JP2015078974A - Method for quantitative analysis of fluorine by mineral kind, system for quantitative analysis of fluorine by mineral kind, method for sorting inorganic oxide materials each containing fluorine-containing mineral, and method for producing inorganic oxide-based fabricating material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an analysis method and an analysis system, capable of easily and rapidly quantifying fluorine in an inorganic oxide material, particularly in steel slag, by mineral kind by a humidifying pyrolysis method and an emission spectroscopic analysis method using helium plasma.SOLUTION: A method for quantitative analysis of fluorine by mineral kind, extracts fluorine in an analyzed sample and performs quantitative analysis. When pyrolytically decomposing the analyzed sample, the analyzed sample is heated in a range from a normal temperature to 1,200°C by use of humidified gas as a carrier gas, and the carrier gas containing generated fluoride gas is continuously subjected to the quantitative analysis by a helium plasma emission spectroscopic analysis method. Furthermore, quality management such as sorting of inorganic oxide materials is performed, and production of them is performed.

Description

  The present invention relates to a method for quantitative analysis of a fluorine mineral type in an inorganic oxide material, particularly steel slag, a fluorine mineral type quantitative analysis system, a method for fractionating an inorganic oxide material containing a fluorine-containing mineral, and an inorganic oxide. The present invention relates to a method for manufacturing a system processed material.

  Fluorine is an environmentally hazardous substance. For example, there are restrictions on the content of 0.4 mass% and elution amount of 0.8 mg / L based on soil environmental standards. Therefore, various analysis methods are being studied. Regarding the content determination method, in general, after extracting fluorine from the sample to be analyzed by distillation or thermal hydrolysis and collecting it in a collection solution, the concentration of fluoride ions in the collection solution Is quantitatively analyzed using an absorptiometric method, an ion electrode method, an ion chromatography method, or the like to quantify the fluorine content in the sample to be analyzed.

  Non-Patent Document 1 below discloses a method for quantifying the fluorine content in cement by decomposing with a perchloric acid-phosphoric acid solution and performing steam distillation, and then quantifying the fluorine content by absorptiometry. It is prescribed.

  Moreover, in the following nonpatent literature 2, after collecting the fluorine content in steel slag in the phosphate ion solution which is a collection liquid after thermally analyzing a to-be-analyzed sample at 1200 degreeC, ion chromatography is carried out. Quantified by the method.

Patent Document 1 below describes that the sample is analyzed by thermal hydrolysis at a temperature of 1100 ° C. or higher in a state where a reaction accelerator is mixed with the sample to be analyzed, and quantitatively determined by absorptiometry, ion chromatography, or the like.
Further, in the following Patent Document 2, in a method of quantifying fluoride in a sample by reacting a sample to be analyzed with a strong acid, collecting the resulting fluoride with a collection liquid, and measuring the fluoride ion concentration, A method and system for quantitatively determining the fluorine content with high accuracy by using a closed analysis system in which two syringes, a reaction tank, and a collection tank are connected by a tube has been proposed.
In Patent Document 3 below, a reaction accelerator such as tungsten trioxide is mixed with the sample to be analyzed, and the non-humidified air is heated as a carrier gas. A method and system for quantifying by flow injection analysis after collection in an absorbing solution has been proposed.

  On the other hand, various methods have been proposed for insolubilization in order not to release fluorine into the environment, mainly environmental water.

For example, Patent Document 4 below proposes a method for insolubilizing fluorine effectively into water-insoluble fluoroapatite with an alkali metal phosphate added to an acidic solution.
Patent Document 5 below describes a technique for immobilizing fluorine by aging slag whose main phase is calcia-silica based in a steam atmosphere and incorporating fluorine into calcium silicate hydrate. ing.
In Patent Document 6 below, by controlling the cooling converter slag in steel, hydration reactivity greater _{(2CaO · SiO 2) 2 ·} CaF 2 _{phases, (3CaO · SiO 2) 3} · CaF 2 phases rather than 3CaO _· SiO ₂ -CaF 2 phases, a method of precipitating the hydration reactivity small 3CaO · 2SiO ₂ · CaF ₂ phases and 2CaO _· SiO ₂ -CaF 2 phases have been proposed.

  In addition to the techniques described in Patent Documents 4 to 6, various methods for controlling the mineral species of the fluorine-containing mineral have been proposed. Each of these methods is a method in which a fluorine mineral species is changed to an insoluble one in water using a chemical reaction and is immobilized.

  The analysis methods described in Patent Documents 1 to 3 and Non-Patent Documents 1 and 2 are all methods for knowing all the fluorine contents in the sample to be analyzed. On the other hand, the inventions described in Patent Documents 4 to 6 are inventions that convert fluorine-containing mineral species in order to control the elution amount of fluorine. In other words, it is important to know the fluorine-containing mineral species in order to effectively suppress the fluorine elution amount assuming the elution amount of fluorine, but there is a method to know all the fluorine content. However, no method has been proposed for quantitative analysis of specific fluorine-containing mineral species.

  General methods for knowing fluorine-containing mineral species, for example, surface mineral species analysis methods such as electron microscopy, X-ray photoelectron spectroscopy, and X-ray absorption fine structure analysis, provide comprehensive information including the inside of the sample. There is a disadvantage that it cannot be obtained. On the other hand, if the solid nuclear magnetic resonance method is used, overall information including the inside of the sample to be analyzed may be obtained, but it is difficult to apply to, for example, steel slag having a large iron content. In addition, if powder X-ray diffraction method is used, there is a possibility that quantitative information can be obtained to some extent for each mineral. For example, in soil and steel slag, the fluorine content is very small, so general powder X-ray diffraction It is difficult to obtain information for each fluorine-containing mineral with the sensitivity of the law.

  Based on the above, with regard to fluorine-containing minerals, on-site daily management analysis methods in factories where inorganic oxide materials must be manufactured and processed, although there is a method for quickly determining the content, fluorine-containing There is no way to obtain quantitative information for each mineral species.

Japanese Patent Laid-Open No. 02-92802 JP 2005-99002 A JP 2010-44034 A JP 2009-189927 A JP 2003-293023 A JP 2011-37644 A

Cement Association Standard Test Method (CAJSI-51), 1981 Kazuo Yanagihara, Yoshikatsu Giiga: Electric Steelmaking, 78, 1, p. 5-11, 2007

  In view of the above problems, the present invention provides a technique for quantifying the content of each fluorine mineral species contained in an inorganic oxide material containing fluorine, such as so-called steel slag, and a fluorine-containing mineral using such a quantification technique. It is an object of the present invention to provide a method for fractionating an inorganic oxide material and a method for producing an inorganic oxide material.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors thermally analyzed a fluorine-containing mineral, continuously analyzed the generated fluorine-containing gas, and the generation temperature of fluorine was a mineral. We thought that there was a possibility of identifying fluorine-containing minerals. Therefore, in order to achieve the above object, the sample containing fluorine is thermally hydrolyzed while quantitatively raising the temperature, and the fluorine in the generated gas is analyzed by an analyzer (more preferably, equipped with an excitation mechanism by helium plasma). The present inventors have invented a method for quantifying fluorine-containing minerals in a sample for each type by continuously measuring using an analytical device. The method according to the present invention is simple and rapid, and enables fine separation of materials at the production site of inorganic oxide materials.

The summary of this invention completed based on the said knowledge is as follows.
(1) A method of extracting fluorine in a fluorine-containing inorganic oxide material into a carrier gas and quantitatively analyzing the fluorine by mineral type, the step of humidifying the carrier gas, and the humidified carrier gas, The fluorine-containing inorganic oxide material is introduced into a furnace in which the fluorine-containing inorganic oxide material is held, and the fluorine-containing inorganic oxide material is thermally hydrolyzed by heating the furnace in a range from room temperature to 1200 ° C. A step of extracting fluorine in the inorganic oxide material into the carrier gas as a fluoride gas, and analyzing the carrier gas containing the extracted fluoride gas to measure the fluorine content in the carrier gas A hydrolyzed fluorine-containing mineral species from the measured thermal hydrolysis temperature, and quantifying the fluorine-containing mineral amount from the measured fluorine content Mineral type method for quantitative analysis of fluorine.
(2) The fluorine mineral type quantitative analysis method according to (1), wherein in the step of measuring the fluorine content, the fluoride gas is excited by helium plasma to quantitatively analyze the fluorine content.
(3) The fluorine mineral type quantitative analysis method according to (1) or (2), wherein the fluorine-containing inorganic oxide material is steel slag.
(4) A system for extracting fluorine in a fluorine-containing inorganic oxide material into a carrier gas and quantitatively analyzing the fluorine by mineral type, a humidifying unit for humidifying the carrier gas, and the fluorine held inside The humidified carrier gas is introduced into the inorganic oxide material, and the fluorine-containing inorganic oxide material is thermally hydrolyzed by heating in a range from room temperature to 1200 ° C. A heating unit that extracts fluorine in the inorganic oxide material into the carrier gas as a fluoride gas, and an analysis unit that analyzes the carrier gas containing the extracted fluoride gas, and measured heat Fluorine-containing mineral species that are thermally hydrolyzed are identified from the hydrolysis temperature, and the amount of fluorine-containing minerals is quantified from the measured fluorine content. Analysis system.
(5) The fluorine mineral type quantitative analysis system according to (4), wherein the analysis unit excites the fluoride gas with helium plasma to quantitatively analyze the fluorine content.
(6) The inorganic oxide material is analyzed by the fluorine mineral type quantitative analysis method according to any one of (1) to (3), and according to the type and content of the obtained fluorine-containing mineral species. A method for separating an inorganic oxide material, wherein the inorganic oxide material is separated.
(7) Fluorine mineral type determination step for quantifying the amount of fluorine-containing mineral in the inorganic oxide material by the fluorine mineral type quantitative analysis method according to any one of (1) to (3), and the fluorine mineral A step of obtaining a water-soluble fluorine concentration index from the type quantification result, and fluorine that insolubilizes the fluorine-containing mineral in the inorganic oxide material with respect to water when the water-soluble fluorine concentration index exceeds a certain reference value. A method for producing an inorganic oxide-based processed material, comprising: a roadbed material for road paving, a civil engineering material, a building material, a cement raw material, a fertilizer, and a refractory. .

  The present invention is a method in which a fluorine-containing mineral is thermally decomposed according to temperature by a thermal hydrolysis method, and a gas containing a generated fluoride is analyzed, and the fluorine mineral species can be quantitatively analyzed by simple and rapid measurement. Can know. Therefore, it is possible to estimate the possibility of fluorine elution by applying it to environmental impact surveys during civil engineering work. In addition, by obtaining information for each mineral species, it is possible to sort the inorganic oxide material, or to control the mineral oxide to hardly elute fluorine in the manufacturing process of the inorganic oxide material.

It is a mimetic diagram showing an example of an analysis system concerning an embodiment of the present invention. It is the graph which showed the fluoride gas generation | occurrence | production behavior at the time of thermal hydrolysis of fluorite. It is the graph which showed the fluoride gas generation | occurrence | production behavior at the time of thermal hydrolysis of caspidine. It is the graph which showed the fluoride gas generation | occurrence | production behavior at the time of thermal hydrolysis of fluoroapatite. It is a part of the flow when manufacturing a roadbed material for road pavement and the like using an inorganic oxide material as a raw material. It is the graph which showed the fluoride gas generation | occurrence | production behavior at the time of the thermal hydrolysis of the steel slag 1. It is the graph which showed the fluoride gas generation | occurrence | production behavior at the time of the thermal hydrolysis of the steel slag 2. This is a flow for producing roadbed materials for road paving from steel slag.

  Exemplary embodiments of the present invention will be described below in detail with reference to the accompanying drawings. In the present specification and drawings, components having substantially the same functional configuration are denoted by the same reference numerals, and redundant description is omitted.

  FIG. 1 shows an example of a preferable analysis system in the embodiment of the present invention. The carrier gas is supplied from the inert gas cylinder 1 and the flow rate is controlled by the flow rate regulator 2. A humidifier 3 is installed in the middle of the carrier gas flow path to make the inert gas wet. The sample to be analyzed is inserted into the crucible 6 and then installed in the furnace core tube 5 for flowing the carrier gas. The wet carrier gas and the sample to be analyzed are heated in the tubular furnace 4. That is, in the example shown in FIG. 1, the heating unit that heats the sample to be analyzed includes the tubular furnace 4 and the core tube 5.

  The fluoride hydrolyzed in the tubular furnace 4 is continuously introduced into the helium plasma 8 generated using the helium plasma torch 7 together with the carrier gas and excited. Luminescence or ions 9 generated by excitation are continuously analyzed by a luminescence or ion detector 10. These analysis systems are controlled by a control computer 11. Further, data indicating the temperature state of the tubular furnace 4, data indicating the detection result of light emission or ions in the detection device 10, and the like are output to the control computer 11 as needed.

  The gas used for the thermal hydrolysis is preferably an inert gas such as helium or argon that has no reactivity with the sample. The carrier gas contains the fluoride gas extracted from the sample to be analyzed and is directly introduced into the helium plasma. However, helium is more preferable because it does not interfere with the stable generation of the plasma. The inert gas is preferably 3N grade or higher which does not contain impurity components, particularly fluorine. If the flow rate of helium is too small, the extracted fluoride gas cannot be properly conveyed, and if a large volume is passed too much, the fluoride gas after thermal hydrolysis will be diluted. About 0.3-2.0 L / min is preferable.

  The carrier gas is transported through a pipe, but is humidified by providing a humidifier 3 such as a gas humidifier in the flow path. The humidifier 3 preferably has a pressure / flow rate adjusting function, or has a structure with a small pressure loss / flow rate loss such as a bubbling method or a hollow fiber membrane type humidification method. Further, the humidification amount depends on the amount of fluoride gas expected to be generated from the sample to be analyzed, but it is desirable that the humidification amount be close to the saturated vapor pressure at room temperature. The carrier gas pipe is directly connected to a furnace for heating the sample to be analyzed.

  The furnace for heating the sample to be analyzed is preferably a closed type and has a small internal volume and dead volume as much as possible. More specifically, as shown as a tubular furnace 4 and a core tube 5 in FIG. 1, it is a tubular furnace type and has a cylindrical core tube, a sample is placed at the center, and a carrier gas is introduced from one end. It is desirable that a carrier gas containing a fluoride gas extracted by thermal hydrolysis and extraction be taken from the other end. In addition, the tubular furnace 4 and the core tube 5 can be controlled in temperature from 100 ° C. to 1200 ° C., and equipped with a thermometer such as a thermocouple, and can monitor the actual temperature in the sample to be analyzed or in the vicinity of the sample to be analyzed. Method is desirable. Although the rate of temperature rise depends on the performance of the furnace, if it is too slow, it takes time for analysis, and if it is fast, it becomes difficult to control the soaking of the furnace, so it is desirable to carry out at about 5 to 20 ° C./min.

  The sample to be analyzed is a fluorine-containing inorganic oxide material containing one or more fluorine-containing mineral species. Such a fluorine-containing inorganic oxide material is not particularly limited, and a known material can be used as a sample to be analyzed. One example of such a fluorine-containing inorganic oxide material is steel slag. The sample to be analyzed is inserted into the furnace so that it can be heated uniformly in the soaking zone of the furnace. Note that fluoride gas is not generated quantitatively when the area in contact with the carrier gas is small or when a temperature gradient occurs in the sample to be analyzed. Although it depends on the specifications of the soaking zone of the furnace, for example, the mass of the sample is about 5 to 100 mg, and the finely pulverized product having a size of 75 μm or less is made homogeneous in a container such as an alumina crucible. It is preferable to insert.

Here, the thermal decomposition characteristics of the fluorine-containing mineral will be considered. For example, regarding fluorine-containing minerals that are likely to exist in steel slag, the melting point of fluorite is 1402 ° C., fluoroapatite is 1650 ° C., and caspidine is 1410 ° C., all of which are high temperatures. However, it has been found that all fluorine-containing minerals in slag are thermally decomposed by 1200 ° C. in the thermal hydrolysis method. In this case, fluorine in the fluorine-containing mineral reacts with H ₂ O to form hydrogen fluoride gas as shown in the following reaction formula 1, and is extracted into the carrier gas. Here, in the following reaction formula 1, M represents a metal element contained in the fluorine-containing mineral.

MF _2n + nH ₂ O → MO _n + 2nHF (Reaction Formula 1)

For example, in the case of 20 mg of fluorite, the fluorine content is 9.74 mg, and assuming that it is completely hydrolyzed in 60 minutes under the condition of a carrier gas flow rate of 1.2 L / min, the generated fluoride gas is The average fluorine concentration in the contained carrier gas is about 0.135 mg L- ¹ .

  The carrier gas containing the generated fluoride gas is continuously introduced into the analyzer. The analyzer uses an instrument that can continuously measure the fluorine content in a gas. For example, helium plasma excites and ionizes fluorides at high temperature and high energy to generate atomic emission or fluorine generated from fluorine atoms. An apparatus that continuously and quantitatively measures the mass of ions can be considered. For example, as shown in FIG. 1, such an analyzer includes an apparatus for exciting and ionizing fluoride (for example, a helium plasma torch 7) and an apparatus for detecting generated atomic luminescence and fluorine ions (for example, luminescence or ion emission). And a detection device 10). More specifically, examples of helium plasma include inductively coupled plasma and microwave inductively coupled plasma. In addition, the analysis method includes spectroscopic analysis of luminescence, knowing the element from the luminescence wavelength, knowing its content from the luminescence intensity, and measuring the mass and number of ions generated to identify the element and content. Analytical methods and the like can be mentioned.

  By measuring with the above method and system, the signal intensity reflecting the temperature in the horizontal axis and the fluorine content in the fluoride gas extracted in the carrier gas on the vertical axis can be obtained.

  Here, the example of the generation | occurrence | production profile of the fluoride gas at the time of thermally hydrolyzing a fluorine-containing mineral reagent was shown to FIGS. The thermal hydrolysis temperature of the fluorine-containing mineral reagent varies depending on the mineral. The fluorite shown in FIG. 2 has a profile that starts decomposing at about 550 ° C., reaches a maximum at about 880 ° C. and ends at about 1150 ° C., and caspidine shown in FIG. 3 starts decomposing at about 650 ° C. The profile was maximum at about 970 ° C. and ended at about 1200 ° C. Since the maximum values of the two differ by nearly 100 ° C., it is possible to perform quantitative quantification using a peak separation technique such as deconvolution. On the other hand, the fluoroapatite shown in FIG. 4 started to decompose at about 250 ° C., had multiple peaks at about 380 ° C. and about 520 ° C., and ended at about 730 ° C. Although there is a peak at about 840 ° C. in FIG. 4, the fluoroapatite reagent used this time contains fluorite, which is one of the raw materials at the time of synthesis, as an impurity, as verified by the solid state NMR method. The peak appearing near 840 ° C. is considered to be due to fluorite.

  That is, if there is a difference in the thermal hydrolysis temperature of the fluorine-containing mineral, according to the present invention, the type of the fluorine-containing mineral contained in the sample to be analyzed can be identified. Furthermore, after measuring the fluorine content in the sample to be analyzed, and further specifying the fluorine-containing mineral species in the present invention, from the integral value of the thermal hydrolysis profile of the fluorine-containing mineral species whose content is to be known, The content of the fluorine-containing mineral to be known can be calculated using the formula (1).

(Content of fluorine-containing minerals you want to know)
= (Integrated value of the fluorine-containing mineral profile obtained by peak separation or deconvolution) / (Integrated value of the total fluorine profile) × Fluorine content × (Molecular weight of the fluorine-containing mineral to be known) / (Fluorine to be known) Atomic weight of fluorine in minerals contained) (1)

  Various signal processing, image processing for the signal intensity reflecting the fluorine content in the fluoride gas obtained by the analyzer, and calculation processing of the fluorine-containing mineral content as shown in the above formula (1) For example, it is implemented by an arithmetic processing unit such as the control computer 11 or various servers or computers (not shown) connected to the analysis system. A measurement graph reflecting the temperature in the horizontal axis and the fluorine content in the fluoride gas extracted in the carrier gas on the vertical axis, the calculation result of the content of the fluorine-containing mineral, etc. It is displayed on the display screen of the apparatus or output to a paper medium via a printer or the like. Thereby, the user of the analysis system can grasp the fluorine content of the fluorine-containing mineral on the spot.

Next, the method for separating inorganic oxide materials according to the present invention will be described in detail.
The inorganic oxide material is a raw material for inorganic oxide processing materials such as road pavement materials for road pavement, civil engineering materials, building materials, cement raw materials, fertilizers, and refractories. Specifically, examples of the inorganic oxide material include steel slag obtained in the steel manufacturing process, recycled materials for inorganic oxide processing material factories such as recycled roadbed materials and refractories.

  The environmental properties of inorganic oxide materials depend on the type and content of fluorine-containing minerals. Below, steel slag is mentioned as an example and explained as an inorganic oxide material. Steel slag is roughly classified into steelmaking slag, electric furnace slag, and blast furnace slag. In the case of steelmaking slag and electric furnace slag, fluorine is inevitably mixed from the flux during refining and casting. When it is recycled at slag, it is distributed to the slag side and mixed unavoidably. In addition, inevitably mixed fluorine becomes a problem from the environmental aspect such as elution when steel slag is used as a roadbed material. Similarly, with respect to other inorganic oxide materials, the use and environmental influence of the inorganic oxide-based processed material can be further characterized by separating the inorganic oxide material based on the content of the fluorine-containing mineral. Moreover, by using the inorganic oxide processing material thus sorted, the quality can be further improved, for example, a material having no environmental influence can be shipped.

  Here, the separation of the inorganic oxide material means identifying the inorganic oxide material according to the type and content of the fluorine-containing mineral. Thus, by classifying an inorganic oxide material, when mix | blending an inorganic oxide material and manufacturing a roadbed material etc., a compounding quantity can be determined according to content of a fluorine-containing mineral classification. For example, what is necessary is just to determine the compounding quantity of an inorganic oxide material so that the water-soluble fluorine density | concentration of the inorganic oxide type processing material after a mixing may not exceed a fixed reference value. In addition, inorganic oxide materials identified as having a very high concentration of water-soluble fluorine should be stored strictly so that there is no elution of fluorine into the environment during storage, and in some cases, they may be insolubilized or rendered harmless and discarded. It is possible to safely perform such treatments without harming the environment.

  Unlike the conventional chemical analysis method, the method for measuring the content of fluorine-containing minerals according to the present invention can be measured quickly and is therefore suitable for flow work in factories and the like. In the present embodiment, the type of fluorine-containing mineral is identified in the production line of the factory, and the content of the fluorine-containing mineral is measured.

Next, a method for producing inorganic oxide processing materials such as roadbed materials for road paving, civil engineering materials, building materials, cement raw materials, fertilizers, and refractories proposed by the present invention will be described.
FIG. 5 shows a part of a flow for manufacturing an inorganic oxide processing material such as a road pavement material using an inorganic oxide material as a raw material.

The received inorganic oxide material is crushed or sieved as necessary.
In the fluorine-containing mineral type quantification step, after the treatment such as pulverization and sieving, samples representing each lot are extracted, and the extracted samples are analyzed by the above-described fluorine mineral type quantification analysis method of the present invention.

Next, a water-soluble fluorine concentration index X is calculated from the result of quantification of the fluorine mineral type. The water-soluble fluorine concentration index X is, for example, when n fluorine-containing mineral species are present and the content of each fluorine-containing mineral species is X _i (i = 1 to n), the following formula (2 ). Here, in the following formula (2), a _i was obtained by previously measuring the solubility of each fluorine-containing mineral species in water in consideration of the pH during the dissolution test and the ionic strength of coexisting ions. This is a coefficient calculated from the result.

  When the water-soluble fluorine concentration index X thus obtained falls below a certain reference value, the inorganic oxide material in such a lot is directly subjected to the blending process. Here, in the blending step, the same kind or different kinds of inorganic oxide materials of a plurality of lots are mixed and homogenized. Here, the fixed reference value can be determined in advance as an amount that does not exceed the regulation of the soil environment standard elution amount 0.8 mg / L, for example.

  On the other hand, when it is found that the water-soluble fluorine concentration index X exceeds a certain reference value, the inorganic oxide material of the lot is directed to the fluorine insolubilization process. The inorganic oxide material sent to the fluorine insolubilization treatment is treated by a method as disclosed in Patent Document 4, for example. The fluorine-containing mineral type determination step and the fluorine insolubilization step can be repeated a plurality of times. If the water-soluble fluorine concentration index X falls below a certain reference value as a result of the fluorine-containing mineral type determination performed after the fluorine insolubilization treatment step, the lot is sent to the blending step.

  On the other hand, if the amount of fluorine-containing mineral that is soluble in water is very large, or if it is found that the fluorine insolubilization treatment does not proceed effectively for some reason, the cost required for the fluorine insolubilization treatment is taken into account. The lot is sent to the final disposal process. The inorganic oxide material sent to the final disposal process is strictly controlled and properly disposed of after detoxification treatment such as fluorine separation and insolubilization.

  As shown in FIG. 5, the manufacturing method of the inorganic oxide processing material according to the present embodiment sorts the inorganic oxide material based on the calculated water-soluble fluorine concentration index X, while the inorganic oxide processing material. It can be said that this is a method of manufacturing.

  The production line may be a system that can automatically separate the inorganic oxide material based on the measurement result of the content of fluorine-containing minerals. A system that separates materials may also be used.

  Road pavement materials for road paving, harbor civil engineering materials, building materials, cement raw materials, refractory materials, etc. must not have fluorine elution into the surrounding environment during long-term use. It is important to use an inorganic oxide material having a low content of highly functional fluorine-containing minerals. By carefully managing the environmental impact of inorganic oxide materials, safe and secure shipment of materials becomes possible.

  Examples of the present invention will be described below. In the examples shown below, the fluorine mineral type quantitative analysis method, the fluorine mineral type quantitative analysis system, the method of fractionating inorganic oxide materials containing fluorine-containing minerals, and the inorganic oxide-based processed material according to the present invention This is merely an example of the production method of the present invention, and the fluorine mineral type quantitative analysis method, the fluorine mineral type quantitative analysis system, the method of fractionating inorganic oxide materials containing fluorine-containing minerals, and the inorganic oxide processing according to the present invention The manufacturing method of the material is not limited to the examples shown below.

(Example 1)
In Example 1, the analysis system according to FIG. Helium was used as a carrier gas and water was added with a bubbler. The flow rate of the helium carrier gas was 1.2 L / min. In addition, it was confirmed that the concentration of water contained in helium under the hydration condition was a large excess (100 mg / L or more) for extracting all the fluorine in Example 1 as a fluoride gas. Yes. The mass of the sample subjected to pyrolysis was 20 mg, and it was put in an alumina crucible and pyrolyzed using a tubular furnace equipped with a quartz furnace core tube. The temperature rising rate was about 60 minutes (average 15 ° C./min) from 100 ° C. to 1000 ° C. The temperature rise pattern was measured from time to time using a thermocouple installed in the soaking zone of the furnace.

  Further, fluorine in the generated gas was detected by exciting it with microwave-induced helium plasma having a high-frequency output of 0.7 kW and a plasma gas flow rate of 11 L / min, and measuring the emission of fluorine with an emission spectroscopic analyzer. As for the analysis wavelength of fluorine, we selected 703.747 nm for which the linearity of the calibration curve was good in the previous examination and confirmed the quantitativeness, and by continuously monitoring the emission at 703.747 nm, the fluorine-containing mineral The thermal hydrolysis behavior of was observed.

  Using this system, samples of arbitrary steel slag 1 and steel slag 2 were analyzed. Each sample was sampled with good representativeness and then finely pulverized to 75 μm or less, and was sampled from the finely pulverized sample and used for measurement.

The result of measuring the steel slag 1 is shown in FIG. The fluorine release profile from the actual slag is almost the same as that of the reagent fluorite, and no peaks are observed in other temperature ranges. Therefore, the fluorine-containing mineral in the steel slag 1 is a single-phase fluorite. Was assumed to exist. The content of fluorine in the iron and steel slag 1, so was 0.32Mass% According to the analysis method described in Comparative Example 1, when the chemical structure of fluorite and CaF _2, the content of fluorite about It was calculated to be 0.66 mass% (Table 1).

  Next, the result of measuring the steel slag 2 is shown in FIG. In steel slag 2, peaks assumed to be fluorapatite at about 380 ° C and 520 ° C, peaks assumed to be fluorite at about 870 ° C, and peaks assumed to be caspidine at about 1000 ° C were detected. It was. Assuming that the background assumed to be a crucible blank is removed based on the liner method and that the resulting peak is a composite of multiple peaks, each peak is devolved using a forked function to deconvolute the peaks. Separated and approximated.

As a result, assuming that the sum of all peaks is 1, the total area of peaks having a maximum at about 380 ° C. and about 520 ° C. considered to be fluorine generated from fluoroapatite is 0.33, and fluorine generated from fluorite The area of the peak having a maximum at about 870 ° C. considered to be 0.19 was 0.19, and the area of the peak having a maximum at about 1000 ° C. considered to be caspidine was 0.48. Regarding the chemical structural formula of each mineral, fluoroapatite is Ca ₅ (PO ₄ ) ₃ F, fluorite is CaF ₂ , caspidine is 3CaO · 2SiO ₂ · CaF ₂ , formula (1), and the coating shown in Comparative Example 1 Based on the content of fluorine in the analysis sample, when converted into the content of each mineral, as shown in Table 1, fluorite contains 0.01 mass%, cuspidin contains 0.12 mass%, and fluoroapatite contains 0.23 mass%. Has been calculated.

  In addition, the time required for the measurement was about half a day including sampling, crushing and measurement.

(Comparative Example 1)
Samples of steel slag 1 and steel slag 2 used in Example 1 were collected with good representativeness in the same manner as in Example, and pulverized to 75 μm or less and subjected to thermal decomposition. After trapping in a certain water, the fluorine ions contained in the collected liquid were quantitatively analyzed by ion chromatography. The obtained results are shown in Table 1 as Comparative Example 1. As shown in Table 1, the fluorine content in the steel slag 1 was 0.32 mass%, and the fluorine content in the steel slag 2 was 0.025 mass%. The obtained information relates to the content of fluorine as an element, and information on the mineral type cannot be obtained.

(Comparative Example 2)
About the sample of the steel slag 1 and the steel slag 2 used in Example 1, the cross section was cut and polished, and observed with an electron microscope. In the steel slag 1, focusing on fluorine, a mineral phase coexisting only with calcium was observed, and as shown in Table 1, it was assumed that most of the fluorine contained was contained as fluorite. As for steel slag 2, it is assumed that fluorine coexists with calcium alone or with calcium and silicon and exists as fluorite or caspidine as shown in Table 1. It was unclear what was clear. Furthermore, neither the steel slag 1 nor the steel slag 2 has been able to obtain quantitative information on how much each mineral is contained in the entire sample to be analyzed.

  As is clear from the above results, it is possible to quickly and quantitatively know the fluorine mineral type by using the fluorine mineral type quantitative analysis method and the fluorine mineral type quantitative analysis system according to the embodiment of the present invention. It becomes.

(Example 2)
The manufacturing method of the inorganic oxide processing material which concerns on embodiment of this invention was applied to manufacture of the roadbed material which used the steel slag as a raw material. FIG. 8 shows the manufacturing flow.

  Steel slag generated in the steel manufacturing process was blended and mixed, and then pulverized and sized to obtain a product lot of several hundred to several thousand tons. A sample representative of the lot was sampled, and quantified according to the fluorine-containing mineral type according to Example 1.

  Fluorite, caspidine, and fluoroapatite were detected as fluorine-containing mineral species contained in steel slag. The water-soluble fluorine concentration index X = 0.51Xf + 0.76Xc + 0.29Xfap was calculated with the contents of fluorite, caspidine, and fluoroapatite obtained as a result of the quantification as Xf, Xc, and Xfap, respectively. When the calculated water-soluble fluorine concentration index X exceeded 0.8, the fluorine-containing mineral was treated with fluoroapatite as the fluorine insolubilization treatment to make fluorine relatively insoluble in water. Lots with insufficient production of fluorapatite were separated into different yards for separate management and insolubilized again.

  In addition, the coefficient for each fluorine-containing mineral used in the above formula is the elution with respect to the elution standard of fluorine based on the soil environment standard (elution amount is 0.8 mg / L or less in the elution test at a liquid-solid ratio of 10). In consideration of the pH at the time of testing and the ionic strength of coexisting ions, the solubility of each mineral in water is measured in advance, and calculated from the obtained measurement results.

  For roadbed materials manufactured using only lots satisfying the water-soluble fluorine concentration index X ≦ 0.8, a fluorine elution test was conducted by an elution test defined in Environment Agency Notification No. 46. For about half a year, the fluorine elution amount at the time of inspection of product lots never exceeded the environmental standard and could be shipped as it was.

(Comparative Example 3)
In addition to the methods of Comparative Examples 1 and 2, lots were managed by conducting an elution test of fluorine by an elution test defined in Environment Agency Notification No. 46. It took 8 days to complete all analyzes per lot, and it was impossible to manage all lots. As a result, the confirmation of fluorine insolubilization was not in time, and shipping was sometimes delayed.

(Comparative Example 4)
In order to manufacture roadbed materials using steel slag as a raw material, steel slag was blended and mixed and then pulverized and sized to obtain a product lot of hundreds to thousands of tons. Quantification of fluorine-containing mineral species was not performed, and all lots were insolubilized under the same conditions. As a result of the elution test of fluorine by the elution test stipulated in the Environment Agency Notification No. 46, etc., the amount of eluent exceeding the soil environment standard value was detected and shipped at a rate of 1 per 10 lots. I could not.

  As is apparent from the above results, the inorganic oxide material does not exceed environmental standards by using the method for separating the inorganic oxide material and the method for producing the inorganic oxide-based processed material according to the embodiment of the present invention. It becomes possible to manufacture and ship the processing material appropriately.

  The preferred embodiments of the present invention have been described in detail above with reference to the accompanying drawings, but the present invention is not limited to such examples. It is obvious that a person having ordinary knowledge in the technical field to which the present invention pertains can come up with various changes or modifications within the scope of the technical idea described in the claims. Of course, it is understood that these also belong to the technical scope of the present invention.

  According to the method for quantitative analysis of fluoride mineral type according to the present invention, it is possible to quickly and simply know the fluorine mineral species in the sample to be analyzed as general information, and therefore the environment based on the elution prediction based on the fluorine mineral species. Efficient selection of inorganic oxide materials such as steel slag considering the impact can be implemented. Therefore, the quantitative analysis method of the fluoride mineral type according to the present invention is useful for environmental conservation.

DESCRIPTION OF SYMBOLS 1 Inert gas cylinder 2 Flow regulator 3 Humidifier 4 Tubular furnace 5 Furnace core tube 6 Sample and crucible 7 Helium plasma torch 8 Helium plasma 9 Luminescence or ion 10 Luminescence or ion detection device 11 Control computer

Claims (7)

A method of extracting fluorine in a fluorine-containing inorganic oxide material into a carrier gas and quantitatively analyzing the fluorine by mineral type,
Humidifying the carrier gas;
The humidified carrier gas is introduced into a furnace in which the fluorine-containing inorganic oxide material is held, and the furnace is heated in a range from room temperature to 1200 ° C. to heat the fluorine-containing inorganic oxide material. Hydrolyzing and extracting the fluorine in the fluorine-containing inorganic oxide material into the carrier gas as a fluoride gas;
Analyzing the extracted carrier gas containing the fluoride gas and measuring the fluorine content in the carrier gas;
Including
A fluorine mineral type quantitative analysis method for identifying a hydrolyzed fluorine-containing mineral species from a measured thermal hydrolysis temperature and quantifying the amount of the fluorine-containing mineral from the measured fluorine content.   The fluorine mineral type quantitative analysis method according to claim 1, wherein in the step of measuring the fluorine content, the fluoride gas is excited by helium plasma to quantitatively analyze the fluorine content.   The method according to claim 1 or 2, wherein the fluorine-containing inorganic oxide material is steel slag. A system for extracting fluorine in a fluorine-containing inorganic oxide material into a carrier gas and quantitatively analyzing the fluorine by mineral type,
A humidifying section for humidifying the carrier gas;
The humidified carrier gas is introduced into the fluorine-containing inorganic oxide material held inside, and the fluorine-containing inorganic oxide material is heated in a range from room temperature to 1200 ° C. A heating unit for decomposing and extracting fluorine in the fluorine-containing inorganic oxide material as a fluoride gas into the carrier gas;
An analysis unit for analyzing the carrier gas containing the extracted fluoride gas;
With
A fluorine mineral type quantitative analysis system for identifying a hydrolyzed fluorine-containing mineral species from a measured thermal hydrolysis temperature and quantifying the amount of the fluorine-containing mineral from the measured fluorine content.   5. The fluorine mineral type quantitative analysis system according to claim 4, wherein the analysis unit excites the fluoride gas with helium plasma to quantitatively analyze the fluorine content. The inorganic oxide material is analyzed by the fluorine mineral type quantitative analysis method according to any one of claims 1 to 3,
A method for separating an inorganic oxide material, wherein the inorganic oxide material is separated according to the type and content of the obtained fluorine-containing mineral species. Fluorine mineral type quantification step for quantifying the amount of fluorine-containing mineral in the inorganic oxide material by the fluorine mineral type quantitative analysis method according to any one of claims 1 to 3,
A step of calculating a water-soluble fluorine concentration index from the result of mineral type quantification of the fluorine;
A fluorine insolubilization treatment step for insolubilizing the fluorine-containing mineral in the inorganic oxide material with respect to water when the water-soluble fluorine concentration index exceeds a certain reference value;
Including
A method for producing an inorganic oxide-based processed material, comprising producing any one or more of roadbed materials for road paving, civil engineering materials, building materials, cement raw materials, fertilizers, and refractories.

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