EP0004903B1 - Method for preparing chlorine by electrolysis of hydrochloric acid, and electrolytic cell therefor - Google Patents
Method for preparing chlorine by electrolysis of hydrochloric acid, and electrolytic cell therefor Download PDFInfo
- Publication number
- EP0004903B1 EP0004903B1 EP79101017A EP79101017A EP0004903B1 EP 0004903 B1 EP0004903 B1 EP 0004903B1 EP 79101017 A EP79101017 A EP 79101017A EP 79101017 A EP79101017 A EP 79101017A EP 0004903 B1 EP0004903 B1 EP 0004903B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- electrolysis
- hydrochloric acid
- electrolytes
- electrodes
- level
- 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
Links
- 238000005868 electrolysis reaction Methods 0.000 title claims description 29
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 title claims description 26
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 title claims description 5
- 239000000460 chlorine Substances 0.000 title claims description 5
- 229910052801 chlorine Inorganic materials 0.000 title claims description 5
- 238000000034 method Methods 0.000 title claims description 4
- 239000003792 electrolyte Substances 0.000 claims description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 3
- 238000007872 degassing Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/24—Halogens or compounds thereof
- C25B1/26—Chlorine; Compounds thereof
Definitions
- the electrolytic generation of hydrogen and chlorine from hydrochloric acid generally takes place in electrolytic cells in which 30 to 45 vertically arranged bipolar electrodes are combined, the electroylsem chamber formed between two electrodes being subdivided by a diaphragm.
- the electrode area is usually approximately 2.5 m 2 and has a square cross section; see for example DAS 1 216 852 or Chem. lng.technik 39, 731 (1967).
- the hydrochloric acid flows through the electrolysis chamber from bottom to top, hydrogen forming in the catholyte space and chlorine in the anolyte space.
- the catholyte and anolyte are thus enriched with gas bubbles on their way through the electrolysis chamber. The gas bubbles are separated after the electrolytes have left the cell.
- the presence of gas bubbles in the electrolyte increases its electrical resistance and thus the specific power consumption of the electrolytic cell. It is therefore desirable, given the current density, to determine the residence time of the electrolyte in the cell, i.e. choose the time during which the gas bubbles accumulate as short as possible. On the other hand, for the cell to operate economically, it is necessary to sufficiently reduce the concentration of hydrochloric acid while passing through the electrolytic cell. Depletion from about 25% to about 20% HCI is usually aimed for.
- the invention therefore relates to a process for the production of chlorine and hydrogen from hydrochloric acid by electrolysis in an electrolysis cell, consisting of a multiplicity of vertically arranged bipolar electrodes, with an electrode space and an catholyte space being divided between two electrodes for dividing the electrolysis chambers formed between them Diaphragm is arranged, further drain and inflow devices for the electrolytes, which is characterized in that the hydrochloric acid is electrolyzed in at least two successive stages, being degassed after leaving one stage and before entering the next stage.
- the invention also relates to a hydrochloric acid electrolysis cell, consisting of a multiplicity of vertically arranged bipolar electrodes, a diaphragm being arranged between two electrodes for dividing the electrolysis chamber formed between them into an anolyte space and a catholyte space, furthermore drainage and inflow devices for the Electrolytes, which is characterized in that the bipolar electrodes and the electrolysis chambers are each divided into floors in at least one horizontal plane perpendicular to the electrode surface and additional inflow and outflow devices are provided for the electrolytes in this plane, so that electrolyte circuits are independent of one another on each floor are trained.
- the height of the partial electrode surfaces resulting from the subdivision of the electrodes is preferably 40 to 80 cm, particularly preferably approximately 60 cm.
- the bipolar electrodes are expediently each held in holding frames which are stacked together in the manner of filter presses.
- the principle of such arrangements is e.g. in DOS 2 222 637 or DOS 2 317 359.
- the electrolysis frames for receiving the electrodes contain a plurality of windows lying one above the other, the webs containing inflow and outflow channels for the electrolytes.
- the electrolysis is preferably carried out at current densities of 4 to 8 kA / m 2 . preferably operated 5 to 7 kA / m 2 .
- the different levels of an electrolysis cell are preferably connected in parallel.
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Description
Die elektrolytische Erzeugung von Wasserstoff und Chlor aus Salzsäure erfolgt im allgemeinen in Elektrolysezellen, in denen 30 bis 45 vertikal angeordnete bipolare Elektroden, wobei die zwischen je zwei Elektroden gebildete Elektroylsemkammer durch ein Diaphragma unterteilt ist, zusammengefaßt sind. Üblicherweise beträgt die Elektrodenfläche ca. 2,5 m2 und besitzt quadratischen Querschnitt; siehe z.B. DAS 1 216 852 oder Chem. lng. Technik 39, 731 (1967). Die Salzsäure durchströmt die Elektrolysekammer von unten nach oben, wobei sich im Katholytraum Wasserstoff und im Anolytraum Chlor bildet. Katholyt und Anolyt werden also auf ihrem Weg durch die Elektrolysekammer mit Gasblasen angereichert. Did Gasblasen werden nach dem Austritt der Elektrolyte aus der Zelle abgeschieden.The electrolytic generation of hydrogen and chlorine from hydrochloric acid generally takes place in electrolytic cells in which 30 to 45 vertically arranged bipolar electrodes are combined, the electroylsem chamber formed between two electrodes being subdivided by a diaphragm. The electrode area is usually approximately 2.5 m 2 and has a square cross section; see for example DAS 1 216 852 or Chem. lng. Technik 39, 731 (1967). The hydrochloric acid flows through the electrolysis chamber from bottom to top, hydrogen forming in the catholyte space and chlorine in the anolyte space. The catholyte and anolyte are thus enriched with gas bubbles on their way through the electrolysis chamber. The gas bubbles are separated after the electrolytes have left the cell.
Durch die Anwesenheit von Gasblasen im Elektrolyten wird dessen elektrischer Widerstand, und damit der spezifische Leistungsverbrauch der Elektrolysezelle erhöht. Es ist daher wünschenswert, bei gegebener Stromdichte die Aufenthaltszeit des Elektrolyten in der Zelle, d.h. die Zeit, während der sich die Gasblasen anreichern, möglichst kurz zu wählen. Andererseits ist es zum wirtschaftlichen Betrieb der Zelle notwendig, die Konzentration der Salzsäure während des Durchgangs durch die Elektrolysezelle hinreichend zu verringern. Üblicherweise wird eine Verarmung von ca. 25% auf ca. 20% HCI angestrebt.The presence of gas bubbles in the electrolyte increases its electrical resistance and thus the specific power consumption of the electrolytic cell. It is therefore desirable, given the current density, to determine the residence time of the electrolyte in the cell, i.e. choose the time during which the gas bubbles accumulate as short as possible. On the other hand, for the cell to operate economically, it is necessary to sufficiently reduce the concentration of hydrochloric acid while passing through the electrolytic cell. Depletion from about 25% to about 20% HCI is usually aimed for.
Gegenstand der Erfindung ist daher ein Verfahren zur Herstellung von Chlor und Wasserstoff aus Salzsäure durch Elektrolyse in einer Elektrolysezelle, bestehend aus einer Vielzahl von vertikal angeordneten bipolaren Elektroden, wobei zwischen je zwei Elektroden zur Unterteilung der zwischen diesen gebildeten Elektrolysekammern in einen Anolytraum und einen Katholytraum ein Diaphragma angeordnet ist, ferner Abfluß- und Zuflußeinrichtungen für die Elektrolyte, das dadurch gekennzeichnet ist, daß die Salzsäure in mindestens zwei aufeinanderfolgenden Stufen elektrolysiert wird, wobei sie nach Austritt aus einer Stufe und vor Eintritt in die jeweils nächste Stufe entgast wird.The invention therefore relates to a process for the production of chlorine and hydrogen from hydrochloric acid by electrolysis in an electrolysis cell, consisting of a multiplicity of vertically arranged bipolar electrodes, with an electrode space and an catholyte space being divided between two electrodes for dividing the electrolysis chambers formed between them Diaphragm is arranged, further drain and inflow devices for the electrolytes, which is characterized in that the hydrochloric acid is electrolyzed in at least two successive stages, being degassed after leaving one stage and before entering the next stage.
Gegenstand der Erfindung ist auch eine Salzsäure-Elektrolysezelle, bestehend aus einer Vielzahl von vertikal angeordneten bipolaren Elektroden, wobei zwischen je zwei Elektroden zur Unterteilung der zwischen diesen gebildeten Elektrolysekammer in einen Anolytraum und einen Katholytraum ein Diaphragma angeordnet ist, ferner Abfluß- und Zuflußeinrichtungen für die Elektrolyte, die dadurch gekennzeichnet ist, daß die bipolaren Elektroden und die Elektrolysekammern jeweils in mindestens einer horizontalen Ebene senkrecht zur Elektrodenfläche in Etagen unterteilt sind und in dieser Ebene zusätzliche Zufluß- und Abflußeinrichtungen für die Elektrolyte vorgesehen sind, so daß in jeder Etage voneinander unabhängige Elektrolytkreisläufe ausgebildet sind.The invention also relates to a hydrochloric acid electrolysis cell, consisting of a multiplicity of vertically arranged bipolar electrodes, a diaphragm being arranged between two electrodes for dividing the electrolysis chamber formed between them into an anolyte space and a catholyte space, furthermore drainage and inflow devices for the Electrolytes, which is characterized in that the bipolar electrodes and the electrolysis chambers are each divided into floors in at least one horizontal plane perpendicular to the electrode surface and additional inflow and outflow devices are provided for the electrolytes in this plane, so that electrolyte circuits are independent of one another on each floor are trained.
Vorzugsweise beträgt die Höhe der durch die Unterteilung der Elektroden entstehenden Teilelektrodenflächen 40 bis 80 cm, besonders bevorzugt ca. 60 cm.The height of the partial electrode surfaces resulting from the subdivision of the electrodes is preferably 40 to 80 cm, particularly preferably approximately 60 cm.
Zweckmäßigerweise werden die bipolaren Elektroden jeweils in Halterahmen gehalten, die nach Art von Filterpressen aneinander geschichtet werden. Das Prinzip solcher Anordnungen ist z.B. in der DOS 2 222 637 oder DOS 2 317 359 beschrieben. Erfindungsgemäß enthalten die Elektrolyserahmen zur Aufnahme der Elektroden mehrere übereinander liegende Fenster, wobei die Stege Zufluß- und Abflußkanäle für die Elektrolyte enthalten.The bipolar electrodes are expediently each held in holding frames which are stacked together in the manner of filter presses. The principle of such arrangements is e.g. in DOS 2 222 637 or DOS 2 317 359. According to the invention, the electrolysis frames for receiving the electrodes contain a plurality of windows lying one above the other, the webs containing inflow and outflow channels for the electrolytes.
Die Erfindung wird nachfolgend anhand der Figuren näher erläutert. Fig. 1 zeigt beispielhaft einen Querschnitt durch eine zwei etagige Elektrolysezelle. Fig. 2 zeigt stark vereinfacht einen Elektrodenrahmen, senkrecht zu der in Fig. 1 gezeigten Schnittrichtung. Den in den Figuren angegebenen Ziffern kommt im Einzelnen folgende Bedeutung zu:
- 1 Elektrodenrahmen
- 2 Bipolar Elektrode
- 3 Kathode
- 4 Anode
- 5 Anolytkammer
- 6 Katholytkammer
- 7 Diaphragma
- 8 Anolytzufuhr
- 9 Katholytzufuhr
- 10 Katholyt
- 11 Anolyt- und Chlorgasableitung
- 12 Katholytentgasung
- 13 Anolytentgasung
- A Anolyt
- K Katholyt
- 1 electrode frame
- 2 bipolar electrodes
- 3 cathode
- 4 anode
- 5 anolyte chamber
- 6 catholyte chamber
- 7 diaphragm
- 8 Anolyte supply
- 9 Catholyte supply
- 10 catholyte
- 11 Anolyte and chlorine gas discharge
- 12 Catholyte degassing
- 13 Anolyte degassing
- A anolyte
- K catholyte
Das erfindungsgemäße Verfahren unter Einsatz der erfindungsgemäßen Elektrolysezelle, wird so betrieben, daß sowohl Katholyt als auch Anolyt die einzelnen Etagen der Elektrolysezelle nacheinander durchströmen und jeweils nach Austritt aus einer Etage und vor Eintritt in die nächste Etage entgast werden, wobei die Elektrolyte stufenweise verarmt werden. Der Elektrolysezelle wird sowohl in Anolyt- als auch im Katholytkreislauf ca. 25%ige Salzsäure zugeführt, wobei die Anolytsäure eine etwas höhere Konzentration aufweisen kann. Die Säure wird in mehreren Stufen auf schließlich 20%ige Salzsäure verarmt.The method according to the invention using the electrolysis cell according to the invention is operated in such a way that both catholyte and anolyte flow through the individual levels of the electrolysis cell one after the other and are degassed each time they exit one level and before entering the next level, the electrolytes being gradually depleted. Approx. 25% hydrochloric acid is fed to the electrolytic cell both in the anolyte and in the catholyte circuit, the anolyte acid being able to have a somewhat higher concentration. The acid is depleted in several stages to finally 20% hydrochloric acid.
Die Elektrolyse wird vorgzugsweise bei Stromdichten von 4 bis 8 kA/m2. vorzugsweise 5 bis 7 kA/m2 betrieben. Dabei werden vorzugsweise die verschiedenen Etagen einer Elektrolysezelle parallel geschaltet.The electrolysis is preferably carried out at current densities of 4 to 8 kA / m 2 . preferably operated 5 to 7 kA / m 2 . The different levels of an electrolysis cell are preferably connected in parallel.
Um Druckdifferenzen in den Elektrolyten zu vermeiden, wird die Säure vorzugsweise zunächst in die oberste Etage einer Elektrolysezelle eingeführt und nach dem Austritt aus einer Etage und Entgasung jeweils in die nächste darunter liegende Etage eingeführt. Jede Etage wird vorzugsweise von unten nach oben durchströmt, un so eine Mitnahme und damit einen beschleunigten Austrag der Gasblasen zu gewährleisten. Für den Fall einer zwei-etagigen Elektrolysezelle ist der bevorzugte Strömungsweg von Anolyt und Katholyt in Fig. 2 durch die eingezeichneten Pfeile dargestellt.To avoid pressure differences in the electrolytes, the acid is preferably increased It is first inserted into the top floor of an electrolysis cell and, after exiting from one floor and degassing, inserted into the next floor below. Each floor is preferably flowed through from bottom to top, so as to ensure entrainment and thus an accelerated discharge of the gas bubbles. In the case of a two-tier electrolysis cell, the preferred flow path of anolyte and catholyte is shown in FIG. 2 by the arrows.
Mit der Erfindung wird der spezifische Energieverbrauch bei der Elektrolyse von Salzsäure herabgesetzt, wobei gleichzeitig durch' Verringerung der notwendigen aktiven Elektrodenflächen etwa 20% Graphit eingespart wird. Die Elektrolyse kann gegenüber den bisher üblichen Stromdichten von ca. 4 kA/m2 bei gleicher Spannung mit erheblich erhöhter Stromdichte betrieben werden. Andererseits wird, wenn die Stromdichte erhalten bleiben soll, ein Spannungsgewinn erreicht, der z.B. bei bestehenden Anlagen die Hintereinanderschaltung von einer erhöhten Zahl von bipolaren Elektroden ermöglicht.With the invention, the specific energy consumption in the electrolysis of hydrochloric acid is reduced, at the same time saving about 20% of graphite by reducing the necessary active electrode areas. Compared to the current densities of approx. 4 kA / m 2 which have been customary up to now, the electrolysis can be operated at the same voltage with a considerably increased current density. On the other hand, if the current density is to be maintained, a voltage gain is achieved which, for example in existing systems, enables the connection of an increased number of bipolar electrodes in series.
Claims (5)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2816152 | 1978-04-14 | ||
| DE2816152A DE2816152C2 (en) | 1978-04-14 | 1978-04-14 | Process for the production of chlorine from hydrochloric acid by electrolysis and hydrochloric acid electrolysis cell |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0004903A2 EP0004903A2 (en) | 1979-10-31 |
| EP0004903A3 EP0004903A3 (en) | 1979-11-14 |
| EP0004903B1 true EP0004903B1 (en) | 1980-12-10 |
Family
ID=6036937
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP79101017A Expired EP0004903B1 (en) | 1978-04-14 | 1979-04-04 | Method for preparing chlorine by electrolysis of hydrochloric acid, and electrolytic cell therefor |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4236983A (en) |
| EP (1) | EP0004903B1 (en) |
| JP (1) | JPS54137496A (en) |
| DE (2) | DE2816152C2 (en) |
| ES (1) | ES479479A1 (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6039757B2 (en) * | 1979-02-02 | 1985-09-07 | クロリンエンジニアズ株式会社 | Hydrochloric acid electrolysis method |
| DE2908269C2 (en) * | 1979-03-02 | 1984-04-26 | Uhde Gmbh, 4600 Dortmund | Hydrochloric acid electrolysis cell |
| IN156372B (en) * | 1980-05-15 | 1985-07-06 | Ici Plc | |
| DE3041897A1 (en) * | 1980-11-06 | 1982-06-09 | Bayer Ag, 5090 Leverkusen | SALT ACID ELECTROLYSIS CELL FOR THE PRODUCTION OF CHLORINE AND HYDROGEN |
| US4402809A (en) * | 1981-09-03 | 1983-09-06 | Ppg Industries, Inc. | Bipolar electrolyzer |
| US4999284A (en) * | 1988-04-06 | 1991-03-12 | E. I. Du Pont De Nemours And Company | Enzymatically amplified piezoelectric specific binding assay |
| US5501986A (en) * | 1988-04-06 | 1996-03-26 | E. I. Du Pont De Nemours And Company | Piezoelectric specific binding assay with mass amplified reagents |
| US5348579A (en) * | 1993-08-11 | 1994-09-20 | Silberline Manufacturing Co., Inc. | Water resistant metal pigment-containing paste and method for making |
| DE19956787A1 (en) * | 1999-11-25 | 2001-05-31 | Bayer Ag | Electrolysis plate |
| ITMI20012003A1 (en) * | 2001-09-27 | 2003-03-27 | De Nora Elettrodi Spa | DIAPHRAGM CELL FOR THE PRODUCTION OF CHLOR-SODA OF INCREASED ELECTRODICAL SURFACE AND METHOD TO REALIZE IT |
| CN100557085C (en) * | 2007-06-28 | 2009-11-04 | 马来西亚大光蓄电池有限公司 | The tandem type electrolytic tank that no lead connects |
| CN112759036A (en) * | 2020-12-28 | 2021-05-07 | 云南驰宏国际锗业有限公司 | Method for treating hydrochloric acid wastewater by electrolysis method and electrolytic cell for hydrochloric acid wastewater electrolysis |
| WO2024126607A1 (en) | 2022-12-14 | 2024-06-20 | Basf Se | Process for preparing at least one polyisocyanate from co2 |
| EP4403589A1 (en) | 2023-01-19 | 2024-07-24 | Basf Se | A process for preparing at least one polyisocyanate from solid material w |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA743083A (en) * | 1966-09-20 | S. Kircher Morton | Electrolytic cell | |
| FR358245A (en) * | 1905-10-03 | 1906-02-02 | Eugene Francois Cote | Method of manufacturing chlorine by electrolysis of hydrochloric acid |
| US1485461A (en) * | 1922-07-13 | 1924-03-04 | Knowles Albert Edgar | Electrolytic cell |
| US2719822A (en) * | 1952-01-10 | 1955-10-04 | Universal Oil Prod Co | Production of chlorine from hydrogen chloride |
| US3236760A (en) * | 1959-11-09 | 1966-02-22 | Oronzio De Nora Impianti | Cells for the production of chlorine from hydrochloric acid |
| DE2162487A1 (en) * | 1971-12-16 | 1973-06-28 | Dow Chemical Co | Chlorine prepn - by electrolysis of hydrochloric acid and polyvalent metal chlorides |
| DE2222637A1 (en) * | 1972-05-09 | 1973-11-29 | Bayer Ag | SUPPORTING FRAME FOR ELECTRODES OF ELECTROLYSIS DEVICES |
| US3915836A (en) * | 1973-04-06 | 1975-10-28 | Bayer Ag | HCl electrolysis frame with a graphite plate arranged therein |
| US3876517A (en) * | 1973-07-20 | 1975-04-08 | Ppg Industries Inc | Reduction of crevice corrosion in bipolar chlorine diaphragm cells by locating the cathode screen at the crevice and maintaining the titanium within the crevice anodic |
-
1978
- 1978-04-14 DE DE2816152A patent/DE2816152C2/en not_active Expired
-
1979
- 1979-03-28 US US06/024,748 patent/US4236983A/en not_active Expired - Lifetime
- 1979-04-04 DE DE7979101017T patent/DE2960061D1/en not_active Expired
- 1979-04-04 EP EP79101017A patent/EP0004903B1/en not_active Expired
- 1979-04-10 ES ES479479A patent/ES479479A1/en not_active Expired
- 1979-04-12 JP JP4369579A patent/JPS54137496A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| EP0004903A3 (en) | 1979-11-14 |
| EP0004903A2 (en) | 1979-10-31 |
| DE2960061D1 (en) | 1981-02-19 |
| JPS54137496A (en) | 1979-10-25 |
| ES479479A1 (en) | 1979-07-16 |
| DE2816152B1 (en) | 1979-10-18 |
| DE2816152C2 (en) | 1980-07-03 |
| US4236983A (en) | 1980-12-02 |
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