 9 or 10, wherein is carried out using the container on granule truck.
[Requested item 12]
　The method according to any one of claims 8-11 wherein the solid-liquid mixture is mud.
[Requested item 13]
　It includes moving and mounted on a mobile low fluidity mixture obtained by the method according to any one of claims 8-12, the transport method of low flow mixture.
[Requested item 14]
　The granules having a communication of voids in the cotton-like structure formed by intertwining fibers are dispersed in the solid-liquid mixture, by capturing by entering the solid and liquid phases of the solid-liquid mixture to the communication of the air gap, how to improve the degree of fluidity decrease in the solid-liquid mixture.
[Requested item 15]
　The granules having a communication of voids in the cotton-like structure formed by intertwining fibers are dispersed in the solid-liquid mixture, by capturing by entering the solid and liquid phases of the solid-liquid mixture to the communication of the air gap, method for improving the flexibility of the chemical composition of the solid-liquid mixture to be fluidity dropping.
[Requested item 16]
　The granules having a communication of voids in the cotton-like structure formed by intertwining fibers are dispersed in the solid-liquid mixture, by capturing by entering the solid and liquid phases of the solid-liquid mixture to the communication of the air gap, method of inhibiting the increase in volume of the solid-liquid mixture after fluidity dropping.