CN1556251A - Anode structure of electrolysis type ozone generator and its preparation method - Google Patents
Anode structure of electrolysis type ozone generator and its preparation method Download PDFInfo
- Publication number
- CN1556251A CN1556251A CNA2004100003148A CN200410000314A CN1556251A CN 1556251 A CN1556251 A CN 1556251A CN A2004100003148 A CNA2004100003148 A CN A2004100003148A CN 200410000314 A CN200410000314 A CN 200410000314A CN 1556251 A CN1556251 A CN 1556251A
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- CN
- China
- Prior art keywords
- anode
- positive plate
- solid polymer
- ozone generator
- catalyst
- 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.)
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- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000005868 electrolysis reaction Methods 0.000 title claims description 19
- 238000002360 preparation method Methods 0.000 title claims description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 30
- 239000002245 particle Substances 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000010276 construction Methods 0.000 claims description 29
- 239000007787 solid Substances 0.000 claims description 24
- 239000008187 granular material Substances 0.000 claims description 17
- 239000002131 composite material Substances 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 239000005518 polymer electrolyte Substances 0.000 claims description 12
- 229920000642 polymer Polymers 0.000 claims description 11
- 239000010936 titanium Substances 0.000 claims description 11
- 229910052719 titanium Inorganic materials 0.000 claims description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 10
- YADSGOSSYOOKMP-UHFFFAOYSA-N lead dioxide Inorganic materials O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 abstract description 4
- 239000007789 gas Substances 0.000 description 10
- 238000005260 corrosion Methods 0.000 description 8
- 239000007784 solid electrolyte Substances 0.000 description 8
- 230000007797 corrosion Effects 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- 229910052787 antimony Inorganic materials 0.000 description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 4
- 229910052718 tin Inorganic materials 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 102000010637 Aquaporins Human genes 0.000 description 2
- 108010063290 Aquaporins Proteins 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 description 2
- 229940124530 sulfonamide Drugs 0.000 description 2
- 108010022579 ATP dependent 26S protease Proteins 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
Abstract
An adobe structure for electrolysis-type ozone generator and its preparing process are disclosed. Said anode structure is composed of the impervious air-tight compact anode plate and the catalyst particles layer which is freely spread in the space between said anode plate and anode frame. The gap between periphery of anode plate and the inner surface of anode frame is less than the least diameter of catalyst particles but can allow the raw water and generated gas to pass through it.
Description
Technical field:
The present invention relates to be used for the anode construction of the solid polymer electrolyte film composite electrode of electrolysis type ozone generator, and relate to the preparation method of this anode construction.
Technical background:
In order to utilize ozone, people have developed the ozonizer of various ways, and the electrolysis type ozone generator that adopts solid polymer electrolyte film composite electrode is a kind of of present comparatively advanced person.The core of such ozonizer is an electrolyzer, and electrolyzer mainly comprises anode, negative electrode, ionogen and raw water.What described ionogen was now current is solid polymer electrolyte, and this dielectric film has not only played electrolytical effect, but also has played the membranous effect that separates anode and negative electrode.The anode and the negative electrode that are positioned at these solid electrolyte film both sides have been formed combined electrode with it, the anode in this combined electrode is made of solid anodes catalyzer and positive plate.This anode construction is found in the Chinese patent application (November 19 1997 applying date) that is numbered 97122126.x.Catalyzer in this anode is β-plumbic oxide.Described β-plumbic oxide particle is bonded together by the tetrafluoroethylene binding agent, is rolled into the anode catalyst film then.Described positive plate is one to be used for this catalyst film is pressed on the solid polymer dielectric film, the POROUS TITANIUM PLATE of ventilative, permeable, conduction.In this titanium plate the passage of many perforations is arranged, so that raw water and product gas are flow through through it.Because product gas-ozone has very strong corrodibility,, make its surface and internal passages form platiniferous, the antimony of skim, the conduction corrosion resistant coating of tin so must handle this POROUS TITANIUM PLATE with the organic solution that contains platinum, antimony, tin.Such ozonizer anode construction and manufacture craft thereof have following shortcoming:
1. owing to catalyzer β-plumbic oxide particle is bonded together by tetrafluoroethylene when making diaphragm, therefore the particle surface of this plumbic oxide is just with tetrafluoroethylene, tetrafluoroethylene does not have the function of catalyzed reaction, it has reduced β-effective contact area of plumbic oxide particulate, thereby reaction efficiency is descended, finally cause the production rate of ozone to descend.
2. because POROUS TITANIUM itself is expensive, so the positive plate cost made from it is also very high, in order to improve its solidity to corrosion, need it is done complicated surface treatment, this has increased the manufacturing cost of ozonizer again further.In addition, handle even done above-mentioned corrosion protection meticulously, also difficulty guarantees that the totality passage is tightly covered by the described anticorrosion layer that contains the conduction of platinum, antimony, tin.And the corrosion protection of POROUS TITANIUM PLATE processing quality is the deciding factor that influences ozonizer life-span and efficient.
Above-mentioned two shortcomings are to improve the efficient of electrolysis type ozone generator and the restricted link in life-span.
For overcoming above-mentioned shortcoming, industry provides some solutions, a kind of electrode structure is disclosed as European patent application EP 0318442, the kind electrode structure is to form one deck earlier to contain β-plumbic oxide particulate adhesion layer on a side of solid polymer dielectric film, forms the electrolytic coating of one deck plumbic oxide again on this adhesion layer.The kind electrode structure has guaranteed electrically contacting between running contact and the electrolytic coating, but its used running contact, and promptly positive plate is still and makes with porous metal material; U.S. Pat 6365026 discloses a kind of electrode structure, according to this configuration, with electrolytic catalyst morsel or little lattice, thereby where necessary, only need the catalyzer of local replacing inefficacy and need not to change whole catalyzer, the result is the life-span of having improved electrolytic system.But it is still unresolved as the problem that the porous metal positive plate of the weak link of this class ozone electrolytic system is brought; The flat 3-61391 of Japanese patent application discloses a kind of electrolysis type ozone generator device, and anode catalyst is wherein fixed with the resistant metal net and be bonding without tackiness agent.This structure makes the diameter of gas, aquaporin of anode one side increase, and helps improving ozone generation efficiency, still is complicated and expensive but handle as the making of the small-bore resistant metal net of stagnant catalyst means and surface corrosion resistance thereof.
With regard to the preparation method of described ozonizer anode construction, prior art or do not break away from and make POROUS TITANIUM PLATE (net) and it is made the complicated technology that corrosion protection is handled, do not break away from processes such as bonding, plating, pressed-powder anode granules of catalyst, and prior preparation method can't guarantee that the ozonizer anode construction has high working life.
By above citation, do not find anode construction of ideal electrolysis type ozone generator and preparation method thereof as can be known at present as yet to prior art.
The solution that the present invention proposes at the problems referred to above just.
Summary of the invention:
The invention provides a kind of anode construction that is used for the solid polymer electrolyte film composite electrode of electrolysis type ozone generator, it comprises solid polymer dielectric film, positive plate, be clipped in the layer of catalyst particles that forms through free lay between this dielectric film and the positive plate and surround the described layer of catalyst particles that forms through free lay and the anode framework of described positive plate from periphery, it is characterized in that the periphery of described positive plate and the gap between adjacent described anode framework internal surface can make raw water and product gas pass through, again less than the minimum grain size of the granules of catalyst of described free lay.
The above-mentioned used catalyzer of anode construction that is used for the solid polymer electrolyte film composite electrode of electrolysis type ozone generator device is the plumbic oxide particle, and its particle diameter is 0.05～0.9mm.
The above-mentioned anode construction that is used for the solid polymer electrolyte film composite electrode of ozone generating-device, used positive plate are metal sheet or the non-metallic plates of surface through the closely knit atresia of anti-corrosion processing, preferred commercially pure metallic titanium plate.
The present invention also provides the above-mentioned preparation method who is used for the anode construction of electrolytic ozone generator solid electrolyte film composite electrode, it is characterized in that in described solid polymer dielectric film and the formed space of described positive plate lay granules of catalyst freely, and make gap between described positive plate periphery and adjacent described anode framework internal surface, raw water and product gas are passed through, again less than the minimum grain size of described granules of catalyst.
Positive plate periphery with and adjacent anode framework internal surface between the concrete size in gap can determine according to factors such as the capacity of ozonizer, efficient, shape, sizes by the technician, do not lose but this size should guarantee granules of catalyst, guarantee again raw water and product gas to pass through then be vital.
Compare with the anode construction of the solid polymer electrolyte film composite electrode that is used for the electrolysis type ozone generator device of routine, the anode construction of making by the present invention has two significantly differences:
1. granules of catalyst of the present invention, be to be laid between described solid electrolyte film and the positive plate " freedom ", and by prior art, usually with binding agent catalyzer is made catalyzer diaphragm (seeing Chinese patent application 97122126.X), maybe this granules of catalyst is sticked to a side (seeing EP0318442) of solid polymer dielectric film, or granules of catalyst is embedded on the solid polymer dielectric film with the method for machinery.The mode of above-mentioned placement catalyzer makes it be in the state that is fixed and can not relatively moves, and the gap between the granules of catalyst is less or do not have, thereby has reduced surface availability of catalyst, thereby has influenced the catalytic efficiency of this catalyzer.The mode that " freely " of the present invention places catalyzer is meant granules of catalyst is laid between solid polymer dielectric film and the positive plate, and need not push, the chemical means of physical means such as chimeric, bonding or plating and so on makes it fixing.The granules of catalyst of freely being placed can relatively move before being clamped by positive plate, thereby just left bigger gap between the particle, and the effective surface rate of granules of catalyst-both the ratio on the surface of not bonded dose covering was higher.
2. the positive plate of the anode construction of the solid electrolyte film composite electrode that is used for electrolytic ozone generator of prior art mostly is expanded metal, and as POROUS TITANIUM PLATE, the hole of expanded metal is made the usefulness of passage for raw water and product gas one ozone.Positive plate of the present invention is that a surface is covered with the closely knit of conductive protecting layer, waterproof, air-locked metal sheet or non-metallic plates, and the passage of raw water and product gas is made in the gap between the periphery of this positive plate and adjacent anode framework internal surface.Closely knit positive plate of the present invention only is used to clamp granules of catalyst and the passage of not making water, gas, thereby has simplified the function and the manufacture craft of positive plate.
The solid polymer dielectric film of the anode construction of the solid electrolyte film composite electrode that is used for electrolytic ozone generator of the present invention, the 26S Proteasome Structure and Function of anode framework is identical with routine techniques.Described solid electrolyte film is commercially available perfluorinated sulfonic acid cationic exchange membrane (Nafion117 of Du Pont), and anode frame body and function tetrafluoroethylene is made.The component parts of above-mentioned anode construction assembles with usual manner.
The granules of catalyst of the anode construction of the solid electrolyte film composite electrode of making by the present invention that is used for electrolytic ozone generator is owing to freely is placed, so it has bigger effective catalysis area and more gas, aquaporin; Replace expanded metal to make positive plate with closely knit positive plate and not only reduced its manufacture difficulty, but also improved the working life of this positive plate.Because positive plate is the weak link in the electrolytic ozone generator, the raising of its working life directly causes the prolongation of the working life of this ionogen producer.Make anode with the employing expanded metal of routine, placing the existing electrolysis type ozone generator of granules of catalyst in a fixed manner compares, adopt the working life of the ozonizer of anode construction of the present invention to prolong, the ozone productive rate can improve, and because the simplification of manufacture craft helps the stable and commercial scale production of quality product.
Further specify the present invention below by accompanying drawing.
Description of drawings:
Fig. 1 is the sectional view of anode construction that is used for the solid electrolyte film composite electrode of electrolytic ozone generator.
Embodiment:
See also Fig. 1, specific embodiments of the invention are as follows: with particle diameter is that the plumbic oxide particle 2 of 0.05～0.15mm is laid in the space that the anode framework 4 by perfluor sulfanilamide (SN) cationic exchange membrane (Nafion117 of Du Pont) 1 and poly-fluorine tetrem alkene system surrounds, particulate lay thickness is 3mm, cover then with industrially pure titanium and make, thickness is the closely knit waterproof gentle commercially pure metal titanium positive plate 3 of 3mm; Described positive plate 3 forms the surface corrosion resistance conductive layer that the conductive oxide by platinum, tin, antimony constitutes in advance according to a conventional method, after building this positive plate 3, make the gap 5 between the adjacent internal surface of the periphery of positive plate 3 and anode framework 4 be 0.03mm, with joint bolt 6 above-mentioned parts are joined together at last, thereby be assembled into the anode construction of electrolysis type ozone generator.
The electrolysis type ozone generator that above-mentioned anode construction is housed is when operation, raw water arrives ion-exchange membrane 1 through gap 5 and catalytic materials gap between particles, in this electrolytic reaction takes place, the product gas oxygen of generation and ozone are drawn through intergranular gap of catalytic materials and gap 5.
Life-span of electrolysis type ozone generator that above-mentioned anode construction is housed was greater than 6000 hours.
Claims (5)
1. anode construction that is used for the solid polymer electrolyte film composite electrode of electrolysis type ozone generator, this anode construction comprises solid polymer dielectric film, positive plate, be clipped in the layer of catalyst particles that forms through free lay between this solid polymer dielectric film and the positive plate and surround the described layer of catalyst particles that forms through free lay and the anode framework of described positive plate from periphery, it is characterized in that the periphery of described positive plate and the gap between adjacent described anode framework internal surface can make raw water and product gas pass through, again less than the minimum grain size of described granules of catalyst.
2. by the described anode construction that is used for the solid polymer electrolyte film composite electrode of electrolysis type ozone generator of claim 1, it is characterized in that described catalyst layer is that the plumbic oxide particle of 0.05～0.9mm constitutes by particle diameter.
3. by claim 1 or the 2 described anode constructions that are used for the solid polymer electrolyte film composite electrode of electrolysis type ozone generator, it is characterized in that described positive plate is covered with closely knit, waterproof, the airtight metal sheet or the non-metallic plates of conduction anticorrosion layer for the surface.
4. by the described anode construction that is used for the solid polymer electrolyte film composite electrode of electrolysis type ozone generator of claim 3, it is characterized in that described metal sheet is commercially pure metallic titanium plate.
5. aforementioned each preparation method by the anode construction of the described solid polymer electrolyte film composite electrode that is used for electrolysis type ozone generator of claim, it is characterized in that in described solid polymer dielectric film and the formed space of described positive plate, lay anode catalyst particle freely, and make the periphery of described positive plate and the gap between adjacent described anode framework internal surface that raw water and product gas are passed through, again less than the minimum grain size of described granules of catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410000314 CN1281790C (en) | 2004-01-07 | 2004-01-07 | Anode structure of electrolysis type ozone generator and its preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410000314 CN1281790C (en) | 2004-01-07 | 2004-01-07 | Anode structure of electrolysis type ozone generator and its preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1556251A true CN1556251A (en) | 2004-12-22 |
| CN1281790C CN1281790C (en) | 2006-10-25 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200410000314 Expired - Lifetime CN1281790C (en) | 2004-01-07 | 2004-01-07 | Anode structure of electrolysis type ozone generator and its preparation method |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007009311A1 (en) * | 2005-07-20 | 2007-01-25 | Yantai United Ozonetec Corporation | An anode structure for electrolysis-type ozone generator |
| WO2009146653A1 (en) * | 2008-06-04 | 2009-12-10 | Hsu Mingyung | An anode with fastening spring pressure plate for electrolytic ozone generator |
| CN102899685A (en) * | 2012-09-12 | 2013-01-30 | 金华市广源环保科技有限公司 | Cathode and anode catalyst for low-voltage electrolytic ozone generator module and preparation method thereof |
| CN108411330A (en) * | 2018-02-11 | 2018-08-17 | 中氧科技（广州）有限公司 | A kind of membrane electrode assembly and preparation method thereof for electrolysis ozone generator |
| CN113862697A (en) * | 2021-09-29 | 2021-12-31 | 中检陆桥(中山市)科技有限公司 | Device for hydrolyzing ozone by using multilayer PEM (proton exchange membrane) |
-
2004
- 2004-01-07 CN CN 200410000314 patent/CN1281790C/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007009311A1 (en) * | 2005-07-20 | 2007-01-25 | Yantai United Ozonetec Corporation | An anode structure for electrolysis-type ozone generator |
| WO2009146653A1 (en) * | 2008-06-04 | 2009-12-10 | Hsu Mingyung | An anode with fastening spring pressure plate for electrolytic ozone generator |
| CN102899685A (en) * | 2012-09-12 | 2013-01-30 | 金华市广源环保科技有限公司 | Cathode and anode catalyst for low-voltage electrolytic ozone generator module and preparation method thereof |
| CN108411330A (en) * | 2018-02-11 | 2018-08-17 | 中氧科技（广州）有限公司 | A kind of membrane electrode assembly and preparation method thereof for electrolysis ozone generator |
| CN113862697A (en) * | 2021-09-29 | 2021-12-31 | 中检陆桥(中山市)科技有限公司 | Device for hydrolyzing ozone by using multilayer PEM (proton exchange membrane) |
| CN113862697B (en) * | 2021-09-29 | 2022-06-14 | 中检陆桥(中山市)科技有限公司 | Device for hydrolyzing ozone by using multilayer PEM (proton exchange membrane) |
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| Publication number | Publication date |
|---|---|
| CN1281790C (en) | 2006-10-25 |
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Owner name: XU WEIJUN Free format text: FORMER OWNER: CHEN LIXUE Effective date: 20061229 |
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| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20061229 Address after: 264006 Hua River Industrial Park, No. 106, Taishan Road, Yantai Economic Development Zone, Shandong, China Patentee after: Xu Weijun Address before: 067200, No. 7, building No. seven, Ying Zi Town, Ying Ying mine, Chengde, Hebei, 333 Patentee before: Chen Lixue |
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| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: BIOTEK ENVIRONMENTAL SCIENCE (YANTAI) Ltd. Assignor: Xu Weijun Contract record no.: 2012990000034 Denomination of invention: Anode structure of electrolysis type ozone generator and its preparation method Granted publication date: 20061025 License type: Common License Open date: 20041222 Record date: 20120130 |
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| CX01 | Expiry of patent term |
Granted publication date: 20061025 |
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| CX01 | Expiry of patent term |