阅读说明：本技术 一种硼氢化钠生产新工艺 (Novel process for producing sodium borohydride ) 是由 郑志浩 杨彬 张顺利 于 2018-08-28 设计创作，主要内容包括：本发明公开了一种硼氢化钠生产新工艺,包括以下制备步骤：1)、将NaBO<Sub>2</Sub>放入高能球磨机中500～1200rmp,球磨8～16小时；2)、将甲醇溶液与所述NaBO<Sub>2</Sub>于50℃-90℃下进行反应,制得NaB(OCH<Sub>3</Sub>)<Sub>4</Sub>；3)、将NaB(OCH<Sub>3</Sub>)<Sub>4</Sub>配置成5％-15％的THF溶液,加入MgH<Sub>2</Sub>在氢压下进行合成反应制得目标产物NaBH<Sub>4</Sub>。本发明摒弃以前必需的昂贵氢化物原料,使用成本低廉的有机硅烷作为反应原料,引入NaBO<Sub>2</Sub>在高能球磨机内进行球磨的步骤,NaBO<Sub>2</Sub>再次还原为NaBH<Sub>4</Sub>反应条件简单易控,且最大转化率可达到90％以上,可见,上述方法不仅降低了制造成本,而且具有较高的硼氢化钠产率,有利于硼氢化钠实现产业化生产。(The invention discloses a new process for producing sodium borohydride, which comprises the following preparation steps: 1) NaBO is added 2 Putting the mixture into a high-energy ball mill for 500-1200 rmp, and ball-milling for 8-16 hours; 2) and mixing the methanol solution with the NaBO 2 Reacting at 50-90 deg.C to obtain NaB (OCH) 3 ) 4 (ii) a 3) Mixing NaB (OCH) 3 ) 4 Preparing into 5-15% THF solution, adding MgH 2 The target product NaBH is prepared by the synthetic reaction under the hydrogen pressure 4 . The invention eliminates the expensive hydride raw material which is necessary before, uses organosilane with low cost as the reaction raw material, and introduces NaBO 2 Ball milling in a high energy ball mill, NaBO 2 Is reduced to NaBH again 4 The reaction conditions are simple and easy to control, and the maximum conversion rate can reach more than 90 percent, so that the method not only reduces the manufacturing cost, but also has higher yield of the sodium borohydride, and is beneficial to realizing the industrial production of the sodium borohydride.)

1. A new process for producing sodium borohydride is characterized by comprising the following preparation steps:

1) NaBO is added₂Putting the mixture into a high-energy ball mill for 500-1200 rmp, and ball-milling for 8-16 hours;

2) and mixing the methanol solution with the NaBO₂Reacting at 50-90 deg.C to obtain NaB (OCH)₃)₄；

3) Mixing NaB (OCH)₃)₄Preparing into 5-15% THF solution, adding MgH₂The target product NaBH is prepared by the synthetic reaction under the hydrogen pressure₄。

2. The novel process for producing sodium borohydride according to claim 1, wherein the high-energy ball mill is a planetary ball mill, and the ball-to-feed ratio of the ball mill is 20-30: 1.

3. The novel process for producing sodium borohydride according to claim 2, wherein the time of ball milling is 12 hours.

4. The novel process for producing sodium borohydride according to claim 1, wherein the reaction temperature in step 3) is 100-200 ℃ and the heating rate is 5-10 ℃ for a minute.

5. The novel process for producing sodium borohydride according to claim 1, wherein MgH in step 3)₂With NaB (OCH)₃)₄The molar ratio of (A) to (B) is 2.5-3.2: 1.

6. The novel process for producing sodium borohydride according to claim 1, wherein the hydrogen pressure is 2 to 5 MPa.

Technical Field

The invention relates to the technical field of preparation of hydrogen storage materials, in particular to a novel process for producing sodium borohydride.

Background

The metal borohydride, especially the light metal borohydride has higher hydrogen storage capacity compared with the hydrogen storage alloy, which far exceeds the requirements of the energy source part on the mass hydrogen storage density and the volume hydrogen storage density of the hydrogen storage material on the vehicle-mounted hydrogen storage or the portable energy source. Therefore, metal borohydride is one of the most promising hydrogen storage materials and a major research direction. However, when the metal borohydride is used as a hydrogen storage material, the problems of poor hydrogen release kinetics, high hydrogen release temperature, and the release of impurity gases possibly accompanied by the hydrogen release process exist, so that the practical application of the borohydride is limited; in addition, hydrolysis of metal borohydride is an alternative method for producing hydrogen, but the hydrogen production process by hydrolysis of borohydride is an irreversible process, so the production cost of borohydride is a key problem limiting the practical application of borohydride.

Disclosure of Invention

The invention aims to solve the technical problems that the preparation cost of the hydrogen storage material is high, the production process is complex and the industrial development is difficult to realize, and provides a new process for producing sodium borohydride.

In order to solve the technical problems, the invention provides the following technical scheme:

a new process for producing sodium borohydride comprises the following preparation steps:

1) NaBO is added₂Putting the mixture into a high-energy ball mill for 500-1200 rmp, and ball-milling for 8-16 hours;

2) reacting the methanol solution with the NaBO2 at 50-90 ℃ to prepare NaB (OCH)₃)₄；

3) Mixing NaB (OCH)₃)₄Preparing 5-15% THF solution, adding MgH2, and synthesizing under hydrogen pressure to obtain NaBH 4.

Furthermore, the high-energy ball mill is a planetary ball mill, and the material-ball ratio of the ball mill is 20-30: 1. Preferably, the time of ball milling is 12 hours.

Further, the reaction temperature in the step 3) is 100-200 ℃, and the heating rate is 5-10 ℃ for minutes.

Further, MgH₂With NaB (OCH)₃)₄The molar ratio of (A) to (B) is 2.5-3.2: 1.

Further, the hydrogen pressure is 2-5 MPa.

The invention has the following beneficial effects: the invention eliminates the expensive hydride raw material which is necessary before, uses organosilane with low cost as the reaction raw material, and introduces NaBO₂In a high-energy ball millInternally ball-milling, NaBO₂Is reduced to NaBH again₄The reaction conditions are simple and easy to control, and the maximum conversion rate can reach more than 90 percent, so that the method not only reduces the manufacturing cost, but also has higher yield of the sodium borohydride, and is beneficial to realizing the industrial production of the sodium borohydride.

Detailed Description

The following description of the preferred embodiments of the present invention is provided for the purpose of illustration and description, and is in no way intended to limit the invention.