EP0000085B1 - Procédé pour la production et la séparation de l'acide iodhydrique et de l'acide sulfurique et leurs utilisations pour la production d'hydrogène et d'oxygène - Google Patents

Procédé pour la production et la séparation de l'acide iodhydrique et de l'acide sulfurique et leurs utilisations pour la production d'hydrogène et d'oxygène Download PDF

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Publication number
EP0000085B1
EP0000085B1 EP78200029A EP78200029A EP0000085B1 EP 0000085 B1 EP0000085 B1 EP 0000085B1 EP 78200029 A EP78200029 A EP 78200029A EP 78200029 A EP78200029 A EP 78200029A EP 0000085 B1 EP0000085 B1 EP 0000085B1
Authority
EP
European Patent Office
Prior art keywords
sulphuric acid
hydrogen
hydrogen iodide
production
phase
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP78200029A
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German (de)
English (en)
Other versions
EP0000085A1 (fr
Inventor
Giancarlo De Beni
Giancarlo Pierini
Bruno Spelta
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
European Atomic Energy Community Euratom
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European Atomic Energy Community Euratom
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Filing date
Publication date
Application filed by European Atomic Energy Community Euratom filed Critical European Atomic Energy Community Euratom
Publication of EP0000085A1 publication Critical patent/EP0000085A1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B7/00—Halogens; Halogen acids
    • C01B7/13—Iodine; Hydrogen iodide
    • C01B7/135—Hydrogen iodide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/02—Preparation of oxygen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/69—Sulfur trioxide; Sulfuric acid
    • C01B17/90—Separation; Purification
    • 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
    • C01B3/068—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 the hydrogen being generated from the water as a result of a cyclus of reactions, not covered by groups C01B3/063 or C01B3/105
    • 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

  • This invention relates to a process for the production and separation of hydrogen iodide and sulphuric acid produced in the Bunsen Reaction when using liquid sulphur dioxide as a solvent, and to use of the hydrogen iodide and sulphuric acid so separated, for the production of hydrogen and oxygen, respectively, by decomposition of the hydrogen iodide and sulphuric acid.
  • Hydrogen is an important intermediate product in the chemical industry where it is used in particular in the synthesis of ammonia and for hydrogenation processes, although it has many other uses. Consequently much effort has been directed over the years towards finding methods of producing hydrogen more cheaply.
  • Reaction (1) is well-known as the Bunsen Reaction.
  • the Bunsen Reaction runs at ambient temperatures.
  • Reaction (2) runs at a temperature of 400°C. and above, and reaction (3) runs at a temperature of 650°C. and above.
  • Belgian Patent Specification No. 852674 proposes a separation process in which the Bunsen Reaction is carried out in liquid sulphur dioxide as a solvent.
  • the sulphuric acid which is formed in the reaction is insoluble in liquid sulphur dioxide and consequently it forms a separate phase.
  • the sulphuric acid layer becomes more dilute and the hydrogen iodide produced in the reaction then tends to dissolve in the sulphuric acid phase rather than in the sulphur dioxide phase. Consequently the difficulty of separating the hydrogen iodide from the sulphuric acid again arises.
  • the phosphates and phosphonates used in the process of this invention have high boiling points by which is meant that they boil at a temperature sufficiently high that their volatility at the temperature at which the process is carried out does not cause them, along with their useful effect, to be lost from the reaction mixture.
  • alkyl groups of the phosphates and phosphonates may be the same or different. They will usually be lower alkyl groups, by which is meant generally containing no more than eight carbon atoms, and preferably no more than four carbon atoms. Either straight-chain or branched chain alkyl groups may be used.
  • variable parameters of the process are selected such as to produce a sulphuric acid phase having a concentration of at least 40% by weight of H Z SO 4 , since it has been found that above this concentration of H Z SO Q little if any hydrogen iodide tends to migrate into the sulphuric acid phase.
  • the phosphate or phosphonate may be diluted with an organic solvent, such as benzene, white spirit, dodecane or mesitylene, in order to enhance the effect of the phosphate or phosphonate, as is known hereafter in the specific examples.
  • an organic solvent such as benzene, white spirit, dodecane or mesitylene
  • a particularly preferred organic compound for use in the process of this invention is tributyl phosphate (herein referred to as T.B.P.).
  • T.B.P. tributyl phosphate
  • An advantage of the use of tributyl phosphate is that at room temperature sulphur dioxide is quite soluble in it and consequently it is not necessary to use a pressure higher than normal atmospheric pressure in order to keep the sulphur dioxide in liquid form.
  • the scope of the present invention extends not only to a process for the production and separation of hydrogen iodide and sulphuric acid as described herein but also to the use of the hydrogen iodide and sulphuric acid so separated for the production of hydrogen and oxygen, respectively by decomposition of the hydrogen iodide into hydrogen and iodine and of the sulphuric acid into sulphur dioxide, water and oxygen.
  • No invention is claimed in these decomposition procedures themselves, which may be performed by procedures well-known in the art and for which therefore the skilled man requires no detailed instruction. Consequently no detailed exemplification of these procedures is given.
  • the sulphur dioxide phase contains most, if not all, of the hydrogen iodide, and a small amount of sulphuric acid. This phase is first washed with a little water to remove the sulphuric acid. The washings could then be recycled to the main process. Most of the sulphur dioxide is then removed by evaporation and the hydrogen iodide extracted with water. The extracted solution may then be fed to an electrolytic cell for decomposition of the hydrogen iodide to hydrogen and iodine. Complete electrolysis is not required because it is advantageous to have some hydrogen iodide remaining in which the iodine formed can be dissolved. Iodine is very soluble in hydrogen iodide soiutions. The resulting iodine solution is then recycled for a successive hydrogen iodide extraction.
  • the aqueous sulphuric phase contains most of the sulphuric acid produced in the reaction and a little hydrogen iodide if the concentration of H 2 SO 4 is below 40% by weight.
  • This phase is readily concentrated from its usual concentration of around 50-55% e.g. by a multi-effects evaporator, to 65-70% and then thermally decomposed to S0 2 , H 2 0 and 0 2 .
  • Run 38 was performed at a pressure higher than atmospheric pressure using 60 g. of SO2.
  • the H 2 SO 4 concentration in the sulphuric phase depends on the amount of T.B.P. used. When its concentration is above 40% by weight, no hydrogen iodide is present, nor T.B.P. which is water insoluble.
  • the amount of sulphur dioxide required by the reaction can be reduced by increasing the amount of T.B.P. or water, or otherwise by increasing the reaction time and the stirring rate.
  • the water added for the reaction could be reduced by at least 20% if the reaction time had been longer. Consequently the H 2 SO 4 concentration becomes higher.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)

Claims (6)

1. Procédé de production et de séparation d'acide iodhydrique et d'acide sulfurique qui consiste à faire réagir un mélange d'iode, d'eau et un excès d'anhydride sulfureux de manière à former deux phases, la première contenant de l'acide sulfurique aqueux et l'autre de l'acide iodhydrique en solution; à séparer les deux phases et à recueillir de celles-ci respectivement l'acide sulfurique et l'acide iodhydrique, caractérisé en ce qu'on ajoute au milieu réactionnel au moins un compsé organique insoluble dans l'eau choisi parmi les trialylphosphates et les dialkylalkylphosphonates ainsi que leurs mélanges.
2. Procédé suivant la revendication 1, caractérisé en ce qu'on choisit les paramètres variables du procédé, y compris la quantité du compsé organique utilisé, de manière à former une phase d'acide sulfurique ayant une concentration d'au moins 40% en poids d'H2SO4'
3. Procédé suivant la revendication 1 ou 2, caractérisé en ce que le composé ou l'un des composés organiques utilisés est le tributyl- phosphate.
4. Procédé suivant l'une quelconque des revendications précédentes, caractérisé en ce qu'on dilue le composé organique dans un solvant organique.
5. Utilisation de l'acide iodhydrique produit et séparé par le procédé suivant l'une quelconque des revendications précédentes, pour produire de l'hydrogène par décomposition de l'acide iodhydrique en hydrogène et en iode.
6. Utilisation de l'acide sulfurique produit et séparé par le procédé suivant l'une quelconque des revendications précédentes, pour produire de l'oxygène par décomposition de l'acide sulfurique en anhydride sulfureux, en eau et en oxygène.
EP78200029A 1977-12-16 1978-06-01 Procédé pour la production et la séparation de l'acide iodhydrique et de l'acide sulfurique et leurs utilisations pour la production d'hydrogène et d'oxygène Expired EP0000085B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB5254277 1977-12-16
GB5254277 1977-12-16

Publications (2)

Publication Number Publication Date
EP0000085A1 EP0000085A1 (fr) 1978-12-20
EP0000085B1 true EP0000085B1 (fr) 1980-10-29

Family

ID=10464308

Family Applications (1)

Application Number Title Priority Date Filing Date
EP78200029A Expired EP0000085B1 (fr) 1977-12-16 1978-06-01 Procédé pour la production et la séparation de l'acide iodhydrique et de l'acide sulfurique et leurs utilisations pour la production d'hydrogène et d'oxygène

Country Status (5)

Country Link
EP (1) EP0000085B1 (fr)
DE (1) DE2860249D1 (fr)
DK (1) DK565278A (fr)
IE (1) IE47499B1 (fr)
IT (1) IT1158164B (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5960099B2 (ja) * 2012-07-20 2016-08-02 富士フイルム株式会社 エッチング方法及びこれを用いた半導体基板製品及び半導体素子の製造方法
CN115520835B (zh) * 2022-11-24 2023-05-12 浙江百能科技有限公司 一种硫碘循环制氢中能量回收利用的方法与装置
CN116177486B (zh) * 2023-04-23 2023-08-11 浙江百能科技有限公司 基于高效分层的硫碘循环制氢方法及装置

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2339330A (en) * 1942-04-08 1944-01-18 Colgate Palmolive Peet Co Preparing anhydrous hydrogen halides
US3333924A (en) * 1964-01-10 1967-08-01 Hazen Research Recovery of acids
JPS547515B2 (fr) * 1974-04-27 1979-04-07
GB1519397A (en) * 1976-04-01 1978-07-26 Euratom Process for the production of hydrogen

Also Published As

Publication number Publication date
IE782349L (en) 1979-06-16
DE2860249D1 (en) 1981-01-29
EP0000085A1 (fr) 1978-12-20
IT1158164B (it) 1987-02-18
IE47499B1 (en) 1984-04-04
DK565278A (da) 1979-06-17
IT7852292A0 (it) 1978-12-14

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