DE3925694A1 - Hydrogen storage in cooled pressure vessels - using synthetic adsorbers produced by thermal treatment of ion exchange resins based on styrene-di:vinylbenzene copolymers - Google Patents
Hydrogen storage in cooled pressure vessels - using synthetic adsorbers produced by thermal treatment of ion exchange resins based on styrene-di:vinylbenzene copolymersInfo
- Publication number
- DE3925694A1 DE3925694A1 DE3925694A DE3925694A DE3925694A1 DE 3925694 A1 DE3925694 A1 DE 3925694A1 DE 3925694 A DE3925694 A DE 3925694A DE 3925694 A DE3925694 A DE 3925694A DE 3925694 A1 DE3925694 A1 DE 3925694A1
- Authority
- DE
- Germany
- Prior art keywords
- thermal treatment
- synthetic
- styrene
- adsorbers
- ion exchange
- 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.)
- Withdrawn
Links
Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C11/00—Use of gas-solvents or gas-sorbents in vessels
- F17C11/005—Use of gas-solvents or gas-sorbents in vessels for hydrogen
-
- 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
- C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
- C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
- C01B3/0015—Organic compounds; Solutions thereof
-
- 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
- Y02E60/32—Hydrogen storage
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Filling Or Discharging Of Gas Storage Vessels (AREA)
Abstract
Description
Wasserstoff ist die materielle und energetische Grundlage des Uni versums, welches zu 99% aus Wasserstoff besteht und seine Ener gie aus Kernfusion des Wasserstoffs bezieht. Es ist durchaus denk bar, daß Wasserstoff zum Energielieferant der Zukunft wird. Seine Gewinnung aus Wasser durch Hydrolyse mit Strom aus Sonnenkollekto ren bedeutet, daß Wasserstoff uneingeschränkt zur Verfügung steht. Einer breiten Verwendung des Wasserstoffs als Energiespen der steht seine schwierige Speicherung im Wege: Mit einer kriti schen Temperatur von 33°K birgt die Speicherung in Flüssigform eine Reihe von Gefahren, die eine solche Verwendungsform im Stra ßenverkehr wohl kaum gestatten würden.Hydrogen is the material and energetic basis of the university versums, which consists of 99% hydrogen and its energies relies on nuclear fusion of hydrogen. It is quite thinkable bar that hydrogen will become the energy supplier of the future. His Extraction from water by hydrolysis with electricity from solar panels ren means that hydrogen is fully available stands. Wide use of hydrogen as an energy pen it stands in the way of its difficult storage: with a crit The temperature of 33 ° K is stored in liquid form a number of dangers that such a use in the Stra would hardly allow public transport.
Es wurde deshalb versucht, den Wasserstoff chemisch oder physika lisch zu binden, wobei die Speicherung als Metallhydride die be kannteste ist, aber bei weitem keine Ideallösung darstellt. Daim ler Benz testet seit längerer Zeit Kraftfahrzeuge mit Wasserstoff als Kraftstoff, jedoch verhindert der große Metallhydride-Tank eine breite Anwendung. Nimmt man Drücke und Temperaturen bis maxi mal 55 atü bzw. 150°K in Kauf, die wesentlich problemloser sind als die kritischen Bedingungen für flüssigen Wasserstoff, so läßt sich mit Hilfe von Adsorptionstechniken bei gleichem Speicherge wicht etwa 2½-mal soviel Wasserstoff binden als mittels Metall hydriden. Als Adsorbens wird Aktivkohle genannt. Die Temperatur von 150°K verlangt jedoch noch immer den Einsatz flüssigen Stick stoffs. Fernziel ist es, Adsorbentien zu finden, welche nur mehr Temperaturen, die mit der klassischen Gefriertechnik erreicht werden können, verlangen. Das Beladen der Kohle mit Metallsalzen bzw. die Einführung saurer Gruppen in die innere Oberfläche führte zwar zu einer um bis zu ¹/₃ höherer Speicherkapazität, aber die maximale Arbeitstemperatur lag kaum günstiger. It has therefore been attempted to chemically or physically hydrogen bind binding, the storage as metal hydrides the be is the best known, but is by no means an ideal solution. Daim ler Benz has been testing vehicles with hydrogen for a long time as fuel, but the large metal hydride tank prevents it a wide application. If you take pressures and temperatures up to maxi times 55 atü or 150 ° K in purchase, which are much easier than the critical conditions for liquid hydrogen, so lets with the help of adsorption techniques with the same storage ge bind about 2½ times as much hydrogen as metal hydrides. Activated carbon is mentioned as the adsorbent. The temperature of 150 ° K, however, still requires the use of a liquid stick fabric. The long-term goal is to find adsorbents that only more Temperatures reached with classic freezing technology can be demand. Loading the coal with metal salts or the introduction of acidic groups into the inner surface led to a storage capacity that was up to ¹ / ₃ higher, but the maximum working temperature was hardly more favorable.
Es wurde nun überraschenderweise gefunden, daß sich Adsorbentien, die durch thermische Behandlung von Copolymeren aus Styrol und Di vinylbenzol gewonnen wurden, wesentlich besser für Wasserstoff speicher eignen als Aktivkohle. Es wurde festgestellt, daß mit zu nehmender Pyroloysetemperatur das Speichervermögen zunimmt und we niger gekühlt werden muß bzw. weniger Druck anzuwenden ist. Die thermische Behandlung konnte nicht über 1250°C hinaus durchge führt werden, jedoch war bis dorthin noch keine Umkehr des positi ven Trends feststellbar, so daß es möglich ist, daß eine weitere Temperatursteigerung zu einem noch höheren Speichervermögen führt.It has now surprisingly been found that adsorbents, by the thermal treatment of copolymers of styrene and di vinylbenzene were obtained, much better for hydrogen stores are suitable as activated carbon. It was found that with too increasing Pyroloys temperature the storage capacity increases and we must be cooled less or less pressure is to be applied. The thermal treatment could not go beyond 1250 ° C be led, but there was still no reversal of the positive trends can be identified, so that it is possible that another Temperature increase to an even higher storage capacity leads.
Die normale Form der Absorber sind Kügelchen, da sie durch eine Tröpfchenpolymerisation gewonnen werden. Ihre Größe hängt weitge hend von der Differenz in der Oberflächenspannung der 2 Phasen sowie der mechanischen Energie, die mit dem Rührer, dessen Form ebenfalls einen Einfluß hat, in das System eingepumpt wird. Die Kügelchen selbst bestehen aus Aglomeraten feinster, manchmal ku gelförmiger Teilchen, in denen sich die eigentlichen Adsorptions stellen befinden, während die Hohlräume zwischen den Teilchen deren Zugänglichkeit sicherstellen. Die Verwendung von Kügelchen verschiedener Größen gestattet eine optimale Nutzung des vorhande nen Behältervolumens.The normal form of the absorbers are beads, as they are separated by a Droplet polymerization can be obtained. Their size largely depends based on the difference in the surface tension of the 2 phases as well as the mechanical energy with the stirrer, its shape also has an impact on the system being pumped. The Beads themselves consist of the finest aglomerates, sometimes ku gel-like particles in which the actual adsorption places while the voids between the particles ensure their accessibility. The use of beads Different sizes allow an optimal use of the existing container volume.
Die thermische Behandlung (Dauer 30 min) wurde in Stickstoffatmos phäre, welche fallweise bis zu 15% Wasserdampf enthielt, in einer dem Fachmann als Rinne bekannten Anordnung durchgeführt, sollte aber auch in Wirbelschicht einwandfrei realisierbar sein. Dabei werden bei den angewandten Temperaturen hohe Ansprüche an das Material gestellt.The thermal treatment (duration 30 min) was in nitrogen atmosphere sphere, which occasionally contained up to 15% water vapor, in an arrangement known to the person skilled in the art as a gutter, but should also be feasible in a fluidized bed. High demands are made on the temperatures used put the material.
In einem Druckgefäß wurden bei verschiedenen Temperatu ren behandelte Adsorber eingeführt, auf 150 bzw. 180°K gekühlt und unter 60 atü mit Wasserstoff beladen. Wegen des variierenden Schüttgewichts schwankte die Adsorbermenge von 116 bis 128 g und die Ergebnisse wurden auf 100 g zurückgerechnet: In a pressure vessel at different temperatures ren treated adsorber introduced, cooled to 150 or 180 ° K. and loaded with hydrogen under 60 atm. Because of the varying Apparent density fluctuated from 116 to 128 g and the results were calculated back to 100 g:
Der Zusatz von Wasserdampf wurde nur bei 900°C praktiziert, weil sonst zu viel Abbrand auftrat. Die Aktivierung bei 900°C brachte eine Verbesserung der Kapazität, die im Rahmen der Meßgenauigkeit lag. Das Beladen der Absorber mit Nickel und Palladium, in der Art wie Hydrierungskatalysatoren hergestellt werden, führte zu keinen eindeutigen Ergebnissen.The addition of water vapor was only practiced at 900 ° C because otherwise too much burn-up occurred. Activation at 900 ° C brought an improvement in capacity within the measurement accuracy lay. Loading the absorbers with nickel and palladium in the The way hydrogenation catalysts are made has led to no clear results.
Claims (4)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3925694A DE3925694A1 (en) | 1989-08-03 | 1989-08-03 | Hydrogen storage in cooled pressure vessels - using synthetic adsorbers produced by thermal treatment of ion exchange resins based on styrene-di:vinylbenzene copolymers |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3925694A DE3925694A1 (en) | 1989-08-03 | 1989-08-03 | Hydrogen storage in cooled pressure vessels - using synthetic adsorbers produced by thermal treatment of ion exchange resins based on styrene-di:vinylbenzene copolymers |
Publications (1)
Publication Number | Publication Date |
---|---|
DE3925694A1 true DE3925694A1 (en) | 1991-02-07 |
Family
ID=6386437
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DE3925694A Withdrawn DE3925694A1 (en) | 1989-08-03 | 1989-08-03 | Hydrogen storage in cooled pressure vessels - using synthetic adsorbers produced by thermal treatment of ion exchange resins based on styrene-di:vinylbenzene copolymers |
Country Status (1)
Country | Link |
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DE (1) | DE3925694A1 (en) |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0025919A1 (en) * | 1979-09-04 | 1981-04-01 | Rohm And Haas Company | A process for preferentially removing more planar molecules from mixtures with less planar molecules |
DE3234832A1 (en) * | 1981-09-21 | 1983-03-31 | MPD Technology Corp., 07481 Wyckoff, N.J. | HYDROGEN STORAGE |
EP0230384A2 (en) * | 1986-01-17 | 1987-07-29 | Syracuse University | Method and apparatus for cold storage of hydrogen |
-
1989
- 1989-08-03 DE DE3925694A patent/DE3925694A1/en not_active Withdrawn
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0025919A1 (en) * | 1979-09-04 | 1981-04-01 | Rohm And Haas Company | A process for preferentially removing more planar molecules from mixtures with less planar molecules |
DE3234832A1 (en) * | 1981-09-21 | 1983-03-31 | MPD Technology Corp., 07481 Wyckoff, N.J. | HYDROGEN STORAGE |
EP0230384A2 (en) * | 1986-01-17 | 1987-07-29 | Syracuse University | Method and apparatus for cold storage of hydrogen |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
OM8 | Search report available as to paragraph 43 lit. 1 sentence 1 patent law | ||
8110 | Request for examination paragraph 44 | ||
8139 | Disposal/non-payment of the annual fee |