CN1239748C - Process for preparing boron hydride by electrolytic method - Google Patents
Process for preparing boron hydride by electrolytic method Download PDFInfo
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- CN1239748C CN1239748C CN 02135357 CN02135357A CN1239748C CN 1239748 C CN1239748 C CN 1239748C CN 02135357 CN02135357 CN 02135357 CN 02135357 A CN02135357 A CN 02135357A CN 1239748 C CN1239748 C CN 1239748C
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- borohydride
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Abstract
The present invention relates to technology for preparing borohydride by an electrolytic method, which belongs to the field of the preparation of hydrogen raw materials in fuel cells, more specifically to the preparation of the borohydride from metaborate in the electrolytic method. The present invention is characterized in that the present invention is the technology for circularly reutilizing the metaborate, alkali metal borohydride is hydrolyzed to generate hydrogen gas, and the byproduct, namely metaborate, is electrolyzed again to generate the borohydride. The present invention uses three-dimensional electrodes and DSA electrodes to increase the surface area of the electrodes, improves mass transfer conditions to increase the speed of electrochemical reactions, and current efficiency can reach more than 30%. Electricity is repeatedly charged or discharged by hydrogen releasing fuel in the present invention, the hydrogen releasing fuel is circularly used, the efficiency of the electrodes is increased, the cost is reduced, and the present invention is green, high and new technology.
Description
Technical Field
The invention discloses a process for preparing borohydride by an electrolytic method, belongs to the field of hydrogen raw material preparation in fuel cells, and particularly relates to a process for preparing borohydride from metaborate by an electrolytic method, namely, the borohydride is prepared by catalyzing and hydrolyzing alkali metal borohydride to generate hydrogen, and the metaborate serving as a byproduct is electrolyzed again to generate the borohydride, so that the metaborate is recycled.
Background
Nowadays, fuel cells are regarded as the first choice in the 21 st century because of the importance of various countries, and are regarded as a clean and efficient power generation technology. Fuel electric vehicles have become a hot spot for the development and competition of various automobile companies in the world.
The best fuel for fuel cells is hydrogen, and recently, a new type of fuel cell using alkali metal borohydride as a fuel is being developed by the chryler group in the U.S. and H-Gene tech. Indicating direct use of BH4 -The performance of the fuel cell is much better than that of the traditional hydrogen fuel cell. The principle is that Recycling metaborate while producing fuel hydrogen is an attractive route for the substantial cost reduction of oxyhydrogen fuel cells. Namely, it is (e.g. using )。
At present, NaBH is available at home and abroad4The synthesis of (A) is mainly Schlesinger and Bayer process. NaBH of China4The production development is slow, only small-scale production is available in Shanghai, Chongqing and the like, but the product is expensive and cannot be used as a hydrogen source of a fuel cell. Suda.seisiirau (ep1067091.a) reported the production of hydrogen by the catalytic hydrolysis of sodium borohydride; lee Jai y (US5599640) reported the use ofBorohydride is used as hydrogen source of fuel cell, Cooper (US3437842) reports that sodium borohydride is prepared by electrolysis method, but the reaction rate is slow, the current efficiency is low (<25%), and the borohydride is not recycled. Literature on the reduction to regenerate borohydride and the formation of boron cycles has not been reported. Researchers in the united states, japan, and the like publicly state that they will make intensive research and development. The problem of fuel recycling has not been solved.
Disclosure of Invention
The invention discloses a preparation method for recycling borohydride fuel, aiming at overcoming the defects of the prior art.
The process for preparing the borohydride by the electrolytic method adopts the electrolytic method to decompose the borohydride to generate the metaborate which is a byproduct of hydrogen and regenerate the borohydride. The process adopts an anode chamber and a cathode chamber, the middle part of the anode chamber is isolated by a cationic membrane, the anode material adopts a corrosion-resistant titanium-based oxide electrode and titanium and other metal alloys, the cathode adopts a three-dimensional electrode (the main components are graphite, nickel, iron, stainless steel and alloys thereof), and the solution of the anode chamber is 0.5-5.0 mol.l-1The acid may be H2SO4、HNO3、H3PO4HCl, etc.; or 1.0 to 5.0mol.l-1An alkali metal hydroxide of (1). The cathode chamber solution is 10 to 50 percent of metaborate (borax and boric acid) and 1.0 to 5.0mol.l-1An alkali metal hydroxide of (1). The temperature is 10-80 ℃, andthe current density is 50-200mA/cm2The electrolysis time is 1-3 h. The current efficiency of the cathode for generating borohydride is more than 30 percent.
Compared with the prior art, the invention has the following advantages:
the process for preparing borohydride by the electrolytic method has the greatest advantage of recycling the boron compound. No report of preparing borohydride from metaborate by an electrolytic method is seen at home. The foreign method has low electrochemical reaction rate, low current efficiency and no recycling. The technique for preparing borohydride by the electrolytic method adopts the three-dimensional electrode to increase the surface area of the electrode, improve the transfer condition and improve the current density, thereby improving the electrochemical reaction rate, improving the current efficiency to be more than 30 percent and simultaneously recycling the raw materials.
Detailed Description
Example 1
Selecting titanium-based manganese dioxide as an anode, nickel as a cathode and 2.0mol.l-1NaOH and 2.0mol.l-12.0mol.l of the metaborate salt as a cathode solution-1H2SO4Is an anode solution with the temperature of 40 ℃ and the current density of 80mA/cm2And 2 hours of electrolysis, the current efficiency is 32%.
Example 2
Selecting titanium-based manganese dioxide as an anode, iron as a cathode and 2.0mol.l-1NaOH and 2.0mol.l-12.0mol.l of the metaborate salt as a cathode solution-1HCL is anode solution, temperature is 48 ℃, current density is 100mA/cm2And the current efficiency is 30 percent after 2 hours of electrolysis.
Example 3
Lead dioxide is selected as an anode, graphite is selected as a cathode, and the volume of the anode is 2.0mol.l-1NaOH and 2.0mol.l-12.0mol.l of the metaborate salt as a cathode solution-1HCl as anode solution at 45 deg.C and current density of 100mA/cm2And the current efficiency is 30 percent after 2 hours of electrolysis.
Example 4
Lead dioxide is selected as an anode, graphite oxide is selected as a cathode, and the concentration of lead dioxide is 2.0mol-1NaOH and 2.0mol.l-12.0mol.l of borate as a cathode solution-1HCl as anode solution, temperature 48 deg.C, current density 100mA/cm2And the current efficiency is 30 percent after 2 hours of electrolysis.
Claims (6)
1.A process for preparing borohydride by electrolysis method features that the borohydride is hydrolyzed by alkali borohydride to generate hydrogen, the metaborate as by-product is electrolyzed again to generate borohydride, which is then reused repeatedly, and the electrolysis system is composed of anode and cathode isolated by cationic membrane, and the electrolysis temp. is controlled at 10-80 deg.C and current density is controlled at 50-200mA/cm in acidic or alkaline solution of anode and alkaline solution of metaborate2Electrolysis is carried out.
2. The process for preparing borohydride by electrolysis according to claim 1, wherein the anode material is titanium-based manganese dioxide or lead dioxide.
3. The process for the preparation of borohydride by electrolysis according to claim 1, wherein a three-dimensional electrode is selected as the cathode.
4. The process for preparing borohydride by electrolysis according to claim 3, wherein said cathode material is selected from the group consisting of nickel, iron, graphite, and graphite oxide.
5. The process for preparing borohydride by electrolysis according to claim 1, wherein the anodic solution is H2SO4、HNO3、H3PO4HCl, NaOH or KOH.
6. The process for preparing borohydride by electrolysis according to claim 1, wherein the cathode solution is a solution of 1.0-5.0mol/L NaOH and borax or a solution of 1.0-5.0mol/L NaOH and boric acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02135357 CN1239748C (en) | 2002-08-10 | 2002-08-10 | Process for preparing boron hydride by electrolytic method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02135357 CN1239748C (en) | 2002-08-10 | 2002-08-10 | Process for preparing boron hydride by electrolytic method |
Publications (2)
| Publication Number | Publication Date |
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| CN1396307A CN1396307A (en) | 2003-02-12 |
| CN1239748C true CN1239748C (en) | 2006-02-01 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 02135357 Expired - Fee Related CN1239748C (en) | 2002-08-10 | 2002-08-10 | Process for preparing boron hydride by electrolytic method |
Country Status (1)
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| CN (1) | CN1239748C (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7108777B2 (en) | 2002-03-15 | 2006-09-19 | Millennium Cell, Inc. | Hydrogen-assisted electrolysis processes |
| CN100337352C (en) * | 2003-03-21 | 2007-09-12 | 乐金电子(天津)电器有限公司 | Mixed electrode structure of fuel cell |
| CN100376051C (en) * | 2003-05-13 | 2008-03-19 | 乐金电子(天津)电器有限公司 | Fuel battery mix electrode structure |
| CN1308489C (en) * | 2004-06-15 | 2007-04-04 | 武汉大学 | Apparatus for preparing boron hydride by electrolysis |
| US8021536B2 (en) * | 2006-04-13 | 2011-09-20 | Air Products And Chemical, Inc. | Method and apparatus for achieving maximum yield in the electrolytic preparation of group IV and V hydrides |
| CN112981427B (en) * | 2021-01-26 | 2023-06-27 | 江苏师范大学 | Three-chamber two-membrane electrolytic tank for preparing sodium borohydride by direct-current electrolytic reduction |
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2002
- 2002-08-10 CN CN 02135357 patent/CN1239748C/en not_active Expired - Fee Related
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| CN1396307A (en) | 2003-02-12 |
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