JP7070066B2 - Method for producing tetrahydroborate - Google Patents

Description

The present disclosure relates to a method for producing tetrahydroborate.

As a method for producing tetrahydroborate by hydrogenating borate, a method of reacting sodium metaborate powder and magnesium powder for about 2 hours under a hydrogen atmosphere of about 550 ° C and 2.3 MPa is known. .. (See, for example, Patent Document 1). Further, as another method, a method is known in which sodium metaborate powder and granular aluminum are reacted in a hydrogen atmosphere at about 300 ° C. and 1 MPa for about 1 hour while rolling and pulverizing the granular aluminum (for example, patent). Document 2).

Japanese Unexamined Patent Publication No. 2004-224648 International Publication No. 2015/190403

Since the techniques described in these patent documents consume magnesium and aluminum, which are reducing metals, as consumables, they include a very high-cost process when applied industrially.

The present disclosure has been made in view of the above circumstances, and an object of the present disclosure is to provide a lower cost method for producing tetrahydroborate.

In the method for producing tetrahydroborate according to one aspect of the present disclosure, a object to be treated containing borate and an iron-based reducing agent is treated with mechanochemicals using a pulverized medium in a gas atmosphere containing hydrogen as a constituent element. It is provided with a mechanochemical treatment process for applying the above.

In one embodiment, the mechanochemical treatment step may be carried out so that E represented by the following formula (A) is more than 100 kJ · s / kg.
E = 1 / 2m ₁ v ² · t / m ₂ (A)
In formula (A), E is the time product of crushing energy per unit weight of the object to be processed (kJ · s / kg), m ₁ is the total weight of crushing media (kg), and v is the speed of crushing media (m / kg). s) and m ₂ indicate the weight (kg) of the object to be processed, and t indicates the processing time (s).

In one embodiment, the processing time t may be 1500 to 36000 (s).

In one embodiment, the production method may further include a preheating step of heating borate before the mechanochemical treatment step.

In one embodiment, the mechanochemical treatment step may be carried out while heating borate.

In one embodiment, the ratio of the average particle size of the iron-based reducing agent to the average diameter of the pulverized media may be 1/3 or less.

In one embodiment, the average particle size of borate may be 1 mm or less.

In one embodiment, the borate may be sodium metaborate.

In one embodiment, the above-mentioned production method may further include a borate preparation step of reacting a tetrahydroborate with water to obtain a borate before the mechanochemical treatment step.

According to the present disclosure, it is possible to provide a lower cost method for producing tetrahydroborate. It can be said that the manufacturing method of the present disclosure is very suitable for industrial applications.

It is a schematic diagram which shows the manufacturing apparatus of tetrahydroborate.

Hereinafter, embodiments of the present disclosure will be described in detail with reference to the drawings as the case may be. However, the present disclosure is not limited to the following embodiments.

<Manufacturing method of tetrahydroborate>
The method for producing tetrahydroborate according to the present embodiment is a mechanochemical using a pulverized medium in a gas atmosphere containing hydrogen (H) as a constituent element with respect to an object to be treated containing borate and an iron-based reducing agent. It is provided with a mechanochemical treatment step for performing treatment.

(Mechanochemical treatment process)
Based on the findings of the prior literature, the inventors studied by simply replacing aluminum with an iron-based material in order to reduce costs, but it was not possible to hydrogenate sodium metaborate to produce sodium hydride. There was found. The reason for this is not clear, but the inventors speculate as follows. Hereinafter, a case where hydrogen gas is used as a gas containing hydrogen (H) as a constituent element, sodium metaborate (NaBO ₂ ) as a borate, and pure iron as an iron-based reducing agent will be described as an example.

In this case, it is considered that the following three chemical reactions occur in this step.
3NaBO ₂ + 4Fe + 6H ₂ → 3NaBH ₄ + 2Fe ₂ O ₃ (1)
2NaBO ₂ + 3Fe + 4H ₂ → _{2NaBH 4} + Fe 3O ₄ (2)
Fe ₂ O ₃ + H ₂ → 2 Fe ₃ O ₄ + H ₂ O (3)

Specifically, in the above reaction, it is considered that first, the positive ions generated on the iron surface by the mechanochemical reaction come into contact with hydrogen to form iron hydride, and protide (H ⁻ ) is generated. In addition, since the bond energy between iron and oxygen is higher than the dissociation energy of the BO bond of sodium metaborate, the oxygen bonded to the borate atom is dissociated by iron, and the protide is substituted. .. Thereby, iron oxide and sodium tetrahydroborate (NaBH ₄ ) can be obtained in an environment of normal temperature and pressure.

As described above, it is important that iron hydride is produced as the first step in the above chemical reaction. However, even if an attempt is made to proceed with this reaction based on the disclosure contents of the prior art and various conditions of the media type pulverization treatment generally considered to be optimal, it is possible that the required iron hydride is not produced in the first place. I thought there was sex. Therefore, as a result of repeated trial and error to generate iron hydride, it was found that it is extremely important to make the treatment conditions harsher than before, and the following formula (A) was defined. The fact that iron can be used as a reducing agent instead of aluminum or magnesium to obtain tetrahydroborate is a great merit from the viewpoint of cost reduction.

In a system using an iron-based reducing agent, triiron tetroxide (Fe ₃ O ₄ ) is finally produced. Since triiron tetroxide has magnetism, it can be easily separated from tetrahydroborate by magnetic separation after the completion of this step. Compared with the case of using magnesium or aluminum which cannot rely on magnetic separation, the manufacturing efficiency and cost can be significantly improved.

Examples of the gas containing hydrogen (H) as a constituent element include hydrogen gas, hydrocarbon gas, NH ₃ gas and the like. By using a gas containing carbon, which is easier to oxidize than hydrogen, such as hydrocarbons (CH ₄ , C ₂ H ₂ , C ₆ H ₆ , etc.), oxygen dissociated by mechanochemical treatment is adsorbed by carbon. Can be done. As a result, it is possible to suppress the generation of water in the system and further improve the production efficiency. Aiming at the same effect, the raw material gas may contain a gas containing an element that is more easily oxidized than hydrogen, such as carbon monoxide. By using such a gas in combination with a gas containing hydrogen (H) as a constituent element, oxygen dissociated by the mechanochemical treatment can be adsorbed by carbon. As a result, it is possible to suppress the generation of water in the system and further improve the production efficiency.

Specifically, as shown in the following formula (A), the mechanochemical treatment step is carried out so that the time product E of the crushing energy per unit weight of the object to be treated is more than 100 kJ · s / kg. be able to. As a result, iron and hydrogen react to form iron hydride, and as a result, tetrahydroborate can be obtained.
E = 1 / 2m ₁ v ² · t / m ₂ (A)
E: Time product of crushing energy per unit weight of the object to be treated (kJ · s / kg)
m ₁ : Total weight of crushed media (kg)
v: Speed of crushing media (m / s)
m ₂ : Weight of the object to be treated (kg)
t: Processing time (s)

The time product E of the energy may be 150 kJ · s / kg or more, or 300 kJ · s / kg or more. The upper limit of E is not particularly limited, but can be 2500 kJ · s / kg from the viewpoint of suppressing a decrease in productivity and an increase in production cost due to long-term treatment.

In the above formula (A), m ₁ : total weight of crushed media, v: speed of crushed media, m ₂ : weight of object to be processed, and t: processing time are appropriately adjusted so as to obtain a desired E value. can do. None of them is particularly limited, but for example, m ₁ can be 5 to 15000 kg, v can be 5 to 30 m / s, m ₂ can be 1 to 3000 kg, and t. Can be 1500 to 36000 s. In addition, t may be 1800 to 10000s or may be 1800 to 5000s. However, these numerical ranges are merely examples and can be adjusted according to the scale of the equipment used for mechanochemical treatment.

Examples of the material of the pulverized media include chrome steel, stainless steel, zirconia, alumina, stabilized zirconia, partially stabilized zirconia, silicon nitride, silicate, titania, and tungsten. Further, the average diameter of the pulverized media can be 2 to 500 mm. The crushing medium is preferably spherical and may be true sphere. The closer the crushed media is to a spherical shape, the more likely it is that a local high energy field will be generated when the crushed media collides with the object to be processed.

Examples of the material of the iron-based reducing agent include iron-based materials such as pure iron, triiron tetroxide, diiron trioxide, SS material, and carbon steel. Further, the average particle size of the iron-based reducing agent can be 0.1 to 15 mm. The iron-based reducing agent can be in the form of particles (spherical), but may have a shape such as a columnar shape or a flat shape. When the iron-based reducing agent has a columnar shape or a flat shape, the length in the major axis direction of the iron-based reducing agent may be the particle size of the iron-based reducing agent.

The ratio of the average particle size of the iron-based reducing agent to the average diameter of the crushed media (average particle size of the iron-based reducing agent / average diameter of the crushed media) can be 1/3 or less, and is 1/10 or less. May be good. The lower limit of the ratio can be set to 1/5000 from the viewpoint of availability and cost of a minute-sized iron-based reducing agent. As described above, since the iron-based reducing agent is sufficiently smaller than the pulverized medium, it becomes easy to be involved in the above-mentioned local high energy field.

The ratio of the total volume of the object to be treated to the total volume of the pulverized media can be 0.01 to 1.5, and may be 0.05 to 1.

As a means for carrying out the mechanochemical treatment step, for example, a ball mill can be mentioned. The ball mill has high pulverization processing efficiency and can efficiently produce a mechanochemical effect. As a result, tetrahydroborate can be produced at high speed, and the production cost can be kept low. At the same time, since the ball mill enables mass pulverization, a large amount of tetrahydroborate can be produced, and the production cost can be kept low. The ball mill device is generally widely used as a pulverization processing device, and since mechanochemical processing can be performed with a relatively simple device configuration, both the device cost and the operating cost can be suppressed at low cost.

In the present embodiment, the ball mill means a ball mill in a broad sense (see Powder Engineering Handbook 2nd Edition), and is a so-called rolling ball mill (pot mill, tube mill and conical mill), vibration ball mill (circular vibration type vibration mill, swivel). A concept that includes a type vibration mill and a centrifugal mill), and a planetary mill.

The conditions for the mechanochemical treatment are not particularly limited, and can be appropriately adjusted within the range satisfying the above formula (A). For example, in the case of a ball mill, the rotation speed of the container can be 10 to 180 rotations / minute. Further, the processing time t is as described above.

The mechanochemical treatment step can be carried out while heating borate. In this step, the mechanochemical treatment of the borate salt causes oxygen dissociated from the borate salt to react with atmospheric hydrogen to produce water. Therefore, by carrying out the mechanochemical treatment while heating the borate, it becomes easier to suppress the reaction between the generated water and the tetrahydroborate generated by hydrogenation of the borate. The heating temperature can be 100 to 500 ° C.

The borate may be subjected to mechanochemical treatment with carbon powder. As a result, it becomes easy to trap the oxygen atom dissociated from the borate by the mechanochemical treatment and suppress the reaction between the oxygen atom and the atmospheric hydrogen to generate water.

The borate may be subjected to mechanochemical treatment with a hygroscopic agent. Examples of the hygroscopic agent include quicklime, silica gel, bentonite, magnesium chloride, calcium chloride and the like. As a result, the water generated by the mechanochemical treatment can be removed as described above, so that the mechanochemical treatment efficiency can be further improved.

(Preheating process)
The production method according to the present embodiment may further include a preheating step of heating borate before the mechanochemical treatment step. By this step, the water contained in the borate hydrate as water of crystallization can be removed in advance. Therefore, unnecessary water does not exist in the mechanochemical treatment step, the mechanochemical treatment efficiency can be improved, and the speed of producing tetrahydroborate can be increased.

The preheating step can be carried out at 40 to 300 ° C. for 0.1 to 1 hour, for example, depending on the type and amount of borate.

(Borate preparation process)
The production method according to the present embodiment further includes a step of reacting tetrahydroborate with water to obtain a borate before the mechanochemical treatment step (and before the preheating step if a preheating step is provided). May be. Tetrahydroborate is used as a hydrogen carrier, and hydrogen is extracted and used by adding water to the tetrahydroborate at the hydrogen demand field, and then the bororate, which is the residue generated in the chemical reaction, is returned to the hydrogen supply field. By hydrogenating again, the tetrahydroborate can be regenerated. Since hydrogen can be transported and stored by repeatedly causing dehydrogenation and rehydrogenation, it becomes possible to transport and store hydrogen at low cost. For example, when sodium tetrahydroborate is used as the tetrahydroborate, the following reaction (4) is considered to occur in this step.
NaBH ₄ + 2H ₂ O → NaBO ₂ + 4H ₂ (4)

<Borate and tetrahydroborate>
(Borate)
Examples of the borate include borates such as metaborate, tetraborate, and pentaborate. Examples of the metaborate include NaBO ₂ , KBO ₂ , LiBO ₂ , Ca (BO ₂ ) ₂ , Mg (BO ₂ ) ₂ , and the like. Examples of the tetraborate include Na ₂ B ₄ O ₇ , Na ₂ O and 2 BO ₃ , K ₂ O and B ₂ O ₃ , Li ₂ B ₄ O ₇ , and Mg ₃ B ₄ O ₉ . Examples of the pentaborate include NaB ₅ O ₈ , Na ₂ O, 5B ₂ O ₃ , KB ₅ O ₈ , K ₂ O, 5B ₂ O ₉ , LiB ₅ O ₈ , and the like. In addition, the natural borate minerals Na ₂ B ₄ O ₇・ 10H ₂ O, Na ₂ B ₄ O ₇・ 4H ₂ O, Ca ₂ B ₆ O _{11.5H 2} O, CaNaB ₅ O ₉・ 6H ₂ O , Mg ₇ Cl ₂ B ₁₇ O ₃₀ and the like can also be used. Sodium metaborate may be used as the borate from the viewpoints of availability, acquisition cost, chemical stability, ease of hydrogen desorption, hydrogen storage density and the like.

The borate can be in powder form from the viewpoint of further improving the mechanochemical treatment efficiency. At that time, the average particle size of borate can be 1 mm or less, and may be 500 μm or less, or 100 μm or less. The lower limit is not particularly limited, but may be 5 μm.

(Tetrahydroborate)
Examples of the tetrahydroborate include hydrides corresponding to the borates exemplified above. For example, when metaborate is used as the borate, NaBH ₄ , KBH ₄ , LiBH ₄ , Ca (BH ₄ ) ₂ , Mg (BH ₄ ) ₂ , and the like can be mentioned.

<Tetrahydroborate production equipment>
FIG. 1 is a schematic diagram showing an example of a device for producing tetrahydroborate. In the device 100 shown in FIG. 1, the cylindrical reaction vessel 10, the first shaft (ball mill shaft) 11 connected to the central portions of both end faces of the reaction vessel 10, and each first shaft 11 are in a rotatable state. It includes a bearing 12 that supports it, a mill mechanism that includes a pedestal 13 that supports the bearing 12, a drive motor 20, and a motor mechanism that includes a second shaft (motor shaft) 21 that rotates by the driving force of the drive motor 20. Further, the drive belt B is hung on the outer periphery of the pulleys (indicated by the dotted line because they are on the back side of the drive belt B in the figure) provided on the first shaft and the second shaft, respectively. The rotational force of the second shaft 21 is transmitted to one of the first shafts 11 via the drive belt B. As a result, the reaction vessel 10 connected to the first shaft 11 rotates.

The reaction vessel 10 is a cylindrical heat-resistant and pressure-resistant vessel, and the inside can be sealed. The material of the reaction vessel 10 can be a metal material (steel material) that does not affect the hydrogenation reaction of the borate and is less affected by hydrogen embrittlement. The atmosphere (temperature, gas pressure, etc.) in the reaction vessel 10 can be appropriately adjusted by an atmosphere adjusting mechanism (not shown). The reaction vessel 10 contains an object to be treated (boric acid 30, iron-based reducing agent 31, pulverized media 32, etc.). Inside the container, the grinding force and impact force generated by the crushing media 32 are generated by the rotation of the reaction vessel 10. As a result, borate 30 is mechanochemically treated to obtain tetrahydroborate.

Hereinafter, the present disclosure will be described in more detail by way of examples, but the present disclosure is not limited to these examples.

Tetrahydroborate was produced using the apparatus shown in FIG. NaBO _{2.4H 2 O} (sodium metaborate tetrahydrate) (manufactured by Kishida Chemical Co., Ltd., content 98% by mass) was prepared as a borate. This was pulverized with a ball mill and heated at 160 ° C. for 15 minutes to remove water of crystallization to obtain NaBO ₂ (anhydrous sodium metaborate). The average particle size of the obtained NaBO ₂ was 100 μm. The average particle size was measured with a digital microscope. In addition, steel shot (carbon steel) was prepared as an iron-based reducing agent. The iron-based reducing agent was granular and had an average particle size of 1.7 mm.

Next, assuming that 40 kg of NaBH ₄ is produced, a predetermined amount of NaBO ₂ , an iron-based reducing agent, and a pulverized medium (chrome steel ball having an average diameter of 30 mm) is placed in the reaction vessel 10, and the inside of the reaction vessel 10 is vacuumed. bottom. As a result, the air (oxygen) in the reaction vessel 10 was exhausted, and then hydrogen was injected.

The power of the drive motor 20 was turned on, and the reaction vessel 10 started to rotate. During the rotation of the reaction vessel 10, the inside of the reaction vessel 10 was heated to 300 ° C., and hydrogen was injected in a circulating flow. The atmosphere inside the reaction vessel 10 taken out by the circulation flow was treated by a cooling capacitor, water and hydrogen were separated, and then hydrogen was reinjected into the reaction vessel 10. The rotation of the reaction vessel 10 was continued until the time product E (kJ · s / kg) of the crushing energy per unit weight of the object to be treated reached a predetermined value.

After that, the rotation was stopped and the processed object was taken out. After separating the mixture of sodium tetrahydroborate and iron (II) oxide and the ground medium from the object to be treated, sodium tetrahydroborate and iron (II) oxide are further separated from the mixture by magnetic separation to obtain the desired sodium tetrahydroborate. Got The details of the above experimental conditions are shown in Table 1 below.

In the table, the hydrogenation rate (conversion rate) was calculated as follows. First, sodium tetrahydroborate contained in the treated object after the treatment was hydrolyzed, and the hydrogen produced thereby was quantified. The amount of hydrogen is measured with a hydrogen detector tube (manufactured by Komei Rikagaku Kogyo Co., Ltd., measurement concentration range 0.05 to 0.8%) after measuring the generated gas volume and diluting the gas 200 times with nitrogen. It was calculated from the hydrogen concentration. Then, the hydrogenation rate was calculated from the amount of hydrogen quantified as described above, based on the amount of hydrogen in the case of 100% conversion.

10 ... reaction vessel, 11 ... first shaft, 12 ... bearing, 13 ... mount, 20 ... drive motor, 21 ... second shaft, 30 ... borate, 31 ... iron-based reducing agent, 32 ... crushed media, 100 ... tetrahydro Borate manufacturing equipment, B ... Drive belt.

Claims (8)

It is provided with a mechanochemical treatment step of performing mechanochemical treatment using a pulverized medium in a gas atmosphere containing hydrogen as a constituent element for an object to be treated containing a borate and an iron-based reducing agent.
A method for producing a tetrahydroborate, wherein the ratio of the average particle size of the iron-based reducing agent to the average diameter of the pulverized media is 1/3 or less. The manufacturing method according to claim 1, wherein the mechanochemical treatment step is carried out so that E represented by the following formula (A) is more than 100 kJ · s / kg.
E = 1 / 2m ₁ v ² · t / m ₂ (A)
[In the formula (A), E is the time product of crushing energy per unit weight of the object to be processed (kJ · s / kg), m ₁ is the total weight of the crushing media (kg), and v is the speed of the crushing media (m). / S), m ₂ indicates the weight of the object to be processed (kg), and t indicates the processing time (s). ] The production method according to claim 2, wherein the processing time is 1500 to 36000 (s). The production method according to any one of claims 1 to 3, further comprising a preheating step of heating the borate salt before the mechanochemical treatment step. The production method according to any one of claims 1 to 4, wherein the mechanochemical treatment step is carried out while heating the borate salt. The production method according to any one of claims 1 to 5, wherein the average particle size of the borate is 1 mm or less. The production method according to any one of claims 1 to 6, wherein the borate is sodium metaborate. The production method according to any one of claims 1 to 7, further comprising a borate preparation step of reacting a tetrahydroborate with water to obtain a borate before the mechanochemical treatment step.

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