JP2018070441A - Iron oxide for red pigment and for catalyst, and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an iron oxide which has excellent color tone and thermal resistance, and to provide a pigment containing the same.SOLUTION: This invention relates to an iron oxide which contains at least one element chosen from the group consisting of aluminum, zirconium, ruthenium, titanium, and hafnium. The iron oxide is in a tube or rod shape and an elemental ratio of the element is 5% or more and less than 25% by atomic number (assuming that the sum total of percent by atomic number of main elements except oxygen, carbon, nitrogen, and hydrogen is 100). This invention further relates to a pigment containing the iron oxide.SELECTED DRAWING: None

Description

  The present invention relates to iron oxide containing various elements, a method for producing the iron oxide, and a pigment containing the iron oxide. Furthermore, the present invention relates to a composite containing various elements and a catalyst including the composite.

Currently, commercially available red iron oxide α-Fe ₂ O ₃ (hematite) has a problem in heat resistance. For example, when hematite is used as an overpainting pigment, it is mixed with a glass glaze and heated at about 800 ° C., but this heating reduces the color tone. This decrease in color tone is because hematite particles aggregate due to reheating and the particle size increases.

  In order to improve color tone and heat resistance, the present inventors have developed powdered Al solid solution hematite (Patent Document 1, Non-Patent Document 1). Although the Al solid solution effect on hematite is remarkable, there is a problem that the Al solid solution effect has a limit in order to further improve the color tone.

  Further, the present inventors have developed red iron oxide having a shape (tube shape) that is completely different from conventional powdered red iron oxide (Non-patent Document 2). This tube-shaped red iron oxide is a tube-shaped iron oxide (component ratio Fe: Si: P = 73: 22: 5) produced by microorganisms that exist in nature (iron-oxidizing bacteria Leptothrix ochracea). It is obtained by heating at about 800 ° C., and not only exhibits excellent color tone, but also has excellent heat resistance. The reason for the excellent color tone of this tubular red iron oxide is due to (i) Si solid solution effect, (ii) tube form, and the like.

  This natural tube-shaped red iron oxide has almost constant constituent element ratio, and the solid solution amount of Si or P element does not change, so the color tone also depends only on the heating temperature, and if the heating temperature is constant, the hue Cannot be changed.

Amides such as acrylamide include, for example, flocculants, paper strength enhancers, paints, crude oil mining chemicals, petroleum (crude oil) enhanced recovery chemicals, lubricants, plasticizers, mold release agents, antifoaming agents, vitamin B ₃ components It is an important compound used in a wide variety of applications such as ingredients. As a method for producing such amides, a method of reacting nitriles with water in the presence of a catalyst is known, and a method using a solid catalyst, a biocatalyst or a metal complex catalyst is mainly used.

  Solid catalysts are generally excellent in heat resistance and have the advantage that they can be recovered and reused, and are widely used in the industrial production of chemicals. New solid catalysts for use in the production of amides have been developed (for example, Patent Document 2, Non-Patent Documents 3 and 4).

  Non-Patent Document 3 and Patent Document 2 report a nitrile hydration reaction using a catalyst in which ruthenium hydroxide is supported on gamma alumina. In this catalyst preparation method, when it is supported on gamma alumina, it is necessary to accurately adjust the pH using sodium hydroxide, which is a strong alkali, and the operation is complicated and a large amount of pH 13.2 generated by the adjustment is required. A strong alkali waste liquid needs to be separately neutralized, and has a disadvantage that the amount of by-products and waste water during catalyst preparation is extremely large. In addition, it is necessary to prepare gamma alumina as a carrier having a special surface area, and the preparation of the carrier is complicated.

  Non-Patent Document 4 reports a nitrile hydration reaction with a ruthenium solid catalyst using chitin, chitosan or cellulose obtained from nature as a carrier. In this catalyst preparation method, it is necessary to heat to 50 ° C. when ruthenium is supported on a carrier of chitin, chitosan or cellulose. Furthermore, this catalyst preparation method requires the use of sodium borohydride. Since sodium borohydride reacts with water to generate hydrogen, it is necessary to pay close attention to storage. Further, when preparing the catalyst, an inert atmosphere in which oxygen is blocked is necessary, and the preparation apparatus becomes complicated. In addition, wastewater discharged during the washing of sodium borohydride added during preparation exhibits strong alkalinity and requires a neutralization step, which requires a large amount of acid, and inorganic salts are by-produced during neutralization. It becomes.

  Non-Patent Document 5 describes an example of development of an industrial Beckmann rearrangement reaction, and reports a gas phase Beckmann rearrangement reaction using a solid catalyst of high silica zeolite. The Beckmann rearrangement described in Non-Patent Document 5 is characterized in that it is carried out in the gas phase, and because it is a reaction under neutral conditions, unnecessary inorganic salts such as sodium sulfate are not by-produced. However, because of the gas phase, the reaction temperature is 350 ° C. That is, a large amount of energy for heating is required to ensure a reaction temperature of 350 ° C., and a solid catalyst that undergoes Beckmann rearrangement under neutral conditions at a lower temperature is demanded. Since the raw material oxime does not vaporize at lower temperatures, a solid catalyst that operates under neutral conditions that can cause Beckmann rearrangement in the liquid phase is required from an industrial viewpoint.

  Patent Document 3 describes a method for producing a carbonyl compound using a ruthenium complex catalyst. This method requires a pressure autoclave because 0.8 MPa of hydrogen is required in the production of the complex catalyst, and there is no mention of catalyst recovery since the catalyst is soluble in the liquid phase.

Japanese Patent No. 03728505 Japanese Unexamined Patent Publication No. 2005-170821 JP 2001-240595 A

ACS Applied Materials & Interfaces, 6 (22), 20282-20289 (2014). Dyes and Pigments, 95 (3), 639-643 (2012) Angew. Chem. Int. Ed., 43 (12), 1576-1580 (2004) RSC Adv., 5 (16), 12152-12160 (2015) Catalyst, 43 (7), 555-558 (2001)

  An object of this invention is to provide the iron oxide which has the outstanding color tone and heat resistance, the manufacturing method of this iron oxide, and the pigment containing this iron oxide. Furthermore, an object of the present invention is to provide a complex that can be easily prepared and has high catalytic activity, and a catalyst containing the complex.

  In order to adjust and improve the color tone of the tubular red iron oxide, it is necessary to introduce factors other than the heating temperature. As a result of intensive studies to achieve the above object, the present inventors have produced an organic pod by culturing a bacterium belonging to the genus Leptolith, and then the cell is maintained by holding the organic pod in an aqueous solution containing various elements. It was found that element-containing tubular iron oxide can be obtained by adsorbing even elements harmful to growth. Thus, it has been found that the color tone can be improved by using various types of elements in the tube-shaped iron oxide, and further, it can be used as a catalyst.

  The present invention has been completed based on these findings and has been completed. The present invention provides the following iron oxide, iron oxide production method, pigment, composite, and catalyst.

(I) Iron oxide
(I-1) Iron oxide containing at least one element selected from the group consisting of aluminum, zirconium, ruthenium, titanium and hafnium,
The shape is tube or rod,
The element ratio of the element is 5% or more and less than 25% in terms of atomic% (here, the total of atomic% of main elements excluding oxygen, carbon, nitrogen and hydrogen is 100) iron oxide.
(I-2) The iron oxide according to (I-1), further containing silicon and / or phosphorus.
(I-3) The iron oxide according to (I-1) or (I-2), which contains α-Fe ₂ O ₃ .
(I-4) The iron oxide according to any one of (I-1) to (I-3), wherein the element ratio is before or after heat treatment of iron oxide.

(II) Iron oxide production method
(II-1) A method for producing iron oxide containing at least one element selected from the group consisting of aluminum, zirconium, ruthenium, titanium and hafnium, comprising the following steps:
(1) producing an organic sheath by culturing iron-oxidizing bacteria; and
(2) The organic sheath obtained in step (1) is suspended in an aqueous solution containing at least one element selected from the group consisting of aluminum, zirconium, ruthenium, titanium and hafnium, and iron, and contains the element. A step of producing iron oxide.
(II-2) The method according to (II-1), further comprising the following steps:
(3) A step of heat-treating the iron oxide obtained in step (2).
(II-3) The method according to (II-2), wherein the temperature of the heat treatment is 600 to 1000 ° C.
(II-4) The method according to any one of (II-1) to (II-3), further comprising the following steps:
(4) A step of pulverizing the iron oxide obtained in the step (2) or (3).
(II-5) The method according to any one of claims (II-1) to (II-4), wherein the iron-oxidizing bacterium is a bacterium belonging to the genus Leptolyx.
(II-6) The iron-oxidizing bacterium is Leptothrix cholodnii OUMS1 (NITE BP-860), according to any one of claims (II-1) to (II-4). Method.

(III) Pigment
(III-1) A pigment containing iron oxide according to any one of (I-1) to (I-4).

(IV) Complex
(IV-1) A composite comprising a metal oxide containing at least one element selected from the group consisting of aluminum, zirconium, ruthenium, titanium and hafnium, and an organic sheath,
The shape is tube or rod,
A complex in which the element ratio of the element is 5% or more in terms of the number of atoms (here, the sum of the number of atoms of the main elements excluding oxygen, carbon, nitrogen, and hydrogen is 100).
(IV-2) The composite according to (IV-1), further comprising iron oxide as the metal oxide.
(IV-3) The iron oxide according to (IV-1) or (IV-2), further containing silicon and / or phosphorus.
(IV-4) A method for producing a composite comprising a metal oxide containing at least one element selected from the group consisting of aluminum, zirconium, ruthenium, titanium and hafnium and an organic sheath, including the following steps:
(1) producing an organic sheath by culturing iron-oxidizing bacteria; and
(2) The organic sheath obtained in step (1) is suspended in an aqueous solution containing at least one element selected from the group consisting of aluminum, zirconium, ruthenium, titanium and hafnium, and metal oxidation containing the element The process of producing a thing.

(V) Catalyst
(V-1) A hydration catalyst used in a hydration reaction, comprising the complex according to any one of (IV-1) to (IV-3).
(V-2) The hydration catalyst according to (V-1), which is used for hydration of nitriles.
(V-3) The nitrile is an aliphatic nitrile having 1 to 30 carbon atoms which may have a substituent, or an aromatic nitrile having 6 to 30 carbon atoms which may have a substituent. The hydration catalyst as described in V-2).
(V-4) The hydration catalyst according to (V-2) or (V-3), wherein the nitrile is acrylonitrile, methacrylonitrile, 3-cyanopyridine, or polyacrylonitrile.
(V-5) A process for producing an amide comprising the following steps:
A mixture of a nitrile and water and / or an organic solvent, to which the hydration catalyst according to any one of (V-1) to (V-4) is added, at a temperature of 0 to 200 ° C, 0.1 to The process of reacting for 48 hours.
(V-6) A catalyst used for the Beckmann rearrangement reaction, comprising the complex according to any one of (IV-1) to (IV-3).
(V-7) A process for producing an amide comprising the following steps:
A step of reacting a mixture of an oxime and water and / or an organic solvent, to which the catalyst described in (V-6) is added, at a temperature of 0 to 200 ° C. for 0.1 to 48 hours.
(V-8) A dehydrogenation catalyst for producing a carbonyl compound by dehydrogenation of an alcohol, comprising the complex according to any one of (IV-1) to (IV-3).
(V-9) The dehydrogenation catalyst according to (V-8), wherein the alcohol is an aliphatic alcohol having 1 to 30 carbon atoms which may have a substituent.
(V-10) A method for producing a carbonyl compound comprising the following steps:
A step of reacting an alcohol, to which the catalyst described in (V-8) or (V-9) is added, at a temperature of 0 to 300 ° C. for 0.1 to 48 hours.

  According to the present invention, elements contained in iron oxide produced by microorganisms can be controlled in type and content, and even elements harmful to cell growth can be contained, and do not exist in nature. Iron oxide can be produced. By controlling the kind and content of the element to be contained and the temperature of the heat treatment, iron oxide having excellent color tone and heat resistance can be produced.

  The complex of the present invention has high catalytic activity and can be used for nitrile hydration reaction, Beckmann rearrangement reaction, and carbonyl compound production by dehydrogenation of alcohols. There is no need for pH adjustment at the time of preparing the composite of the present invention, and therefore there is an advantage over the solid catalyst used in the conventional hydration reaction in that there is no by-product of waste water and inorganic salts generated during neutralization. Furthermore, since it can be prepared at room temperature without the need for heating at the time of preparation of the composite, there is no consumption of heat energy and it is more economical than conventional solid catalysts used in hydration reactions.

  The complex of the present invention can undergo a Beckmann rearrangement reaction in a liquid phase and under neutral conditions. In addition, the composite of the present invention has an advantage over the conventional dehydrogenation catalyst in that a pressure-resistant autoclave is not required at the time of production and can be reused.

It is a graph which shows the relationship between the culture | cultivation days of OUMS1 strain | stump | stock in a Si addition culture medium (left) or Al addition culture medium (right), and the number of viable bacteria. ●: 0 mM, ■: 0.05 mM, ◆: 0.5 mM, ▲: 5 mM (A) SEM image and (b)-(e) element mapping images of Al-containing BIOX. It is an XRD pattern of Al-containing BIOX. They are the STEM image (left), electron diffraction pattern (center), and high-resolution TEM image (right) of Al-containing BIOX. It is a graph which shows the relationship between Al concentration (mM) in a culture medium, and the main element composition ratio (at%) in Al containing BIOX. It is a SEM image of Al containing BIOX in each Al concentration (0 mM, 1 mM, 10 mM) in a culture medium. FIG. 4 is a graph (upper) showing a ^* , b ^* , and L ^* values after heat treatment of Al-containing BIOX, natural BIOX and MC55, and a photograph (lower) showing color tone change with heating temperature. It is a graph which shows a ^* , b ^* , L ^* value before and behind reheating of Al content BIOX, natural type BIOX, and MC55. ○: 800 ℃, heated for 2 hours → ●: 800 ℃, reheated for 2 hours It is an XRD pattern after heat treatment of Al-containing BIOX. It is the SEM image before and behind crushing of Al-containing BIOX and natural BIOX. It is a graph which shows the a ^* , b ^* , L ^* value after heat processing of what crushed Al-containing BIOX and natural type BIOX, and what was not grind | pulverized. It is a graph which shows the a ^* , b ^* , L ^* value after heat processing of Al containing BIOX and Al (20 mol%) containing synthetic iron oxide. It is the SEM image (left) and element mapping image (right) of Zr containing BIOX. It is a XRD pattern of Zr containing BIOX. 2 is a graph showing the relationship between the Zr concentration (mM) in a medium and the composition ratio (at%) of main elements in Zr-containing BIOX. It is a SEM image of Zr containing BIOX in each Zr density | concentration (0 mM, 1 mM, 2 mM, 10 mM) in a culture medium. A graph showing the a ^* , b ^* and L ^* values after heat treatment of Zr-containing BIOX, natural BIOX and MC55 (top), and a photograph showing the color tone after heat treatment (bottom). It is a XRD pattern after heat processing of Zr containing BIOX. It is a SEM image after heat processing of Zr containing BIOX. It is a SEM image of Ru containing BIOX in each Ru density | concentration (1 mM, 5 mM) in a culture medium. The inset is an enlarged view of the end of BIOX.

  Hereinafter, the present invention will be described in detail.

  In the present specification, “comprise” includes the meaning of “essentially consist of” and the meaning of “consist of”.

  In this specification, iron oxides produced by iron-oxidizing bacteria may be referred to as “BIOX (Biogenous Iron oxides)”, and iron oxides produced by iron-oxidizing bacteria in a natural environment are referred to as “natural BIOX”. The iron oxide produced by culturing the isolated iron-oxidizing bacteria may be referred to as “culture system BIOX”.

  In this specification, “sheath-like” and “tube-like” are terms that mean the same shape, and mean a round, elongated, hollow shape. Further, in the present specification, the “rod shape” means a shape that is round and thin and not hollow.

<Iron oxide>
The iron oxide of the present invention contains at least one element selected from the group consisting of aluminum (Al), zirconium (Zr), ruthenium (Ru), titanium (Ti) and hafnium (Hf),
The shape is tube or rod,
The element ratio of the element is 5% or more and less than 25% in terms of atomic% (here, the total of atomic% of main elements excluding oxygen, carbon, nitrogen, and hydrogen is 100).

In the present invention, “iron oxide” means iron oxide in a narrow sense exemplified by α-Fe ₂ O ₃ , β-Fe ₂ O ₃ , γ-Fe ₂ O ₃ , Fe ₃ O ₄ , α-FeOOH, It is a general term for compounds containing iron and oxygen as components, including iron oxyhydroxides such as β-FeOOH and γ-FeOOH, and iron hydroxides with an amorphous structure typified by ferrihydrite. . The “iron oxide” in the present invention includes those containing components other than iron and oxygen. Such components other than iron and oxygen include, for example, silicon (Si), phosphorus (P), sulfur (S), carbon (C), nitrogen other than Al, Zr, Ru, Ti and Hf described above. (N), hydrogen (H), and the like, and the iron oxide of the present invention preferably contains silicon and / or phosphorus. The “iron oxide” in the present invention may contain an organic substance such as an organic sheath.

  The iron oxide of the present invention may be either amorphous or microcrystalline (for example, ferrihydrite, lepidochrosite).

  The iron oxide of the present invention can be used as a pigment when it contains Al, Zr, Ti and Hf, and as a catalyst when it contains Al, Zr, Ru and Ti. Al, Zr, Ru, Ti and Hf contained in the iron oxide of the present invention can be contained even in a solid solution state.

  The element ratio of Al, Zr, Ru, Ti and Hf contained in the iron oxide of the present invention is 5% or more and less than 25%, preferably 10% or more and less than 25%, more preferably 15% or more and 25% in terms of the number of atoms. Is less than 20%, particularly preferably 20% or more and less than 25% (here, the sum of the atomic percentages of main elements excluding oxygen, carbon, nitrogen and hydrogen is 100). The element ratio here means the total element ratio of Al, Zr, Ru, Ti, and Hf. The main elements excluding oxygen are Fe, P, Si, S, Al, Zr, Ru, Ti, Hf, etc., and at least the number of atoms in oxygen oxide other than oxygen, carbon, nitrogen and hydrogen is at least%. Means 1%. The element ratio is that before or after heat treatment of iron oxide.

  The shape of the iron oxide of the present invention is tube-shaped or rod-shaped, and the normal size of each shape is tube-shaped: diameter 0.1-2 μm, length 1-1000 μm, rod-shaped: length 1-1000 μm. is there.

When the iron oxide of the present invention contains α-Fe ₂ O ₃ (hematite), it becomes red and can be suitably used as a red pigment. The color of the iron oxide of the present invention (preferably iron oxide containing α-Fe ₂ O ₃ ) is preferably a ^* (reddish) of 25 or more, more preferably 30 to 50, and b ^* (yellowish) of preferably 25. As mentioned above, More preferably, it is 30-50, L ^* (lightness) becomes like this. Preferably it is 30 or more, More preferably, it is 40-50. The parameters L ^* , a ^* and b ^* here are specified in the color space called CIE1976 L ^* a ^* b ^* color system recommended by the International Commission on Illumination (CIE) in 1976. It can be measured by the method described in the examples. The visual color of the iron oxide of the present invention is bright yellowish red.

The iron oxide of the present invention can be produced by carrying out the following steps.
(1) producing an organic sheath by culturing iron-oxidizing bacteria; and
(2) The organic sheath obtained in step (1) is suspended in an aqueous solution containing at least one element selected from the group consisting of aluminum, zirconium, ruthenium, titanium and hafnium, and iron, and contains the element. A step of producing iron oxide.

  The iron-oxidizing bacterium is not particularly limited as long as it produces an organic sheath. Examples of the iron-oxidizing bacterium that produces such an organic sheath include a Leptothrix sp. And a Sphaerotilus sp. Among them, iron-oxidizing bacteria isolated so as to be able to be artificially cultured can be preferably used. Specific examples of the genus Bacteria belonging to the genus Leptotrix include the Leptotrix Korodini SP-6 strain and the Leptotrix Korodini OUMS1 strain. The Leptothrix Korodini OUMS1 strain was established on December 25, 2009 by the National Institute for Product Evaluation Technology Patent Microorganisms Deposit Center (2-5-8 Kazusa Kamashi, Kisarazu City, Chiba Prefecture, Japan) ) Under the deposit number NITE P-860. This strain has now been transferred to an international deposit and its deposit number is NITE BP-860.

The “organic sheath” in the present invention means a sheath-like structure formed outside of the cell by iron-oxidizing bacteria belonging to β-proteobacteria such as a bacterium belonging to the genus Leptothrix or genus Spherocillus, and this structure is linked. It is a high molecular polymer in which fine fibers composed of heteropolysaccharide and protein secreted on the outer periphery of a cell-like cell are closely woven (see the following documents 1 to 3).
Reference 1: Emerson, D., and Ghiorse, WC (1993) Ultrastructure and chemical composition of the sheath of Leptothrix discophora SP-6. J. Bacteriol. 175: 7808-7818.
Reference 2: Takeda, M., Makita, H., Ohno, K., Nakahara, Y., and Koizumi, J. (2005) Structural analysis of the sheath of a sheathed bacterium, Leptothrix cholodnii. Int'l. Biol. Macromole 37: 92-98.
Reference 3: Kunoh, T., Kunoh, H., and Takada, J. (2015) Perspectives on the Biogenesis of Iron Oxide Complexes Produced by Leptothrix, an Iron-oxidizing Bacterium and Promising Industrial Applications for their Functions. J. Microb. Biochem. Technol. 7: 419-426.

  The culture conditions of the iron-oxidizing bacteria in step (1) are not particularly limited as long as an organic sheath can be generated, and the type of culture medium, culture temperature, culture time, etc. can be appropriately set according to the type of iron-oxidizing bacteria. . As culture | cultivation temperature, 15-30 degreeC is mentioned normally, Preferably 20-25 degreeC can be mentioned. The culture time can be usually about 1 to 35 days, preferably about 2 to 21 days. The culture may be either solid culture or liquid culture, preferably liquid culture. Liquid culture can be performed by shaking culture, stirring culture, aeration culture, or the like. Examples of the medium include SGP medium used in the examples.

In order to contain aluminum, zirconium, ruthenium, titanium and hafnium in the aqueous solution used in step (2), examples of the compound added to the aqueous solution include aluminum chloride, aluminum nitrate, aluminum sulfate, potassium aluminum sulfate, and chloride. Zirconium (IV), zirconium oxide, zirconium oxychloride, ruthenium (III) chloride, ruthenium (II) chloride, bis (dimethylsulfoxide), ruthenium (VIII) oxide, RuCl ₂ (CO) ₂ (P (mC ₆ H ₄ SO _{3 Na) 3) 2, [(} C 5 R 5) RuCl (PTA) 2] (R = H, Me; PTA = 1,3,5-triaza-7-phosphaadamantane), titanium chloride (III), titanium chloride ( IV), titanium oxysulfate, hafnium chloride (IV), hafnium oxide, hafnium oxychloride, and hydrates thereof. The concentration of these compounds is usually 0.1 to 100 mM, preferably 0.5 to 20 mM. In order to contain iron in the aqueous solution used in step (2), examples of the compound added to the aqueous solution include iron (II) sulfate, iron (III) sulfate, iron (II) chloride, iron chloride. (III), iron nitrate (II), iron nitrate (III), iron acetate (II), iron acetate (III), iron citrate (III), hydrates thereof, iron pieces, iron powder, etc. .

  Examples of the aqueous medium used in the step (2) include a buffer (e.g., acetate buffer, phosphate buffer, citrate buffer, citrate phosphate buffer, borate buffer, Tris buffer, HEPES Buffer), medium (for example, SGP medium) and the like. Further, the medium cultured in the step (1) can be continuously used as an aqueous medium. The pH of the aqueous solution is not particularly limited, and can be appropriately set according to the type of target iron oxide.

  The formed organic sheath can be directly suspended in the aqueous solution, or can be suspended in the aqueous solution after lysing the formed organic sheath with lysozyme or the like.

  The conditions for the suspension are not particularly limited, and the temperature, time, and the like can be appropriately set according to the type of the target iron oxide. Moreover, when performing suspension, shaking operation, stirring operation, etc. can be performed as needed.

  By suspending the organic sheath in the aqueous solution, aluminum, zirconium, ruthenium, titanium, and hafnium can be adsorbed on the organic sheath to produce iron oxide containing (solid solution) these elements. By going through these two steps, even elements harmful to cell growth can be contained in iron oxide. In addition, by adjusting the type and concentration of the element in the aqueous solution, it is possible to control the type and content of the element contained in the iron oxide of the present invention. Iron can be made.

In the production of the iron oxide of the present invention, in addition to the above steps (1) and (2), a step of (3) a heat treatment of the iron oxide obtained in the step (2) can also be carried out. By performing such heat treatment, α-Fe ₂ O ₃ (hematite) is formed in the iron oxide, and the iron oxide becomes red. Such red iron oxide can be suitably used as a red pigment.

The temperature of the heat treatment is preferably 600 to 1000 ° C, more preferably 650 to 950 ° C, still more preferably 700 to 900 ° C, and the heat treatment time is preferably 0.1 to 200 hours, more preferably 1 ~ 120 hours. High a ^* , b ^* and L ^* values can be obtained if the temperature and time of the heat treatment are in this range. The heat treatment is usually performed in the atmosphere. The desired a ^* , b ^* , and L ^* values can be obtained by controlling the temperature and time of the heat treatment.

  Prior to the heat treatment step, a step of washing and drying the iron oxide can be performed.

  In the production of the iron oxide of the present invention, in addition to the above steps, (4) a step of pulverizing the iron oxide obtained in the step (2) or (3) may be further performed.

  By pulverizing iron oxide in this way, the shape of iron oxide is changed from a tube shape or a rod shape to a powder shape. The pulverization can be performed using a known method. As an apparatus which grind | pulverizes, a pin mill, a hammer mill, a ball mill, a jet mill, a roller mill etc. are mentioned, for example.

<Pigment>
The pigment of the present invention contains the above iron oxide.

  When used as a pigment, the iron oxide preferably contains Al, Zr, Ti, and Hf, and more preferably contains Al and Zr.

The iron oxide has a high value of a ^* , b ^* , L ^* , and has an unprecedented color tone and color tone, and therefore can be suitably used as a pigment. By controlling the kind and content of the element contained in the iron oxide and the temperature of the heat treatment, iron oxide having such an excellent color tone can be produced. Further, the iron oxide has a slight change in color tone even when reheated, and has high heat resistance. Examples of the use of the pigment include ceramics, paints, paints, inks, and cosmetics.

  The pigment of the present invention may be either one composed only of the iron oxide or one containing a known compounding agent used for the pigment in addition to the iron oxide. The compounding agent can be appropriately selected according to the use of the pigment (for ceramics, for paints, for paints, for inks, for cosmetics, etc.).

  In the cosmetic, a cosmetic base is blended in addition to the iron oxide.

  Cosmetics include all cosmetic compositions applied to animal (including human) skin, mucous membranes, body hair, scalp hair, scalp, nails, teeth, face skin, lips and the like.

  The content of the iron oxide in the cosmetic can be appropriately selected from the range of preferably 0.01 to 100% by weight, more preferably 0.1 to 99% by weight, as the content of the hematite complex.

  Cosmetic bases include, for example, whitening agents, moisturizers, antioxidants, oily components, UV absorbers, surfactants, thickeners, alcohols, powder components, color materials, film-forming polymers, plasticizers, Volatile solvents, gelling agents, aqueous components, water, various skin nutrients, and the like can be mentioned, and they are appropriately blended as necessary.

  Cosmetic dosage forms include solubilization system, aqueous solution system, powder system, emulsification system, oil liquid system, gel system, aerosol system, ointment system, water-oil two-layer system, water-oil-powder three-layer system, etc. A wide range of dosage forms can be taken.

  The use of cosmetics is also arbitrary. For example, for basic cosmetics, face wash, lotion, milky lotion, essence, pack, cream, beauty liquid, gel, mask, etc., for makeup cosmetics, lipstick, foundation, eyeliner, blusher, eye Examples include nail cosmetics, nail polish, top coat, base coat, and light removal liquid. Others include massage agents, facial cleansing agents, cleansing agents, pre-shave lotions, after-shave lotions, and shavings. Examples include creams, body soaps, soaps, shampoos, rinses, hair treatments, hair styling agents, hair restorers, hair art agents, hair manicures, hair colors, antiperspirants, and bath additives.

<Catalyst>
The iron oxide has high catalytic activity, and can be suitably used for carbonyl compound production by hydration reaction of nitriles, Beckmann rearrangement reaction, and dehydrogenation of alcohols.

  When used as a catalyst, the iron oxide preferably contains Al, Zr, Ru and Ti, and more preferably contains Ru.

  The iron oxide is superior to solid catalysts used in conventional hydration reactions because it does not require pH adjustment at the time of preparation, and therefore has no by-product of waste water and inorganic salts generated during neutralization. Furthermore, since the iron oxide can be prepared at room temperature without being heated at the time of preparation, it is excellent in economic efficiency as compared with a solid catalyst used in a conventional hydration reaction without consuming heat energy.

  Since the iron oxide can cause a Beckmann rearrangement reaction in a liquid phase and under neutral conditions, the energy consumption is low and there is no problem of by-products. Further, the iron oxide is superior to the conventional dehydrogenation catalyst in that a pressure-resistant autoclave is not required at the time of production and can be reused.

  In addition, when used as a catalyst, it is not essential that iron is included as a component, so it is not essential to adsorb iron to the organic sheath “selected from the group consisting of aluminum, zirconium, ruthenium, titanium and hafnium. It is possible to use a composite containing a metal oxide containing at least one element and an organic sheath as a catalyst instead of the iron oxide. In this case, “iron oxide” in the present specification is applied by replacing it with “composite”.

  The element ratio of Al, Zr, Ru, Ti and Hf contained in the composite of the present invention is 5% or more, preferably 5% or more and less than 25%, more preferably 10% or more and less than 25%, in addition, the number of atoms%. It is preferably 15% or more and less than 25%, particularly preferably 20% or more and less than 25% (here, the total of the number% of the main elements excluding oxygen, carbon, nitrogen and hydrogen is 100).

Hydration catalyst The hydration catalyst of the present invention comprises the above iron oxide.

  In particular, the iron oxide has a high catalytic activity as a hydration catalyst when amides are produced from nitriles.

  Nitriles to which the hydration catalyst of the present invention can be applied are not particularly limited. For example, each of them may have a substituent, preferably an aliphatic nitrile having 1 to 30 carbon atoms and an aromatic nitrile having 6 to 30 carbon atoms. (The carbon number here does not include carbon of the nitrile group). Specific examples of the aliphatic nitrile include monovalent aliphatic nitriles such as acetonitrile, propionitrile, and butyronitrile, polyvalent aliphatic nitriles such as malononitrile, succinonitrile, adiponitrile, polyacrylonitrile, and polymethacrylonitrile, and acrylonitrile. And unsaturated aliphatic nitriles such as methacrylonitrile. Specific examples of the aromatic nitrile include benzonitrile, 3-cyanopyridine, phthalonitrile, phenylacetonitrile, 3-phenylpropanenitrile, 2-methylbenzonitrile and the like. The hydration catalyst of the present invention is particularly suitable for use in producing acrylamide from acrylonitrile.

  As a method for producing amides by hydrating nitriles using the hydration catalyst of the present invention, a method of adding the catalyst of the present invention to a mixture of nitriles and water and / or an organic solvent and reacting them. Is mentioned. Water and the organic solvent can be used alone or as a mixture, preferably water or a mixture. The amount of water and / or organic solvent used at that time (the amount of water used alone, the amount of organic solvent used alone or the amount of mixture of water and organic solvent) is usually 0.1 to 1 mol of nitrile group. The amount is 10,000 mol, preferably 0.5 to 1000 mol, more preferably 1 to 100 mol. If the usage-amount of water and / or an organic solvent is this range, the fall of the yield of the amide manufactured can be prevented.

  Moreover, reaction temperature can be selected from the range of 0-200 degreeC, Preferably it is 30-180 degreeC, More preferably, it is 40-180 degreeC. If it is reaction temperature of this range, reaction rate will not fall, and problems, such as decomposition | disassembly of a catalyst component and an increase in manufacturing cost, will not arise. The reaction time is usually 0.1 to 48 hours, preferably 0.1 to 24 hours, more preferably 1 to 24 hours.

  The reaction pressure is arbitrary as long as the reaction system is maintained at a liquid phase, and a pressure vessel is not required when the reaction proceeds at a temperature below the boiling point of water. When the operation is performed in a closed system, an inert gas such as nitrogen, argon, helium or carbon dioxide can be used as the atmosphere. The reaction can be carried out either batchwise or continuously. From the reaction product liquid, the product amide compound can be recovered by methods such as distillation and crystallization. In addition, since the catalyst is dissolved in the remaining liquid after the product is recovered (for example, the filtrate after the precipitated amide compound is filtered), it may be directly or indirectly circulated and used again for the reaction. The catalyst can be recovered if desired.

Catalyst used for Beckmann rearrangement The catalyst used for the Beckmann rearrangement of the present invention is characterized by containing the above iron oxide.

  The oxime to which the catalyst of the present invention can be applied is not particularly limited, and examples thereof include an aliphatic oxime having 1 to 30 carbon atoms and an aromatic oxime having 6 to 30 carbon atoms, each of which may have a substituent. (The carbon number here does not include the carbon of the oxime group). Specific examples of the aliphatic oxime include acetone oxime, methyl ethyl ketone oxime, cyclohexanone oxime, and cyclododecanone oxime. Specific examples of the aromatic oxime include α-benzaldoxime, acetophenone oxime, and benzophenone oxime.

  As a method for producing amides by rearrangement of oximes by Beckmann rearrangement reaction using the catalyst of the present invention, the catalyst of the present invention is added to a mixture of oximes and water and / or an organic solvent and reacted. A method is mentioned. Water and the organic solvent can be used alone or as a mixture.

  Moreover, reaction temperature can be selected from the range of 0-200 degreeC, Preferably it is 30-180 degreeC, More preferably, it is 40-180 degreeC. If it is reaction temperature of this range, reaction rate will not fall, and problems, such as decomposition | disassembly of a catalyst component and an increase in manufacturing cost, will not arise. The reaction time is usually 0.1 to 48 hours, preferably 0.1 to 24 hours, more preferably 1 to 24 hours.

Dehydrogenation catalyst for producing carbonyl compounds by dehydrogenation of alcohols The dehydrogenation catalyst for producing carbonyl compounds by dehydrogenation of alcohols according to the present invention comprises the above iron oxide.

  The alcohol to which the catalyst of the present invention can be applied is not particularly limited, and examples thereof include aliphatic alcohols each having a substituent and preferably having 1 to 30 carbon atoms. Specific examples of the aliphatic alcohol include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, cyclohexanol, and cyclopentanol. Examples thereof include polyhydric aliphatic alcohols such as monohydric alcohol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and glycerol.

  Examples of the method for producing a carbonyl compound by dehydrogenation of alcohols using the catalyst of the present invention include a method in which the catalyst of the present invention is added and reacted with a mixture of alcohols and water and / or an organic solvent. . Water and the organic solvent can be used alone or as a mixture. The reaction can also be performed in a solvent-free system that does not use water and / or an organic solvent.

  The reaction temperature can be selected from the range of 0 to 300 ° C, preferably 30 to 250 ° C, more preferably 40 to 250 ° C. If it is reaction temperature of this range, reaction rate will not fall, and problems, such as decomposition | disassembly of a catalyst component and an increase in manufacturing cost, will not arise. The reaction time is usually 0.1 to 48 hours, preferably 0.1 to 24 hours, more preferably 1 to 24 hours.

  Since the catalyst used in the present invention can proceed with a dehydrogenation reaction of alcohols as it is, a reaction aid such as a hydrogen acceptor for capturing hydrogen by-produced with the progress of the dehydrogenation reaction is used in the reaction system. Although it is not necessary to exist in, it may exist if desired. Moreover, there is no restriction | limiting in particular about the time when this hydrogen acceptor exists in a reaction system, It can exist in any step depending on necessity. Here, the hydrogen acceptor is a compound having a function of promoting dehydrogenation reaction of a raw material compound by having multiple bonds in the molecule and binding to a hydrogen atom extracted from the raw material compound. Specific examples include acetone, benzophenone, diphenylacetylene, methyl vinyl ketone, benzal acetone, ethyl methyl ketone, parabenzoquinone, nitrobenzene, acetonitrile, benzonitrile, vinyl chloride, acetaldehyde, formaldehyde, butyraldehyde, benzaldehyde and the like. It is done.

  Examples are given below to illustrate the present invention in more detail. However, the present invention is not limited to these examples.

[Effects of added elements on cell growth]
Aseptically inoculate a 25 ml SGP (silicone-glucose-peptone) liquid medium in a 50 ml centrifuge tube with a colony of Leptothrix Korodini OUMS1 strain (hereinafter referred to as OUMS1 strain) The cells were cultured for 3 days in a stirrer (20 ° C., 70 rpm rotation) (preculture). The composition of SGP liquid medium is 1 g of glucose, 1 g of peptone, 0.2 g of Na ₂ Si0 ₃・ 9H ₂ O, 0.044 g of CaCl ₂・ 2H ₂ O, 0.041 g of MgSO ₄・ 7H ₂ O, Na ₂ HPO ₄・ 12H ₂ O 0.076 g, KH ₂ PO ₄ .2H ₂ O 0.02 g, HEPES 2.838 g, distilled water 1000 ml, pH 7.0. In the case of a plate medium, 1.5% agar was added to solidify.

The bacterial cells (aggregates) in the pre-culture solution are precipitated by centrifugation (4000 rpm, 10 minutes), resuspended in 10 ml of SGP liquid medium, and then passed through a 23G syringe needle three times to remove the aggregates. After dispersion, the number of bacteria was adjusted to 1.0 × 10 ³ cfu / ml using a spectrophotometer. Add 1 ml of this bacterial suspension to 99 ml of Si-modified SGP liquid medium or Al-added SGP liquid medium in a 200 ml Erlenmeyer flask, and culture for 4 days on a constant temperature shaker (20 ° C, 70 rpm rotation) (Main culture). The concentration of Na ₂ SiO ₃ .9H ₂ O and the concentration of AlCl ₃ .6H ₂ O added were 0, 0.05, 0.5, and 5 mM.

  Next, immediately after the addition of the bacterial suspension, 1 day, 2 days, 3 days and 4 days after the culture, 10 ml of the bacterial solution is collected from the culture and passed through a 23G needle three times to give bacterial clumps. Distributed. Dilute this suspension 10-fold at a time, add 10 μl of each suspension on a SGP plate medium, and incubate for several days in a 20 ° C. incubator. Was calculated.

  FIG. 1 shows growth curves of OUMS1 strain in a medium supplemented with various concentrations of Si or Al. Si did not affect the growth of the OUMS1 strain at all concentrations up to 5 mM, but Al was found to inhibit growth at a concentration of 5 mM. This suggests that in the case of an element that inhibits bacterial growth such as Al, the method of incorporating BIOX into the element added to the medium in parallel with the bacterial growth is not applicable.

[Al-containing BIOX]
Pre-culture and main culture of the OUMS1 strain were performed as described above except for the following items. That is, a non-diluted bacterial suspension was used as an inoculum added to the main culture medium, and the main culture period was 3 days. The organic sheath in the main culture was washed by repeating centrifugation (4000 rpm, 10 minutes) and suspension in 10 volumes of sterile distilled water three times, and then 100 ml of 20 mM acetate buffer. Suspended in a liquid (pH 4.0). After adding 500 mg of iron powder and AlCl ₃ · 6H ₂ O to this suspension to a final concentration of 0.5, 1, ₂ , 5, 10 mM, in a constant temperature incubator (20 ° C, 70 rpm rotation) Shake for 1 week. The produced BIOX (precipitate) and the supernatant were separated by decantation, washed 3 times with 10 times the amount of ultrapure water, and then dried using a freeze dryer. By this method, about 100 mg of Al-containing BIOX was obtained per 100 ml of the main culture solution. The physicochemical properties of the produced BIOX were analyzed by the following method.

  The form and microstructure of the produced BIOX were analyzed using a scanning electron microscope (S-4300, manufactured by Hitachi) or a transmission electron microscope (JEM-2100F, manufactured by JEOL Ltd.) equipped with a STEM detector. In addition, the atomic composition ratios of the main elements in BIOX are the energy dispersive X-ray analysis (EDX) equipment equipped with the electron microscope for those related to Ru, and the electron microscope for those related to Al and Zr. Measured using a fluorescent X-ray analyzer (XRF, Orbis, manufactured by EDAX).

  The weight ratio of the constituent elements related to Ru was measured using a high frequency inductively coupled plasma (ICP) emission spectroscopic analyzer.

  The crystallinity of BIOX and its heating material was analyzed using an X-ray diffractometer (XRD, RINTO2500, manufactured by Rigaku, radiation source: Cu-Kα).

The color measurement of the heating material was performed by the following method.
(Heat treatment) Heated at 600 ° C, 700 ° C, 800 ° C, 900 ° C, 1000 ° C, 1100 ° C for 2 hours using an electric furnace (manufactured by Koyo Thermo Systems Co., Ltd.) (Cooling rate 2 ℃ / min).
(Crushing process) It grind | pulverized for about 10 seconds using the mortar and the pestle.
(Color Measurement) Hue and lightness were measured by SCI (Specular Component Include) method using a spectrocolorimeter CM-2600d manufactured by Konica Minolta Japan.

The production of natural BIOX used in the following was basically carried out by the method described in Reference 4 below. That is, (1) Collect the sediment formed in the groundwater purification tank of Okayama University Farm, wash with pure water until the electrical conductivity of the supernatant is 10μS / cm or less, and (2) add ammonia water. Adjust the pH to about 10.5 and stir for 10 minutes. (3) After standing for 40 minutes, wash the precipitate with 2 volumes of distilled water and 1 volume of ethanol. (4) Set the precipitate at 100 ° C. Prepared by drying overnight.
Reference 4: Hashimoto, H., Yokoyama, S., Asaoka, H., Kusano, Y., Ikeda, Y., Seno, M., et al. (2007) Characteristics of hollow microtubes consisting of amorphous iron oxide nanoparticles produced by iron oxidizing bacteria, Leptothrix ochracea. J. Magn. Magn. Mater. 310: 2405-2407.

  FIG. 2 shows the shape (SEM image) and element distribution (EDX mapping image) of BIOX containing 24 at% Al. Al-containing BIOX showed a hollow tubular form with a diameter of 1.0 to 1.2 μm, and most of them formed a mass with dense sheaths. Al was found to be uniformly distributed in BIOX, as was Fe.

  FIG. 3 shows the relationship between the Al content and the crystallinity of BIOX (XRD analysis). BIOX containing no Al and BIOX containing 5 at% and 10 at% Al were found to be single crystals of α-FeOOH. On the other hand, BIOX containing 20at% and 24at% of Al was found to consist of a single phase of low crystalline 2-line-ferrihydrite. From this result, it is considered that the crystallinity of BIOX can be controlled by increasing or decreasing the Al content.

  FIG. 4 shows an electron diffraction image and a high-resolution TEM image of BIOX containing 20 at% Al. As a result, two thin diffraction rings are observed in the electron diffraction pattern of BIOX containing 20 at% Al, which is similar to the electron diffraction pattern of 2-line ferrihydrite, which is a low crystalline iron oxide. . In addition, the high-resolution TEM image of the peripheral edge of the BIOX shows low crystallinity because no lattice fringes are observed.

  FIG. 5 shows the relationship between the Al treatment concentration and the elemental composition ratio in BIOX. It was clarified that the composition ratio of Al in BIOX increased while the composition ratio of Fe decreased as the Al content increased. Moreover, under the conditions of this method, the maximum amount of Al adsorbed on BIOX was about 25 at%. These results suggest that the composition ratio of Al and Fe in BIOX can be controlled by arbitrarily adjusting the amount of Al added.

  FIG. 6 shows the shape (SEM image) of BIOX containing no Al, containing 10% Al, and containing 24% Al. Regardless of the difference in the Al content, BIOX showed a tubular shape with a diameter of 1.0 to 1.2 μm, and formed a mass bundle in which most of the sheaths were dense.

  FIG. 7 shows the hue and brightness after heating at each temperature of the culture system BIOX containing 24 at% Al. For comparison, natural BIOX and commercially available Bengala (MC-55, Morishita Valve Industry Co., Ltd.) were used. It was found that the BIOX heating material containing Al24at% exhibits a bright red tone that exceeds that of the commercial Bengala, particularly in the heating temperature range of 700 ° C to 900 ° C. It was also revealed that heat resistance is higher in a wide temperature range than natural BIOX.

  FIG. 8 shows the resistance to reheating of the culture system BIOX containing 24 at% Al. Compared to the control MC-55 and natural BIOX, it was found that BI24 containing Al24at% had higher color heat resistance against reheating at 800 ° C.

FIG. 9 shows the crystallinity (XRD pattern) after heating of BIOX containing Al24 at%. The results indicate that the crystalline phase of the heating temperature 600 ° C. In Alfeo ₃ coexist, it is a single crystalline phase of heating temperature 700 to 1000 ° C. In α-Fe ₂ O _3, the heating temperature 1100 ° C. At alpha-Fe ₂ It shows that the crystal phase of O ₃ and α-Al ₂ O ₃ coexist.

  FIG. 10 shows the fine shapes (SEM images) before and after the pulverization treatment of BIOX containing Al24at% and natural BIOX before heating.

  FIG. 11 shows the hue and brightness of an 800 ° C. heating material obtained by subjecting BIOX containing Al24at% and natural BIOX to a pulverized state before heating and those not pulverized. Compared to natural BIOX, the culture system BIOX containing Al was found to have a lower degree of color tone reduction in the heated material after pulverization. Therefore, it was suggested that the degree of contribution of the tubular form in the heat resistance of the heating material differs depending on the difference in the composition ratio of Si and Al contained in BIOX.

FIG. 12 shows the hue and brightness after heat treatment of BIOX containing Al (24 at%) and synthetic iron oxide containing Al (20 mol%). Compared to synthetic iron oxide Ferrihydrite containing 20 mol% Al, the culture system BIOX containing 24 at% Al shows significantly higher L ^* value, a ^* value and b ^* value in the heating temperature range of 700-900 ° C, It was found to exhibit a higher saturation red color.

  Chemically synthesized iron oxide Ferrihydrite containing Al was synthesized by the following method. (1) Weigh iron nitrate nonahydrate and aluminum nitrate nonahydrate to Al / (Al + Fe): 0.2 and mix them in a mortar. (2) Carbonate of 12 times molar amount of nitrate Add ammonium hydrogen, knead until pasty in a mortar, (3) leave the paste for about 12 hours, (4) suspend the paste in distilled water, collect by suction filtration and dry under reduced pressure for 2 days (5) Synthesis was performed by drying in a vacuum atmosphere at 120 ° C. for about 12 hours.

[Zr-containing BIOX]
The adsorption treatment of Zr on BIOX was performed in the same manner as the above-described method for producing Al-containing BIOX. That is, the organic sheath primordium which is the main culture product of OUMS1 strain was washed with sterile distilled water, suspended in 20 mM acetate buffer (pH 4.0), iron powder (500 mg / 100 ml) and ZrCl ₄ (Final concentration 0, 0.5, 1, 2, 5, 10 mM) was added and the mixture was shaken under the same conditions as in the main culture. Next, BIOX containing Zr was separated from the supernatant by decantation, washed 3 times with 10 times the amount of ultrapure water, and then dried using a freeze dryer.

  FIG. 13 shows the form (SEM image) and element distribution (EDS mapping) of BIOX containing 40 at% Zr. The Zr-containing culture system BIOX showed a tubular form with a diameter of 1.0 to 1.2 μm, and most of them formed a dense bundle. In addition, Zr was found to be uniformly distributed in BIOX, similar to Fe.

  FIG. 14 shows the crystallinity (XRD analysis) of Zr-containing BIOX. The product was found to have α-FeOOH crystal phase regardless of the difference in Zr treatment concentration.

  FIG. 15 shows the relationship between the Zr treatment concentration and the elemental composition ratio (XRF analysis) in BIOX. This result suggests that the composition of Zr and Fe in the product can be controlled by arbitrarily changing the treatment concentration of Zr.

  FIG. 16 shows the Zr treatment concentration and the form of BIOX (SEM observation image). Regardless of the Zr treatment concentration (content in the product), BIOX was found to maintain a hollow tubular morphology.

  FIG. 17 shows the hue and brightness after heating BIOX containing 20 at% Zr at various temperatures. As a comparative control, MC-55 and natural BIOX heat-treated at 800 ° C. were used. It was found that the BIOX heating material containing Zr20at% exhibits a bright red tone that is significantly higher than the commercial Bengala, particularly in the heating temperature range of 700 to 900 ° C.

FIG. 18 shows the crystallinity (XRD analysis) after heating BIOX containing 20 at% Zr at 900 or 1100 ° C. As a result, a single crystal phase of α-Fe ₂ O ₃ exists at a heating temperature of 900 ° C, and a crystal phase (unidentified) derived from the inclusion of α-Fe ₂ O ₃ and Zr coexists at a heating temperature of 1100 ° C. I understood it.

  FIG. 19 shows a fine shape (SEM image) after heat-treating BIOX containing 5 at% or 20 at% Zr. Compared to Zr5at% -containing BIOX, Zr20at% -containing BIOX was found to suppress the hypertrophy of particles that occurred after heat treatment at 1000 ° C or higher.

[Ru-containing BIOX]
The adsorption treatment of Ru on BIOX was carried out in the same manner as the production method of Al-containing BIOX described above except for the following matters. That is, after the main culture of OUMS1 strain, directly add 50 mg of iron powder and RuCl ₃ 3H ₂ O solution to a final concentration of 1 and 5 mM to 100 ml of the culture solution containing the organic sheath. Furthermore, a shaking treatment was performed for 1 week under the same conditions as in the main culture. In some cases, the organic pod after the main culture is collected, and the cells in the organic pod are removed by LES (lysozyme-EDTA-SDS) treatment, then resuspended in SGP liquid medium, iron powder and RuCl ₃ · 3H. A treatment method of adding ₂ O was used. The LES process was performed by the method described in Document 1 described above. Next, the produced Ru-containing BIOX was subjected to precipitation by centrifugation (4000 rpm, 10 minutes) and washing with 10 times the amount of ultrapure water three times, and then dried using a vacuum freeze dryer.

Samples used for the next assay of catalytic activity were (1) sheath products prepared by adding only 1 mM RuCl ₃ 3H ₂ O to the final culture solution, and (2) 50 mL of the main culture solution. mg of iron powder and a final concentration of 1mM of RuCl ₃ · 3H ₂ O the BIOX prepared by adding, (3) to the culture solution was added RuCl ₃ · 3H ₂ O in 50 mg of iron powder and a final concentration of 5 mM (4) BIOX prepared by adding 50 mg iron powder and final concentration of 5 mM RuCl ₃ 3H ₂ O after LES treatment of the organic sheath after the main culture, (5) Main culture The sheath product recovered after washing the purified organic sheath with purified water (only the organic sheath and not including Ru and Fe), (6) BIOX with 200 mg iron powder added to the medium during main culture (parentheses) The numbers in the figure correspond to the catalyst numbers shown in the following experiments). Catalysts (1) ′ to (3) ′ represent samples obtained by pulverizing (1) to (3) with a mortar and pestle, respectively.

  FIG. 20 shows the form (SEM image) of BIOX containing Ru. The inset is an enlarged view of the end of each BIOX. The iron oxide product containing 20 at% Ru (EDX analysis) showed a hollow tubular sheath form with a diameter of 1.0 to 1.2 μm, and most of the sheaths formed a dense mass. On the other hand, iron oxide containing 60 at% Ru (EDX analysis) showed a non-hollow rod-like form with a diameter of 0.6 to 1.0 μm, and similarly formed agglomerates. As a result of ICP analysis, the weight ratio of Ru in iron oxide containing 20 at% Ru (EDX analysis) and iron oxide containing 60 at% (EDX analysis) was 7.4% and 13.4%, respectively.

  [Synthesis of benzamide from benzonitrile]

  A predetermined amount of catalyst was added to the screw type test tube, 0.5 mL of water as a solvent and 0.3 mmol of benzonitrile were added, and the screw was closed in a predetermined gas atmosphere to close the test tube. Heating was performed at a predetermined temperature for 24 hours in an aluminum block thermostat. Acetone was added to the reaction solution for dilution, naphthalene was added as a standard substance, and the product was analyzed with a gas chromatograph to calculate the yield of benzamide. The results are shown in the table below.

  In the table, (3) -2 indicates that the catalyst (3) once used is reused.

  As shown in Example 1-1, the catalyst (1) effectively functioned as a catalyst for the nitrile hydration reaction, and gave the product benzonitrile in a yield of 70%. Even when this catalyst (1) is pulverized with a mortar and pestle, catalytic activity is exhibited (Example 1-2). That is, even when the catalyst is mechanically pulverized, the catalyst exhibits stable catalytic activity without impairing its activity. As shown in Example 1-3, the catalyst (2) contains an iron component. In this case, the nitrile hydration reaction proceeds. That is, it is clear that the iron component does not interfere with this nitrile hydration reaction. Similar to Example 1-2, even when the catalyst (2) is mechanically pulverized, its catalytic function is maintained (Example 1-4).

  In the catalyst (3) of Example 1-5, the ratio of Fe and Ru was changed as compared with that of the catalyst (2). In this case, the nitrile hydration reaction proceeds. That is, it is an advantage at the time of preparing this catalyst that an active catalyst can be obtained without strictly adjusting the ratio of Fe and Ru. In particular, it is a great manufacturing advantage that a very strict ratio of process control is not required during industrial production of the catalyst. In Example 1-7, the nitrile hydration reaction was carried out in air. Even in this case, benzamide was obtained in a yield of 98%. From this experimental fact, it can be said that there is no need to strictly manage the inside of the container with an inert gas such as argon or nitrogen during the catalytic reaction, which is a great advantage in the production of amides.

  In Example 1-8, the catalyst concentration in the catalytic reaction system was reduced to one-half that of Example 1-5 and the reaction temperature was 150 ° C. Even in this case, benzamide could be obtained. It was. This experimental fact indicates that it is not necessary to strictly control the catalyst concentration and temperature during the catalytic reaction, which is preferable in that it allows a wide range of conditions for production management. Examples 1-9 to 1-13 are the results of changing these conditions, and prove that it is possible to provide a wide range of conditions for production management.

  Examples 1-14 and 1-15 show that the catalyst function is not lost even if the catalyst (3) used once for the catalytic reaction is recovered and reused after the reaction. That is, it can be seen that this catalyst that can be recovered and reused is excellent in terms of economy. In Example 1-16, the influence of the bacterial cells remaining in the organic sheath during culture on the catalytic function was examined. The benzamide yield of Example 1-16 using the catalyst (4) from which the microbial cells were removed was 96%, and the catalytic reaction proceeded even without the bacterial cells, and the bacterial cells were present in the catalytic reaction. It can be seen that the nitrile hydration reaction proceeds smoothly even if it is not. That is, the presence of bacterial cells does not adversely affect the nitrile hydration reaction.

  As shown in Comparative Example 1-1, the catalytic reaction did not proceed with the catalyst (5) having only an organic sheath containing no Ru and Fe. Furthermore, in Comparative Example 1-2 using a catalyst (6) containing no Fe and containing only Fe as a metal element, benzamide was obtained in a yield as low as 22%. From these examples, in order to advance the nitrile hydration reaction with high productivity and to produce the desired industrially useful amides, Ru is essential as a component, and preparation of a catalyst with addition of Ru is essential. It is clear that there is.

  In order to further clarify the effectiveness of the catalyst of the present invention, the following comparative experiment was conducted.

[Preparation of ruthenium / silica catalyst]
From Table 1, the effectiveness of Ru is clear. On the other hand, in order to verify the effectiveness of the organic sheath produced by microorganisms, which is a carrier as a catalyst, a comparative experiment using silica used as a carrier was conducted.

  Silica (silicon oxide (IV), high-purity chemical) (hereinafter: N-silica) and silica for industrial catalysts (silicon (IV), Fuji Silysia Chemical, GRADE: Q-10) (Hereinafter: Q-silica). This industrial catalyst silica is characterized by not swelling with water. 100 mg of silica was added to 100 mL of SGP liquid medium placed in a 200 mL flask. A ruthenium chloride trihydrate solution and iron powder were added and adjusted so as to be a target medium component, followed by stirring with a constant temperature shaker (20 ° C., 70 rpm) for 1 week. The produced ruthenium / silica catalyst and the supernatant were separated by centrifugation, washed with ultrapure water three times, and then dried using a freeze dryer.

  Four types of catalysts (a)-(d) were prepared. In (a), after adding N-silica to the SGP medium, 50 mg of iron powder and a ruthenium chloride trihydrate solution were added so that the ruthenium concentration of the medium was 5 mM. In (b), after adding N-silica to the SGP medium, a ruthenium chloride trihydrate solution was added so that the ruthenium concentration of the medium was 5 mM without adding iron powder. In (c), after adding Q-silica to the SGP medium, 50 mg of iron powder and a ruthenium chloride trihydrate solution were added so that the ruthenium concentration of the medium was 5 mM. In (d), after adding Q-silica to the SGP medium, a ruthenium chloride trihydrate solution was added so that the ruthenium concentration of the medium was 5 mM without adding iron powder. For comparison, an experiment using commercially available powdered quartz (e) was also conducted.

  As a result of ICP analysis, the weight composition ratios of ruthenium in each catalyst were (a) 2.7 wt%, (b) 0.2 wt%, (c) 1.6 wt%, and (d) 0.8 wt%.

  Using the prepared catalysts (a) to (d) and (e), an experiment on benzonitrile hydration was performed. To the screw-type test tube, 2 mol% of a catalyst as Ru with respect to benzonitrile was added, 0.5 mL of water as a solvent and 0.3 mmol of benzonitrile were added, and the screw was closed in an argon atmosphere to close the test tube. Heating was performed at a predetermined temperature for 24 hours in an aluminum block thermostat. Acetone was added to the reaction solution for dilution, naphthalene was added as a standard substance, the product was analyzed with a gas chromatograph, and the yield of the product benzamide was calculated. The results are shown in Table 2.

  First, Ru and Fe immobilized on silica (a) was used as a catalyst (Comparative Example 1-3). Benzamide was obtained as a product in a yield of 83%. Regarding Ru / silica catalyst (b), if the Ru content is as low as 0.2 wt% and the catalyst is 2 mol%, the required amount of catalyst will be as large as 303 mg, and the amount of catalyst is insufficient, so the reaction Did not do. The reaction was also carried out in (c) where Ru and Fe were immobilized on silica for the catalyst, but no significant difference was found in the activity compared with the normal silica of Comparative Example 1-3 (Comparative Example 1-5). On the other hand, the yield decreased by about 10 points in (d) in which only Ru was supported on the catalyst silica (Comparative Example 1-6). In addition, when Ru and Fe were not immobilized and the reaction was carried out with powdered quartz (e), an amide was obtained although the yield was low (Comparative Example 1-7).

  The results of these comparative examples are thought to be because the silanol groups contained in silica functioned as Bronsted acids in water. Considering the effect as a Bronsted acid, the Ru immobilized catalyst shown in Table 1 and the Ru / silica catalyst shown in Table 2 are compared, and the Ru immobilized catalyst shown in Table 1 shows higher catalytic activity. It is clear. That is, the catalyst in which Ru is supported on the organic sheath produced by the microorganism of the present invention is suitable for the production of amides, because of the high production efficiency during the production of amides. Specifically, the high production efficiency requires that the catalyst can be recovered and reused, that the reaction proceeds in air, and that the component ratio of the chemicals (Ru and Fe) during catalyst preparation must be strict. This contributes greatly to operational stability during industrial production.

  Since the catalyst of the present invention is a solid catalyst that is insoluble in solvents including water, it can be separated from the product by a simple operation such as filtration from the reaction solution after completion of the reaction. I can say that. Further, in Examples 1-1 to 1-17 shown in Table 1, undesirable by-products other than the target benzamide could not be detected by the gas chromatograph apparatus. Therefore, in this catalyst system, since only the target product can be obtained, a complicated separation operation from the by-product is unnecessary, and this point is also economical.

  [Synthesis of nicotinamide from 3-cyanopyridine]

  A predetermined amount of catalyst was added to the screw type test tube, 0.5 mL of water as a solvent and 0.3 mmol of 3-cyanopyridine were added, and the screw was closed under a predetermined gas atmosphere to close the test tube. Heating was performed at a predetermined temperature for 24 hours in an aluminum block thermostat. The product was isolated by column chromatography and the yield of nicotinamide was calculated. The results are shown in the table below.

  [Synthesis of acrylamide from acrylonitrile]

  A predetermined amount of catalyst was added to the screw-type test tube, 0.5 mL of water as a solvent and 0.3 mmol of acrylonitrile were added, and the screw was closed in a predetermined gas atmosphere to close the test tube. Heating was performed at a predetermined temperature for 24 hours in an aluminum block thermostat. Acetone was added to the reaction solution for dilution, naphthalene was added as a standard substance, and the product was analyzed with a gas chromatograph to calculate the yield of acrylamide. The results are shown in the table below.

[Synthesis of other amides]
(3) was selected as the catalyst, 2 mol% with respect to the raw material nitrile, 0.5 mL of water as a solvent and 0.3 mmol of the raw material nitrile were added, and the screw was closed under an argon atmosphere to close the test tube. Heated at 180 ° C. for 24 hours in an aluminum block thermostat. Acetone was added to the reaction solution for dilution, naphthalene was added as a standard substance, the product was analyzed with a gas chromatograph, and the yield of the produced amide was calculated. The yield was 73% for phenylacetamide, 91% for benzenepropionamide, 57% for o-methylbenzamide, and 33% for methacrylamide.

  Thus, the catalyst of the present invention is not limited to the benzamide production shown in Table 1. Specifically, nicotinamide of an aromatic amide containing a nitrogen atom that is a hetero atom (Example 2-1), acrylamide (Example 3-1) that is an acrylic amide containing a carbon-carbon double bond, and It can be used for the production of a wide variety of amides such as methacrylamide, aliphatic amide phenylacetamide and benzenepropionamide, and substituted aromatic amide o-methylbenzamide.

  [Reaction to obtain amides by Beckmann rearrangement of oximes]

A predetermined amount of catalyst was added to the screw type test tube, 0.5 mL of solvent and 0.3 mmol of benzaldehyde oxime were added, and the test tube was closed by closing the screw under an argon atmosphere. Heating was performed at a predetermined temperature for 24 hours in an aluminum block thermostat. Acetone was added to the reaction solution for dilution, naphthalene was added as a standard substance, and the product was analyzed with a gas chromatograph to calculate the yield of benzamide. The results are shown in the table below. In addition, K ₂ CO ₃ of Example 4-4 was added in an equimolar amount with respect to ruthenium. The results of Example 4-4 show that the presence of a base such as K ₂ CO ₃ is not essential, but the reaction proceeds even in the presence of a base.

  In Comparative Example 4-1, commercially available ruthenium chloride trihydrate was used as the catalyst. It is well known that the Beckmann rearrangement reaction proceeds even with a Bronsted acid catalyst. In Comparative Example 4-1, when ruthenium chloride trihydrate is dissolved in water as a solvent, hydrogen chloride is generated in the solution and the liquid becomes acidic. At this time, the reaction solution is green. As a result of the hydrogen chloride functioning as a Bronsted acid, benzamide was obtained as a product in a yield of 51%. In contrast, in Example 4-1, the reaction proceeded under neutral conditions where hydrogen chloride was not generated, and benzamide was obtained in a yield of 62%.

[Production of carbonyl compound by dehydrogenation of alcohol]: Production of γ-butyrolactone by dehydrogenation of 1,4-butanediol
Example 5-1
In a screw test tube, 4.5 mg of catalyst (3) and toluene (0.5 mL) as a solvent were placed. Subsequently, 27 μl (0.3 mmol) of 1,4-butanediol and 66 μl (0.9 mmol) of acetone were added, and the screw-type lid was closed. A screw type test tube containing the above components was attached to an oil bath heated to 205 ° C. and heated for 3 hours. Naphthalene was added as a standard substance to the cooled reaction liquid after completion of heating, diluted with 1,2-dimethoxyethane, and the product was quantified with a gas chromatograph apparatus. The yield of γ-butyrolactone was 23%. Here, acetone acts as a hydrogen acceptor, captures hydrogen inside the sealed reaction system, and is converted into 2-propanol.

Example 5-2
Put 22.5 mg of catalyst (3) and 132 μl (1.5 mmol) of 1,4-butanediol in a glass reactor equipped with an air cooler, and place it in an oil bath heated to 205 ° C in an open system with flowing argon gas. It was. After heating for 3 hours, naphthalene was added as a standard substance to the cooled glass reactor, the reaction solution was diluted with 1,2-dimethoxyethane, and the product was quantified with a gas chromatograph. The yield of γ-butyrolactone was 9%.

[Production of carbonyl compounds by dehydrogenation of alcohol]: Production of cyclohexanone by dehydrogenation of cyclohexanol
Example 6-1
In a screw test tube, 4.5 mg of catalyst (3) and water (0.5 mL) as a solvent were added. Subsequently, 32 μl (0.3 mmol) of cyclohexanol was added, and the screw-type lid was closed. The screw type test tube containing the said component was put into the aluminum block heated at 180 degreeC, and it heated for 24 hours. After the heating was completed, dodecane was added as a standard substance to the cooled reaction solution, diluted with toluene, and the product was quantified with a gas chromatograph. The yield of cyclohexanone was 31%.

  Thus, the production of the carbonyl compound by dehydrogenation of the alcohol can be carried out even in the presence of a hydrogen acceptor as in Example 5-1 (acetone in Example 5-1), as in Example 5-2. It was found that good results could be obtained even without body.

  Furthermore, the production of a carbonyl compound by dehydrogenation of an alcohol using this catalyst system can be achieved by using a primary alcohol such as 1,4-butanediol (Examples 5-1 and 5-2) or a secondary alcohol such as cyclohexanol. It was found that (Example 6-1) may be used.

Claims (19)

An iron oxide containing at least one element selected from the group consisting of aluminum, zirconium, ruthenium, titanium and hafnium,
The shape is tube or rod,
The element ratio of the element is 5% or more and less than 25% in terms of atomic% (here, the total of atomic% of main elements excluding oxygen, carbon, nitrogen and hydrogen is 100) iron oxide.   The iron oxide according to claim 1, further comprising silicon and / or phosphorus. The iron oxide according to claim 1 or 2, comprising α-Fe ₂ O ₃ . A method for producing iron oxide containing at least one element selected from the group consisting of aluminum, zirconium, ruthenium, titanium and hafnium, comprising the following steps:
(1) producing an organic sheath by culturing iron-oxidizing bacteria; and
(2) The organic sheath obtained in step (1) is suspended in an aqueous solution containing at least one element selected from the group consisting of aluminum, zirconium, ruthenium, titanium and hafnium, and iron, and contains the element. A step of producing iron oxide. The method of claim 4 further comprising the following steps:
(3) A step of heat-treating the iron oxide obtained in step (2).   The method of Claim 5 whose temperature of heat processing is 600-1000 degreeC. The method according to any one of claims 4 to 6, further comprising the following steps:
(4) A step of pulverizing the iron oxide obtained in the step (2) or (3).   The method according to any one of claims 4 to 7, wherein the iron-oxidizing bacterium is a bacterium belonging to the genus Leptosurix.   The pigment containing the iron oxide as described in any one of Claims 1-3. A composite comprising a metal oxide containing at least one element selected from the group consisting of aluminum, zirconium, ruthenium, titanium and hafnium, and an organic sheath,
The shape is tube or rod,
A complex in which the element ratio of the element is 5% or more in terms of the number of atoms (here, the sum of the number of atoms of the main elements excluding oxygen, carbon, nitrogen, and hydrogen is 100).   The composite according to claim 10, further comprising iron oxide as the metal oxide.   The composite according to claim 10 or 11, further comprising silicon and / or phosphorus.   The hydration catalyst used for a hydration reaction containing the composite_body | complex as described in any one of Claims 10-12.   The hydration catalyst according to claim 13, which is used for hydration of nitriles.   The nitrile is an aliphatic nitrile having 1 to 30 carbon atoms which may have a substituent or an aromatic nitrile having 6 to 30 carbon atoms which may have a substituent. Hydration catalyst.   The hydration catalyst according to claim 14 or 15, wherein the nitrile is acrylonitrile, methacrylonitrile, 3-cyanopyridine, or polyacrylonitrile.   The catalyst used for the Beckmann rearrangement reaction containing the composite_body | complex as described in any one of Claims 10-12.   The dehydrogenation catalyst for carbonyl compound manufacture by dehydrogenation of alcohol containing the composite_body | complex as described in any one of Claims 10-12.   The dehydrogenation catalyst according to claim 18, wherein the alcohol is an aliphatic alcohol having 1 to 30 carbon atoms which may have a substituent.