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CN1028249C - Improved method for electrolytic prodn. of fluorine and the special electrolytic bath - Google Patents

Improved method for electrolytic prodn. of fluorine and the special electrolytic bath Download PDF

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Publication number
CN1028249C
CN1028249C CN 92105835 CN92105835A CN1028249C CN 1028249 C CN1028249 C CN 1028249C CN 92105835 CN92105835 CN 92105835 CN 92105835 A CN92105835 A CN 92105835A CN 1028249 C CN1028249 C CN 1028249C
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negative electrode
heat transfer
electrolyzer
transfer fluid
heat
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CN 92105835
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CN1081473A (en
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吴吉丰
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Abstract

The present invention relates to an improved method for preparing fluorine by electrolysis and a novel electrolytic tank. A cathode in the electrolytic tank is designed to be the only heat exchange component and is insulated from a tank body and a pipeline for conveying heat conducting fluid, and non-conducting heat stability fluid is used as the heat conducting fluid. The danger that a heat exchanger is corroded and penetrated does not exist, and the danger that hydrogen gas and fluorine gas are mixed also does not exist. Simultaneously, the useless consumption of the electric energy of current, which is caused when the current passes through the tank body or the pipeline for conveying heat conducting fluid or the heat conducting fluid, does not exist. The electrolytic tank has the advantages of simple structure and convenient operation, and electrolytic tanks in various specifications can be combined by the cathode heat exchange components in different numbers according to the single tank production capacity differently required.

Description

Improved method for electrolytic prodn. of fluorine and the special electrolytic bath
The present invention relates to a kind of improved electrolysis system fluorine method and be specifically designed to the modified version electrolyzer of this method.
Fluorine has important purposes on Chemical Manufacture, it can be used for various flaorination process, especially is used for producing UF6 on nuclear industry in large quantities.
Usually, fluorine is about 100 ℃, is ionogen with fusion KF2HF, is anode at one with the carbonaceous electrodes, is that electrolysis HF makes in the electrolyzer of negative electrode with the steel plate.
Because the fusing point of KF2HF is 71.7 ℃, it is solid state at normal temperatures, so need be from outside heat supply so that electrolyte melting when electrolyzer starts.On the other hand, in normal electrolytic process, remain on 80-110 ℃ scope in order to make the groove temperature, the heat that must produce electrolytic reaction and because the heat that electrolytic resistance is emitted is in time taken away, otherwise the groove temperature will constantly rise.Therefore a heat exchanger must be set in electrolyzer and, realize electrolytical heating and cooling whereby toward wherein by a kind of heat transfer fluid.
In method in the past, the electrolyzer that is generally used for making fluorine all adds one deck chuck in the outside of cell body wall, as interchanger, as thermophore, this thermophore is flowed with water vapor and water by said chuck with this, realizes electrolytical heating or cooling whereby.
Because general water is electrical conductor, and its transport pipe is ground connection normally, the heat exchanger components of electrolyzer also must be a ground connection in the case, therefore, realizes that as thermophore the electrolyzer heat exchanger components of heat exchange is normally equipotential with cell body with water vapor and water.
In addition, in method in the past, adopt following two types electrolyzer usually:
1, negative electrode is electrically connected with cell body, isolates skirt and cell body electrical isolation;
2, negative electrode and cell body electrical isolation are isolated skirt and are electrically connected with cell body.
Example as first type electrolyzer has US3, and 146,179 and US3,000,801 etc.The cell body of this class electrolyzer and interchanger obtain electro-chemical protection owing to being connected with cathodic electricity; therefore the interchanger perforation that is difficult for being corroded; so just can not cause that thermophore is bled in the electrolyzer yet; but because cell body is connected with cathodic electricity; cell body just has the current potential that equates with negative electrode like this, and therefore cell wall and bottom land all can produce hydrogen in electrolytic process.In order to prevent that the hydrogen that bottom land produces from entering anode region, must cover with electric insulation on the electrolyzer bottom surface.In addition, the isolation skirt of this class electrolyzer must insulate with cell body, and this structurally also is the comparison difficulty.Therefore, the trough body structure of this class electrolyzer and electrolysis procedure are all comparatively complicated.Have, because negative electrode is electrically connected with the cell body and the heat exchanger components of ground connection, like this, in fact negative electrode is exactly ground connection, so has caused the additive decrementation of electric energy again.So this class electrolyzer seldom used after the seventies.
Example as second type of electrolyzer has US4,139,447 and US4,511,440 etc., this class electrolyzer is compared with first type electrolyzer, and its advantage is to avoid hydrogen to sneak into danger in the fluorine gas, and, therefore avoided the additive decrementation of electric energy because the cell body of negative electrode and ground connection and heat exchanger components insulate.But the disadvantage of this class electrolyzer is that cell body and coupled heat exchanger components are owing to can not get electro-chemical protection with cathode insulation; therefore be easy to by electrolyte corrosion; when the interchanger perforation that in a single day is corroded; will bleed immediately in the electrolyzer as the water of thermophore, make ionogen and carbon anode be subjected to grievous injury.Though these two parts of patent documents have all been mentioned the material of available Monel metal as cell body and interchanger, so that they have corrosion resistant performance, yet this has just increased the cost of equipment significantly.
The objective of the invention is to provide a kind of electrolysis system fluorine method of the shortcoming that can overcome above-mentioned two class prior arts and be exclusively used in modified version electrolyzer in this method.That is to say, the present invention should be that the hydrogen that can prevent the electrolysis generation is effectively sneaked in the fluorine gas with electrolysis system fluorine method and the special-purpose electrolyzer that provides, guarantee the safety of production and the purity of product, can eliminate simultaneously the additive decrementation of electric energy again, reduce production costs, and can also eliminate be corroded perforation and cause bleed danger in the electrolyzer of thermophore therefrom of interchanger, and this electrolyzer is simple in structure, equipment cost is low, processing ease.
The inventor sums up some following technical scheme through deep research;
1, Cathode Design is become heat exchanger components, just, cancelled simultaneously and the equipotential heat exchanger components of cell body at the inner passage that allows heat transfer fluid to pass through that exists of negative electrode;
2, with insulating material make negative electrode both with cell body insulation, simultaneously also with the transport pipe insulation of heat transfer fluid;
3, on the electrolysis process method, still adopt conventional processing condition basically, comprise and use same ionogen, service temperature and current density.Different is that method of the present invention has adopted above-mentioned modified version electrolyzer, and has selected for use a kind of nonconducting fluid as thermophore.
As above-mentioned, because negative electrode and cell body insulation, therefore except negative electrode, any parts of cell body are neither can to produce hydrogen, so the danger that does not exist hydrogen and fluorine gas to mix mutually.In addition because the insulation of negative electrode and heat transfer fluid transport pipe, and adopted nonconducting heat transfer fluid, therefore do not existed electric current to pass through cell body or heat transfer fluid transport pipe or pass through the unhelpful consumption of the caused electric energy of heat transfer fluid itself.Have is exactly owing to having cancelled with the equipotential heat exchanger components of cell body negative electrode itself to be designed to heat exchanger components again; therefore make heat exchanger components obtain electro-chemical protection, so do not exist heat exchanger components to be corroded perforation and bleed the danger in the ionogen of the heat transfer fluid that causes therefrom.And such cell construction is simple, and negative electrode and cell body all can be used the plain carbon stool manufacturing, and equipment manufacturing cost is cheap, and easy to operate.Owing to worked out this effective electrolysis system fluorine method and this modified version electrolyzer, so far just finished the present invention with novel structure.
In fact, the advantage that electrolyzer had of electrolysis system fluorine method of the present invention and special use is from the design of its novelty, and they all do not have very strict requirement to the operational condition of technology and the manufacturing of equipment.To do more detailed narration to feature of the present invention below.
The ionogen of Shi Yonging is general system fluorine ionogen in the method for the invention, it is made up of alkali-metal fluorochemical and hydrogen fluoride usually, commonly used is made up of KF and HF, its molar ratio can be KF: HF=1: 1.8-1 usually: the 2.2(mole), the most frequently used is 1: the 2(mole), just a kind of composition is about the ionogen of KF2HF.Electrolysis temperature does not have strict restriction; as long as can guarantee that ionogen is in molten state; for example should be higher than 75 ℃ at least usually; on the other hand, temperature is too high also can bring adverse influence to electrolysis process, but because the interchanger in the used electrolyzer of the present invention is exactly a negative electrode itself; it obtains good electro-chemical protection; so do not have the danger of the perforation that is corroded, therefore in the method for the invention, the upper limit of electrolysis temperature can be higher than the upper temperature limit in the currently known methods significantly.For method of the present invention, electrolysis temperature suits between 75-150 ℃, but adopts 80-130 ℃ usually morely, preferably is 80-110 ℃, and is preferably 95-105 ℃, promptly about 100 ℃.
The non-conductive heat transfer fluid of using in the method for the present invention does not have strict restriction, and is as long as it has thermostability, not only non-conductive simultaneously but also can play heat exchange and get final product.It can be a gas, also can be liquid.Wherein the example of suitable gas has: heat stable non-conductive gases such as air, nitrogen, carbonic acid gas, but wherein comparatively convenient with air.The normally moisture free various oils of liquid that are suitable for, its example has: the various liquefied hydrocarbon mixtures in kerosene, diesel oil, whiteruss, the petroleum by-product, the thermal oil of the various trades mark, comprising transformer oil.In above-mentioned all kinds of oil, be preferable with thermal oil.
One of most important characteristic of electrolyzer of the present invention is, negative electrode itself is as heat exchanger components and be heat exchanger components unique in this electrolyzer, just negative electrode inside must have the passage that can allow heat transfer fluid flow through, but the form for passage does not have strict restriction, as long as it can play heat exchange.For example, suitable passage can be: chuck, serpentine tube, tubulation etc.These passages can connect by different modes between each negative electrode, both can be in parallel, also can connect.For different mode of connection, both can also can realize outward by realizing in the groove by groove.
Negative electrode and thermophore pipe insulation also are one of key characters of the present invention, and it can adopt any way insulation, for example can adopt insulation spacer, also can be with one section pipe of being made by insulating material.
Technical scheme of the present invention and feature thereof have been done detailed description above, have made electrolysis system fluorine method of the present invention and the electrolyzer that is exclusively used in this method have following beneficial effect just because of these novel technical schemes:
1, because negative electrode itself is unique heat exchanger components, therefore there is not the be corroded danger of perforation of heat exchanger components, can use the electrolysis temperature of relative broad range, production process safety and stablize the long service life of equipment;
2, except that negative electrode, other each several parts of electrolyzer all do not have hydrogen to produce, and therefore do not have hydrogen and the danger of fluorine gas blended, the purity height of product;
3, the structure of equipment and working method thereof are all very simple;
4, because therefore the electrical isolation between the transport pipe of the nonconducting heat transfer fluid of employing and realization negative electrode and heat transfer fluid can not cause the unhelpful consumption of electric energy;
5, facility investment and productive expense are all cheaper.
Below accompanying drawing is made simple explanation:
Fig. 1 is the schematic top plan view of electrolyzer of the present invention,
Fig. 2 is the sectional elevation synoptic diagram of electrolyzer of the present invention,
Fig. 3 is the flat cutting face synoptic diagram of electrolyzer of the present invention,
Wherein: 1 ... cell body; 2 ... carbon anode; 3 ... the negative electrode heat exchanger components of holding concurrently; 4 ... the heat transfer fluid passage; 5 ... isolate skirt; 6 ... F 2Outlet; 7 ... H 2Outlet; 8 ... the negative electrode contact tube; 9 ... the negative electrode conducting rod; 10 ... electro bath-lid; 11 ... insulating packing; 12 ... insulation spacer or insulation are taken over; 13 ... electrolyte levels; 14 ... heat transfer fluid channel connection pipe; 15 ... HF feeds mouth.
Below in conjunction with embodiment the present invention is further explained, but should illustrates, these embodiment just implement one of preferred mode of the present invention, and it does not play the qualification effect to scope of the present invention.Those of ordinary skill in the art only needs can make various variation and modification according to substantive distinguishing features of the present invention, as long as but should be understood that to have substantive distinguishing features of the present invention, then all various variations all should be regarded as belonging to scope of the present invention.
Embodiment 1
Equipment 1500A electrolyzer
The material of equipment components and the kind of heat transfer fluid:
The cell body carbon steel
Isolate the skirt carbon steel
The negative electrode carbon steel
Anode decolorizing carbon
Heat transfer fluid thermal oil (trade mark BR280)
Cell body size 220 * 90 * 45cm
Every anode dimension 63 * 18 * 5cm
Several 2 groups of anode group
16 (8 every group) of positive plate sum
Negative plate size 170 * 45 * 3cm
Several 3 of negative electrode plate
(promptly in the middle of two groups of anodic and each side have a negative plate)
Groove total voltage 10V
Ionogen is formed KF: HF=1: 2
Totally 3600 hours electrolytic trial time
Total feeding quantity HF 7100kg
Product F 2Total amount 3490kg
With respect to F 2Current efficiency 91%
The equipment corrosion situation: negative electrode does not have corrosion phenomenon, and cell body and isolation skirt weld seam slightly corrode.
Experimental cell is easy to make, and cost is low, and electrolyzer production is stable, and is easy to operate.Each position temperature of ionogen is even in the groove, and HF consumes low.Even the cell body corrosion failure has only small amount of electrolyte to leak outside, need only stop groove, ionogen to be pulled out, cell body still can continue on for producing after repairing, and certainly, if cell body and isolation skirt are made of Monel metal, effect will be better.

Claims (17)

1, a kind of electrolysis system fluorine method, the composition that uses fused to be made up of alkali-metal fluorochemical and hydrogen fluoride is made ionogen, make anode with carbonaceous material, make negative electrode with plain carbon stool, it is characterized in that, use a kind of electrolyzer with special construction, in this electrolyzer, negative electrode plays interchanger simultaneously, negative electrode inside has the passage that can allow heat transfer fluid flow through, all carry out electrical isolation between negative electrode and the heat transfer fluid transport pipe and between negative electrode and the cell body, use a kind of nonconducting thermostability fluid to make thermophore, in beginning during electrolysis, rely on the heat that mobile non-conductive fluid in negative electrode internal passages imported and make electrolyte melting, in electrolytic process, rely on said heat transfer fluid because the heat that electrolytic action produced is taken away, make electrolytical temperature remain on 75 ℃-150 ℃ of normal service temperatures.
2, electrolysis system fluorine method as claimed in claim 1, the liquid that wherein said nonconducting thermostability heat transfer fluid is a kind of heat conduction.
3, as the electrolysis system fluorine method of claim 1 or 2, wherein said nonconducting thermostability heat transfer fluid is a kind of thermal oil.
4, electrolysis system fluorine method as claimed in claim 3, wherein said nonconducting thermostability heat transfer fluid is transformer oil.
5, electrolysis system fluorine method as claimed in claim 1, wherein said electrolyte temperature are 80 ℃-130 ℃.
6, as the electrolysis system fluorine method of claim 1 or 5, wherein said electrolyte temperature is 80-110 ℃.
7, as the electrolysis system fluorine method of claim 1 or 6, wherein said electrolyte temperature is 95-105 ℃.
8, a kind of electrolyzer that is used to implement the electrolysis system fluorine method of claim 1, this electrolyzer adopts the anode of carbonaceous material and the negative electrode of plain carbon stool, there is the isolation skirt that fluorine and the hydrogen that electrolysis generates is separated between anode and the negative electrode, it is characterized in that, negative electrode (3) itself has the structure of interchanger, its inside has the passage (4) that can allow the heat transfer fluid process, do not exist and the equipotential interchanger of cell body (1), there is insulating packing (11) to separate between negative electrode (3) and the cell body (1), has insulation spacer or insulation to take over (12) between negative electrode and the heat transfer fluid transport pipe and separate.
9, electrolyzer as claimed in claim 8, the heat transfer fluid passage of wherein said negative electrode inside is the chuck shape.
10, electrolyzer as claimed in claim 8, the heat transfer fluid passage of wherein said negative electrode inside is snakelike tubulose.
11, electrolyzer as claimed in claim 8, the heat transfer fluid passage of wherein said negative electrode inside is the tubulation shape.
12, electrolyzer as claimed in claim 8, the heat transfer fluid passage of wherein said negative electrode inside is in parallel to each negative electrode.
13, electrolyzer as claimed in claim 8, the heat transfer fluid passage of wherein said negative electrode inside is placed in-line to each negative electrode.
14, as the electrolyzer of claim 8 or 12, the heat transfer fluid passage of wherein said negative electrode inside is by carrying out parallel connection in the groove.
15, as the electrolyzer of claim 8 or 12, the heat transfer fluid passage of wherein said negative electrode inside carries out parallel connection outward by groove.
16, as the electrolyzer of claim 8 or 13, the heat transfer fluid passage of wherein said negative electrode inside is placed in-line by carrying out in the groove.
17, as the electrolyzer of claim 8 or 13, the heat transfer fluid passage of wherein said negative electrode inside is to carry out placed in-line outward by groove.
CN 92105835 1992-07-24 1992-07-24 Improved method for electrolytic prodn. of fluorine and the special electrolytic bath Expired - Fee Related CN1028249C (en)

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Application Number Priority Date Filing Date Title
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CN1028249C true CN1028249C (en) 1995-04-19

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102834549A (en) * 2010-04-14 2012-12-19 东洋炭素株式会社 Gas generation device and gas generation method

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100515412B1 (en) * 2003-01-22 2005-09-14 도요탄소 가부시키가이샤 Electrolytic apparatus for molten salt
CN101949024A (en) * 2010-10-18 2011-01-19 天津市泰旭物流有限公司 Process for preparing fluorine by electrolyzing potassium fluoride-hydrogen fluoride
CN104651873A (en) * 2014-12-22 2015-05-27 四川聚核科技有限公司 Intelligentized container modularized middle-temperature electrolytic fluorine-preparing device

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102834549A (en) * 2010-04-14 2012-12-19 东洋炭素株式会社 Gas generation device and gas generation method
CN102834549B (en) * 2010-04-14 2015-11-25 东洋炭素株式会社 Gas generation apparatus and gas generating processes

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