WO2008093286A2 - Catalytic hydrolysis process of sodium borohydride for hydrogen generation - Google Patents

Catalytic hydrolysis process of sodium borohydride for hydrogen generation Download PDF

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Publication number
WO2008093286A2
WO2008093286A2 PCT/IB2008/050325 IB2008050325W WO2008093286A2 WO 2008093286 A2 WO2008093286 A2 WO 2008093286A2 IB 2008050325 W IB2008050325 W IB 2008050325W WO 2008093286 A2 WO2008093286 A2 WO 2008093286A2
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Prior art keywords
sodium borohydride
catalyst
chloride
prepared
iron
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PCT/IB2008/050325
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French (fr)
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WO2008093286A3 (en
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Sadig Kuliyev
Beycan Ibrahimoglu
Rafig Alibeyli
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Vestel Elektronik Sanayi Ve Ticaret A.S.
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Publication of WO2008093286A2 publication Critical patent/WO2008093286A2/en
Publication of WO2008093286A3 publication Critical patent/WO2008093286A3/en

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
    • C01B3/065—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents from a hydride
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Definitions

  • the present invention relates to hydrogen production and more particularly to producing hydrogen by means of hydrolyzing sodium borohydride.
  • Sodium borohydride contains 10.6% hydrogen by weight, corresponding to 2 moles. NaBH 4 must be catalytically hydrolyzed in order to release this hydrogen content:
  • the hydrolysis of sodium borohydride is conducted at temperatures typically close to the room temperature by making use of different heterogeneous (solid) [1-4] and homogeneous (liquid) [5] catalysts.
  • the heterogeneous catalysts employed in hydrolyzing sodium borohydride have the following advantages over the homogeneous catalysts:
  • Metal borides also do provide high catalytic activity in the hydrolysis reaction of NaBH 4 with water. These catalytic systems, however, are likewise relatively expensive.
  • the approach in the background art that most closely resembles the present invention is the hydrolysis of NaBH 4 on catalysts containing various active metals (Ni, Cu, Co, etc. ) on various supports (AI 2 O 3 , etc.).
  • the most important advantage of this process is the inexpensiveness of catalysts under use, whilst the drawback here comes from the fact that such catalysts provide lower activity as compared to Ru- or Pt-containing catalysts and metal borides.
  • the objective of the present invention is to provide a relatively higher-efficiency hydrogen production by means of the water-hydrolysis method of sodium borohydride.
  • This objective is achieved by making use of FeCI 2 -NiCI 2 / ⁇ -AI 2 O 3 type catalysts presenting higher activity and requiring a special preparation method according to the process of the present invention.
  • the process proposed here is as following. First of all, the catalyst to be used in the proposed process is prepared. For this purpose, industrial-type Y-AI 2 O 3 is used as the catalyst support, and FeCI 2 and NiCI 2 are employed as active compounds. The concentration of each FeCI 2 and NiCI 2 salt on the catalyst's surface vary between 5 to 20%, with a weight proportion of 1 :1 between themselves, and a total weight of 10- 40%.
  • Such catalysts are prepared by means of adsorbing on the Y-AI 2 O 3 surface the ethyl alcohol solutions of metal salts together in a multi-step (2 to 4-step) method.
  • the method of adsorption on the Y-AI 2 O 3 surface is conducted at room temperature. After the support is subjected to adsorption, the evaporation of solution, and the drying and calcination of catalysts are carried out under air.
  • the FeCI 2 -NiCI 2 / ⁇ -AI 2 O 3 catalyst used in this invention has the following advantages as compared to certain catalysts used for the hydrolysis of sodium borohydride:
  • the catalyst is subjected to drying and calcination operations after each adsorption step conducted on the support surface.
  • Catalysts prepared in this manner is used in the hydrolysis process of sodium borohydride according to the present invention.
  • the process is conducted under atmosphere pressure at 20 to 50°C temperature.
  • An aqueous solution of NaBH 4 in a basic medium is used as the process input.
  • the present invention can be ratified by means of the following examples.
  • 5% FeCI 2 + 5% NiCI 2 / Y-AI 2 O 3 catalyst is prepared for use in the process of hydrolyzing NaBH 4 .
  • 0.56 g FeCI 2 and 0.56 g NiCI 2 salts are dissolved in 20 ml 99.5% ethyl alcohol and the resulting solution is adsorbed in two steps onto the surface of 10 g Y-AI 2 O 3 previously dried for 4 hours at 150 0 C.
  • Half the amount (Yz) of the salt solution is adsorbed in each step and each adsorption period is conducted for 12 hours.
  • the solution is evaporated, the catalyst dried under air at 150 0 C for 4 hours, and is subjected to calcination at 500 0 C for 4 hours.
  • the solution is evaporated and the catalyst is dried under air at 150 0 C for 4 hours again. Then, the catalyst is subjected to a final calcination step under air at 600 0 C for 4 hours.
  • a 1 g-sample is taken from the prepared catalyst and used in hydrolyzing a 10 ml aqueous solution of NaBH 4 .
  • the content of the aqueous solution of sodium borohydride used as raw material in this process is as following (% by weight):
  • the hydrolysis process of sodium borohydride is conducted in a discontinuous manner with respect to the NaBH 4 solution and catalyst and a continuous experimental system respectively, to the hydrogen formed.
  • the amount of hydrogen produced in this process is measured by means of a gas counter over the period the hydrolysis reaction is conducted.
  • the resulting hydrogen is analyzed by gas chromatography.
  • 10% FeCI 2 + 10% NiCI 2 / Y-AI 2 O 3 catalyst is prepared for use in the process of hydrolyzing NaBH 4 .
  • the FeCI 2 and NiCI 2 salts each weighed 1.25 g and dissolved in 30 ml ethyl alcohol for preparing the catalyst.
  • the adsorption of aqueous solutions of metal salts on the surface of 10 g of Y-AI 2 O 3 is conducted in 3 steps.
  • One third (1/3) of the salt solution is used in each adsorption step and each adsorption period is conducted for 12 hours.
  • the catalyst's drying and calcination steps, the catalyst's preparation operation and other conditions of conducting the hydrolysis process of NaBH 4 are identical with those of Example 1.
  • the formation rates of hydrogen produced at 25 and 50 0 C temperatures according to the present process are given in Table 2 below.
  • 20% FeCI 2 + 20% NiCI 2 / Y-AI 2 O 3 catalyst is prepared for use in the process of hydrolyzing NaBH 4 .
  • the FeCI 2 and NiCI 2 salts each weighed 3.33 g and dissolved in 40 ml ethyl alcohol for synthesizing the catalyst.
  • One fourth (1/4) of the salt solution is adsorbed in each step and each adsorption period is conducted for 12 hours.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)
  • Hydrogen, Water And Hydrids (AREA)

Abstract

The catalyst used in the catalytic hydrolysis process of sodium borohydride with water for producing hydrogen is prepared by adsorbing on the surface of gamma-aluminum oxide the salts of iron (II) chloride and nickel chloride in a multi-step manner. Aqueous solutions of iron (II) chloride and nickel chloride salts are adsorbed together in 2 to 4 steps on the surface of gamma-aluminum in preparing the catalyst used in the process, wherein the weight proportion of iron (II) chloride and nickel chloride on the catalyst surface is 1 :1 and their total amounts are 10-40% by weight. While the catalyst used in the process is prepared, it is subjected to drying at 1500C and to calcination at 500°C following each interim adsorption step.

Description

DESCRIPTION
HYDROLYSIS PROCESS OF SODIUM BOROHYDRIDE FOR PRODUCING
HYDROGEN
TECHNICAL FIELD
The present invention relates to hydrogen production and more particularly to producing hydrogen by means of hydrolyzing sodium borohydride.
TECHNICAL PROBLEMS THE PRESENT INVENTION AIMS TO SOLVE
The gradual increase in environmental pollution and decrease in fossil fuels renders hydrogen more considerable as a clean source of energy. Therefore the production, storage, and use of hydrogen as a source of energy in various fields, but specifically in fuel cells became one of the most serious problems in the world. For this reason, safe storage and transportation methods of hydrogen are other crucial problems to be solved in order to provide a wide utilization of hydrogen. The following methods are typically being used to store hydrogen:
• compressing under high pressure,
• liquefying by means of deep cooling,
• storing in the form of metal hydrides, and
• storing with chemicals.
All such methods have both advantages and disadvantages. The storage of hydrogen with chemicals is significant with respect to economy and safety. Among such chemicals, the metal borohydrides and especially sodium borohydride (NaBH4) are the most significant ones with respect to their technical specifications.
Sodium borohydride contains 10.6% hydrogen by weight, corresponding to 2 moles. NaBH4 must be catalytically hydrolyzed in order to release this hydrogen content:
NaBH4 + 2H2O → 4H2 + NaBO2 + heat (300 kJ)
As seen, the hydrolysis of sodium borohydride releases those 2 moles of hydrogen as well, that are contained by the water reactant. Therefore, as a result of hydrolyzing 1 mol of NaBH4 with water, 4 moles of hydrogen, or 21.2% hydrogen by weight of sodium borohydride are formed.
The hydrolysis of sodium borohydride is conducted at temperatures typically close to the room temperature by making use of different heterogeneous (solid) [1-4] and homogeneous (liquid) [5] catalysts. The heterogeneous catalysts employed in hydrolyzing sodium borohydride have the following advantages over the homogeneous catalysts:
• relatively longer functioning period of catalyst,
• convenient removing of catalysts from the sodium metaborate (NaBO2) solution, formed as a side product in the hydrolysis reaction, and
• no formation of gases, as other side products, (diborane, etc.) except sodium borohydride, to possibly contaminate specially the hydrogen produced during the hydrolysis process.
Various heterogeneous catalysts are being employed in the hydrolysis process of sodium borohydride [1-4]. Such catalysts differ according to their chemical structures and other physicochemical features, thereby presenting different catalytic activities.
It is possible to classify the hydrolysis process of sodium borohydride into three groups, based on the type of catalyst employed:
• the use of Ru- or Pt-containing catalysts [1], • the use of metal borides [2], and
• the use of metal-containing catalysts on pure metals or various carriers [3, 4]. Ru- or Pt-containing catalysts on different supports (AI2O3, etc.) present high activity during the hydrolysis of NaBH4. The most significant drawback of such catalysts are their expensiveness.
Metal borides (NixB, etc.) also do provide high catalytic activity in the hydrolysis reaction of NaBH4 with water. These catalytic systems, however, are likewise relatively expensive.
Accordingly, the approach in the background art that most closely resembles the present invention is the hydrolysis of NaBH4 on catalysts containing various active metals (Ni, Cu, Co, etc. ) on various supports (AI2O3, etc.). The most important advantage of this process is the inexpensiveness of catalysts under use, whilst the drawback here comes from the fact that such catalysts provide lower activity as compared to Ru- or Pt-containing catalysts and metal borides.
The objective of the present invention is to provide a relatively higher-efficiency hydrogen production by means of the water-hydrolysis method of sodium borohydride. This objective is achieved by making use of FeCI2-NiCI2/γ-AI2O3 type catalysts presenting higher activity and requiring a special preparation method according to the process of the present invention. The process proposed here is as following. First of all, the catalyst to be used in the proposed process is prepared. For this purpose, industrial-type Y-AI2O3 is used as the catalyst support, and FeCI2 and NiCI2 are employed as active compounds. The concentration of each FeCI2 and NiCI2 salt on the catalyst's surface vary between 5 to 20%, with a weight proportion of 1 :1 between themselves, and a total weight of 10- 40%. Such catalysts are prepared by means of adsorbing on the Y-AI2O3 surface the ethyl alcohol solutions of metal salts together in a multi-step (2 to 4-step) method. The method of adsorption on the Y-AI2O3 surface is conducted at room temperature. After the support is subjected to adsorption, the evaporation of solution, and the drying and calcination of catalysts are carried out under air.
The FeCI2-NiCI2/γ-AI2O3 catalyst used in this invention has the following advantages as compared to certain catalysts used for the hydrolysis of sodium borohydride:
• the solutions of FeCI2 and NiCI2 salts are adsorbed in a multi-step manner on the support in order to have such active metal salts distribute more uniformly on the support surface,
• the solutions of FeCI2 and NiCI2 salts are adsorbed together onto the support surface, and
• the catalyst is subjected to drying and calcination operations after each adsorption step conducted on the support surface.
Catalysts prepared in this manner is used in the hydrolysis process of sodium borohydride according to the present invention. The process is conducted under atmosphere pressure at 20 to 50°C temperature. An aqueous solution of NaBH4 in a basic medium is used as the process input.
The significant advantages with the present invention over known hydrolysis processes of sodium borohydride are as following:
Advantages of the catalyst
• high activity,
• use of inexpensive commercial γ-AI2O3 as the catalyst support,
• use of inexpensive metal salts such NiCI2, and particularly FeCI2 as the active compounds, and
• inexpensive catalyst. Advantages of the process
• high conversion rate of NaBH4,
• high hydrogen efficiency, and
• low-cost H2 production.
The present invention can be ratified by means of the following examples.
Example 1
5% FeCI2 + 5% NiCI2 / Y-AI2O3 catalyst is prepared for use in the process of hydrolyzing NaBH4. For this purpose, 0.56 g FeCI2 and 0.56 g NiCI2 salts are dissolved in 20 ml 99.5% ethyl alcohol and the resulting solution is adsorbed in two steps onto the surface of 10 g Y-AI2O3 previously dried for 4 hours at 1500C. Half the amount (Yz) of the salt solution is adsorbed in each step and each adsorption period is conducted for 12 hours. Following the first interim adsorption step the solution is evaporated, the catalyst dried under air at 1500C for 4 hours, and is subjected to calcination at 5000C for 4 hours. Following the second interim adsorption step, the solution is evaporated and the catalyst is dried under air at 1500C for 4 hours again. Then, the catalyst is subjected to a final calcination step under air at 6000C for 4 hours.
A 1 g-sample is taken from the prepared catalyst and used in hydrolyzing a 10 ml aqueous solution of NaBH4. The content of the aqueous solution of sodium borohydride used as raw material in this process is as following (% by weight):
NaBH4 - 10, NaOH - 5, Pure H2O - 85.
The hydrolysis process of sodium borohydride is conduced in a discontinuous manner with respect to the NaBH4 solution and catalyst and a continuous experimental system respectively, to the hydrogen formed. The amount of hydrogen produced in this process is measured by means of a gas counter over the period the hydrolysis reaction is conducted. The resulting hydrogen is analyzed by gas chromatography.
The formation rates of hydrogen produced at 25 and 500C temperatures according to the present process are given in Table 1 below. Table 1
Figure imgf000006_0001
Example 2
10% FeCI2 + 10% NiCI2 / Y-AI2O3 catalyst is prepared for use in the process of hydrolyzing NaBH4. The FeCI2 and NiCI2 salts each weighed 1.25 g and dissolved in 30 ml ethyl alcohol for preparing the catalyst. The adsorption of aqueous solutions of metal salts on the surface of 10 g of Y-AI2O3 is conducted in 3 steps. One third (1/3) of the salt solution is used in each adsorption step and each adsorption period is conducted for 12 hours. After the first and second interim adsorption steps, the catalyst's drying and calcination steps, the catalyst's preparation operation and other conditions of conducting the hydrolysis process of NaBH4 are identical with those of Example 1. The formation rates of hydrogen produced at 25 and 500C temperatures according to the present process are given in Table 2 below.
Table 2
Figure imgf000006_0002
Example 3
20% FeCI2 + 20% NiCI2 / Y-AI2O3 catalyst is prepared for use in the process of hydrolyzing NaBH4. The FeCI2 and NiCI2 salts each weighed 3.33 g and dissolved in 40 ml ethyl alcohol for synthesizing the catalyst. One fourth (1/4) of the salt solution is adsorbed in each step and each adsorption period is conducted for 12 hours.
After the first, second, and third interim adsorption steps, the catalyst's drying and calcination steps, and the catalyst's preparation and other conditions of conducting the hydrolysis process are identical with those of Examples 1 and 2. The formation rates of hydrogen produced at 25 and 500C temperatures according to the present process are given in Table 3 below.
Table 3
Figure imgf000007_0001

Claims

1. A catalytic hydrolysis process of sodium borohydride with water for producing hydrogen, characterized in that the catalyst used in this process is prepared by adsorbing on the surface of gamma-aluminum oxide (Y-AI2O3) the salts of iron (II) chloride (FeCI2) and nickel chloride (NiCI2) in a multi-step manner.
2. The sodium borohydride hydrolysis process according to Claim 1 , characterized in that the catalyst used in this process is prepared by adsorbing the solutions of iron (II) chloride and nickel chloride salts together on the surface of gamma-aluminum oxide in 2 to 4 steps.
3. The sodium borohydride hydrolysis process according to Claim 1 , characterized in that the weight proportion of the iron (II) chloride and nickel chloride salts on the catalyst's surface used in this process is 1 :1 and their total weight are 10-40% by weight.
4. The sodium borohydride hydrolysis process according to Claim 1 , characterized in that the catalyst used in this process is subjected to drying at 1500C and to calcination at 5000C following each interim adsorption operation while the catalyst is prepared.
PCT/IB2008/050325 2007-02-02 2008-01-30 Catalytic hydrolysis process of sodium borohydride for hydrogen generation WO2008093286A2 (en)

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TR2007/00586A TR200700586A2 (en) 2007-02-02 2007-02-02 Hydrolysis process of sodium boron hydride for hydrogen production.
TR2007/00586 2007-02-02

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11091374B1 (en) * 2019-09-28 2021-08-17 Ge Solartech, LLC Method to produce high purity germane from germanium dioxide or impure germanium compounds

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050036941A1 (en) * 2003-08-14 2005-02-17 Bae In Tae Hydrogen generator
US20050135996A1 (en) * 2003-12-19 2005-06-23 Ortega Jeffrey V. Triborohydride salts as hydrogen storage materials and preparation thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050036941A1 (en) * 2003-08-14 2005-02-17 Bae In Tae Hydrogen generator
US20050135996A1 (en) * 2003-12-19 2005-06-23 Ortega Jeffrey V. Triborohydride salts as hydrogen storage materials and preparation thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE CA [Online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; BAI, YING ET AL: "Anion-effect on hydrogen generation from sodium borohydride solution" XP002510146 retrieved from STN Database accession no. 147:146892 & XIANDAI HUAGONG , 26(10), 40-42, 44 CODEN: HTKUDJ; ISSN: 0253-4320, 2006, *
H. I. SCHLESINGER ET AL.: "Sodium borohydride, its hydrolysis and its use as a reducing agent and in the generation of hydrogen" JOURNAL OF THE AMERICAN CHEMICAL SOCIETY., vol. 75, no. 1, 1953, pages 215-219, XP002510145 USAMERICAN CHEMICAL SOCIETY, WASHINGTON, DC. *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11091374B1 (en) * 2019-09-28 2021-08-17 Ge Solartech, LLC Method to produce high purity germane from germanium dioxide or impure germanium compounds

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