CN105755508A - Method for making tubular anode - Google Patents

Method for making tubular anode Download PDF

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Publication number
CN105755508A
CN105755508A CN201410790036.4A CN201410790036A CN105755508A CN 105755508 A CN105755508 A CN 105755508A CN 201410790036 A CN201410790036 A CN 201410790036A CN 105755508 A CN105755508 A CN 105755508A
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China
Prior art keywords
titanium
pipe
coating
copper
electrodeposition
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CN201410790036.4A
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CN105755508B (en
Inventor
薛小军
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SHAANXI RUIKAI ENVIRONMENTAL PROTECTION & TECHNOLOGY CO., LTD.
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Xi'an Rui Kai Power Tech Corp Inc
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Abstract

The present invention relates to the technical field of machinery, and in particular relates to a method of making a tubular anode. The method is as follows: preparation of 2mm wall thickness fixed-length titanium tube, completion of coating of an outer anti-corrosion coating, alkali dip for degreasing, water washing, oxalic acid corrosion, water washing, internal electrodeposition of an electrically conductive copper layer, scalding at high temperature, preassembling, nitrogen introduction for deoxygenation, sealing and packing; coating of a mechanically-processed finished part with an oxide coating is completed; internal copper electrodeposition of a titanium tube coated with the outer coating is completed; an upper cover head and a cover head closed pad are arranged on the copper-electrodeposited outer coating titanium tube, a conductive copper screw tube is arranged, air is discharged, and after a lower cover head is arranged. The tubular anode prepared by the route can meet cyclone electrodeposition / electrolysis equipment requirements on high anode current density, the production process is simple, and cost is low. The tubular anode can be stable in working for more than two years under high acid corrosion conditions of anode current density of 3000A / m <2>, and system electrochemical process anodic current efficiency can reach more than 95%.

Description

A kind of manufacture method of sheath
Technical field
The present invention relates to mechanical field, particularly relate to the manufacture method of a kind of sheath.
Background technology
Tradition insoluble anode wet method electrodeposition process generally adopts plate and frame structure, the electrolyte participating in electrochemical reaction is slower in negative and positive interpolar flowing velocity, under highfield power effect, electrolyte is very easy between pole plate concentration polarization phenomenon occurs, and causes that non-targeted ion produces side reaction in anode and cathode and reduces the current efficiency of electrochemical process.During for electrolysis water generation concentration polarization phenomenon, solution resistance increases, and electric current plays heat effect to solution by solution and no longer decomposition water;Metallurgical electrodeposition is example in a wet process, and non-targeted cation replaces target cationic and is deposited on negative electrode, reduces cathode product quality.No matter electrolysis or the prime cost of its equipment of electrodeposition all concentrate in the making of insoluble anode, in order to save annode area, under the premise of same anode area, adopt higher anodic current density to become the trend that electrochemical apparatus makes.
The cyclone electrolytic cell technology that the nineties in last century begins one's study, it is by improving electrolyte in interelectrode flowing velocity, eliminate concentration polarization phenomenon, reduce the negative effect that its electrochemical process causes, under geostationary annode area, very high currents intensity is adopted to obtain higher negative electrode production capacity or cathode product quality more preferably.
The insoluble anode being applied to cyclone electrolytic cell is generally made up of outer layer antioxidation washcoat+internal conductive structures, its antioxidation washcoat according to solution anion character unusual by specialty be coated with company complete, and existing patent formed;But then relatively degrees of overtness is little in the making of its internal conductive structures, and the internal conductive structures prepared of existing technique or dependability is low, or complex manufacturing technology, cost are high.
Publication number is the patent of 102758215A: interior contact assembling anode simple structure, initial stage that a kind of Special anode in cyclone electrolyzer is announced use conductive capability strong, but after serving as the tin-phosphor bronze sheet the contacting conduction time about one season of use inside it, due to contact resistance heating and tubular body air oxidation, lose with titanium pipe base material gradually and contact, and finally make whole anode lose conductive capability.
Use the column anode that titanium and copper composite bar material makes, it is impossible to meet the demand of oxide coating coating procedure repeatedly heating and cooling;Use sheath contact resistance prepared by the mode filling copper spring washer in titanium pipe still very big;
In a word, in order to reduce the manufacturing cost of cyclone electrolytic cell process equipment, it is still necessary to study the manufacture method that a kind of reliability is high, electric conductivity is strong, with low cost.
Summary of the invention
The purpose of invention: in order to provide the manufacture method of the sheath of a kind of better effects if.
In order to reach as above purpose, the present invention adopts the following technical scheme that:
The manufacture method of a kind of sheath, it is characterised in that comprise the steps of:
1) taking seamless titanium tube one section, two end threadings, after the reserved conducting copper installation site in titanium pipe bottom, near lower end welding titanium gasket ring, gasket ring is vertical with pipe axis;
2) outside titanium pipe, oxide coating it is coated with;
3) the titanium pipe after coating is installed on eddy flow electrodeposition frame, in circulating slot, adds the warmed up oxalic acid solution to 90 DEG C of 10% concentration;Start circulating pump, corrode titanium inside pipe wall 3.5h with high temperature oxalic acid solution;Oxalic acid solution in emptying system;
4) in circulating slot, add new tap water, start circulating pump, rinse titanium inside pipe wall, empty wash water;
5) in circulating slot, Cu is added2+Ion concentration is 55g/L, containing the copper-bath of acid 140g/L, starts circulating pump, starts rectifier power source, and control solution flow rate is 750L/h, and current intensity is that 200A starts electro deposited copper in titanium inside pipe wall;Continuing electrodeposition 36h, period constantly adds cupric oxide powder in circulating slot, maintains electrolyte cupric and is not less than 15g/L;
6) close rectifier power source, stop circulating pump, emptying system electrolyte, unload titanium pipe;
7) titanium pipe is placed in the weak acid clear water of 90 DEG C scalds 10min;Take out drip washing, dry;
8) prefabricated upper cover and sealing ring are installed;Conductive copper screwed pipe is installed;With high pressure nitrogen, the air within titanium pipe is driven out of, bottom head is installed;Complete insoluble sheath preparation process.
Adopt the present invention of as above technical scheme; have the advantages that relative to prior art: by adopting insoluble conductive anode prepared by above-mentioned steps both to possess the conductive capability almost identical with copper rod; possessed again the corrosion resistance of titanium material, and surface active, anti-corrosion coating protection under can better participate in anode electrochemical reaction.
Accompanying drawing explanation
In order to further illustrate the present invention, it is further illustrated below in conjunction with accompanying drawing:
Fig. 1 is special anode inwall electro deposited copper device;
Fig. 2 is the insoluble sheath general assembly drawing of the present invention;
Fig. 3 is for the present invention relates to titanium pipe upper cover figure lateral plan;
Fig. 4 is for the present invention relates to titanium pipe upper cover figure front view;
Fig. 5 is the titanium pipe low head lateral plan that the present invention relates to;
Fig. 6 is the titanium pipe low head front view that the present invention relates to;
Wherein: 1 upper cover;2 end socket sealing rings;Electro deposited copper titanium pipe in 3 external coatings;4 titanium gasket rings;5 conductive copper screwed pipes;6 low heads;7. external coating titanium rod electrodeposition anode;8. external coating titanium pipe electrodeposition negative electrode;9. electric effusion circulating slot;10. tapping valve;11. circulating pump.
Detailed description of the invention
Below in conjunction with accompanying drawing, embodiments of the invention being illustrated, embodiment is not construed as limiting the invention:
The implementation process of the present invention is further described below in conjunction with example.
1. cut-off footpath is the seamless titanium tube one section of 57mm, wall thickness 2mm, and length is 1.435m, and with lathe at seamless titanium tube two end threading, upper end internal thread length is 20mm, and outside lower end, filament length degree is 85mm;At titanium pipe bottom distance lower end 145mm place welding titanium gasket ring;
2. the coating of titanium pipe external oxide coating is completed;
3. the coated titanium pipe fetched is installed on special small-sized eddy flow electrodeposition frame, in circulating slot, adds the warmed up oxalic acid solution to 90 DEG C of 10% concentration;Start circulating pump, corrode titanium inside pipe wall 3.5h with oxalic acid solution;Oxalic acid solution in emptying system;
4. in circulating slot, add new tap water, start circulating pump, rinse titanium inside pipe wall;Emptying wash water;
5. in circulating slot, add Cu2+Ion concentration is 55g/L, containing the copper-bath of acid 140g/L, starts circulating pump, starts rectifier power source, and control solution flow rate is 750L/h, and current intensity is that 200A starts electro deposited copper in titanium inside pipe wall;Continuing electrodeposition 36h, period constantly adds cupric oxide powder in circulating slot, maintains electrolyte cupric and is not less than 15g/L;
6. close rectifier power source, stop circulating pump, emptying system electrolyte, unload titanium pipe;
7. titanium pipe is placed in the weak acid clear water of 90 DEG C and scalds 10min;Take out drip washing, dry;
8. prefabricated upper cover and sealing ring are installed;Conductive copper screwed pipe is installed;
9. with high pressure nitrogen, the air within titanium pipe is driven out of, bottom head is installed;Complete insoluble sheath preparation process.
It is installed on when the present invention uses in the lower base of swirl electrolysis device, realized cell body by the gasket ring on bottom titanium gasket ring and pedestal to seal, realized anode vertical correction by the locating shaft of top titanium end socket, connect the positive pole of rectifier power source at conductive copper screwed pipe outer wall, namely complete to use and install.The sheath made according to route of the present invention can meet the requirement of the antianode high current density of eddy flow electrodeposition/electrolysis installation, and processing technology is simple, cheap.Under the peracid etching condition of anodic current density 3000A/ can steady operation more than 2 years, system electrochemical process anodic current efficiency is up to more than 95%.
It should be noted that the protection of itself is not caused restriction by the size of the scheme of this patent offer.
As further preferred:
1) taking seamless titanium tube one section, two end threadings, after the reserved conducting copper installation site in titanium pipe bottom, near lower end welding titanium gasket ring, gasket ring is vertical with pipe axis;
2) outside titanium pipe, rhodium iridium oxide coating it is coated with;
3) the titanium pipe after coating is installed on eddy flow electrodeposition frame, in circulating slot, adds the warmed up oxalic acid solution to 90 DEG C of 10% concentration;Start circulating pump, corrode titanium inside pipe wall 3.5h with oxalic acid solution;Oxalic acid solution in emptying system;
4) in circulating slot, add new tap water, start circulating pump, rinse titanium inside pipe wall, empty wash water;
5) in circulating slot, Cu is added2+Ion concentration is 55g/L, containing the copper-bath of acid 140g/L, starts circulating pump, starts rectifier power source, and control solution flow rate is 750L/h, and current intensity is that 200A starts electro deposited copper in titanium inside pipe wall;Continuing electrodeposition 36h, period constantly adds cupric oxide powder in circulating slot, maintains electrolyte cupric and is not less than 15g/L;
6) close rectifier power source, stop circulating pump, emptying system electrolyte, unload titanium pipe;
7) titanium pipe is placed in the weak acid clear water of 90 DEG C scalds 10min;Take out drip washing, dry;
8) prefabricated upper cover and sealing ring are installed;Conductive copper screwed pipe is installed;
With high pressure nitrogen, the air within titanium pipe is driven out of, bottom head is installed;Complete insoluble sheath preparation process.
1. in the external coating described in, electro deposited copper titanium pipe, titanium gasket ring and conductive copper screwed pipe have identical center and axis, and axis based error is not more than 0.2mm;
2. the titanium gasket ring described in is 90 ° of vertical weldings with electro deposited copper titanium pipe axis in external coating;
3. the upper cover external sealing plug footpath described in is identical with the upper end internal thread bore of electro deposited copper titanium pipe in external coating, for fine thread;
4. the conductive copper screwed pipe female thread bore described in matches with the external screw thread bore of electro deposited copper titanium pipe bottom in external coating, for fine thread;
5. the conductive copper screwed pipe female thread bore described in is identical with low head external sealing plug footpath, for fine thread;
6. in the external coating described in, electro deposited copper titanium pipe external coating is coated with according to cyclone electrolytic cell duty requirements, and interior electro deposited copper is completed by anodic electrodeposition system special shown in Fig. 1, and interior deposition copper thickness is not less than 3mm.
The ultimate principle of the present invention, principal character and advantages of the present invention have more than been shown and described.Skilled person will appreciate that the present invention is not restricted to the described embodiments; described in above-described embodiment and description is that principles of the invention is described; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements both fall within claimed scope.

Claims (1)

1. the manufacture method of a sheath, it is characterised in that comprise the steps of:
Taking seamless titanium tube one section, two end threadings, after the reserved conducting copper installation site in titanium pipe bottom, near lower end welding titanium gasket ring, gasket ring is vertical with pipe axis;
Rhodium iridium oxide coating it is coated with outside titanium pipe;
Titanium pipe after coating is installed on eddy flow electrodeposition frame, in circulating slot, adds the warmed up oxalic acid solution to 90 DEG C of 10% concentration;Start circulating pump, corrode titanium inside pipe wall 3.5h with oxalic acid solution;Oxalic acid solution in emptying system;
In circulating slot, add new tap water, start circulating pump, rinse titanium inside pipe wall, empty wash water;
Cu is added in circulating slot2+Ion concentration is 55g/L, containing the copper-bath of acid 140g/L, starts circulating pump, starts rectifier power source, and control solution flow rate is 750L/h, and current intensity is that 200A starts electro deposited copper in titanium inside pipe wall;Continuing electrodeposition 36h, period constantly adds cupric oxide powder in circulating slot, maintains electrolyte cupric and is not less than 15g/L;
Close rectifier power source, stop circulating pump, emptying system electrolyte, unload titanium pipe;
Titanium pipe is placed in the weak acid clear water of 90 DEG C and scalds 10min;Take out drip washing, dry;
Prefabricated upper cover and sealing ring are installed;Conductive copper screwed pipe is installed;
With high pressure nitrogen, the air within titanium pipe is driven out of, bottom head is installed;Complete insoluble sheath preparation process.
CN201410790036.4A 2014-12-19 2014-12-19 A kind of preparation method of sheath Active CN105755508B (en)

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CN105755508B CN105755508B (en) 2017-12-01

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106367779A (en) * 2016-11-07 2017-02-01 南昌专腾科技有限公司 Titanium-based porous electrode material and preparation method thereof

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1313298A (en) * 1969-06-27 1973-04-11 Ici Ltd Anode assembly for electrolytic cells
CN2097209U (en) * 1991-08-19 1992-02-26 郑州市华中环保科技开发研究所 Electrolytic tube of generator for sodium hypochlorite
CN2196125Y (en) * 1994-04-13 1995-05-03 北京夏洋科贸公司 Gas state strong oxidant generator
CN2430432Y (en) * 2000-05-12 2001-05-16 戴继岚 Automatic control static flow processor
CN2760012Y (en) * 2004-01-14 2006-02-22 上海劲钻实业公司 Special-purpose combined anode for cylinder form water electrolysis apparatus
CN201121211Y (en) * 2007-07-25 2008-09-24 飞鹏环境工程有限公司 Card insertion type diaphragm electrolysis apparatus
CN101440633A (en) * 2008-12-22 2009-05-27 李瓯 Method and apparatus for electrochemically cleaning urinous scale
CN202099386U (en) * 2011-05-11 2012-01-04 宝鸡新城钛管股份公司 Titanium anode tube
CN202175581U (en) * 2011-07-27 2012-03-28 金川集团有限公司 Treating device for waste copper sulfate electrolyte liquid
CN102758215A (en) * 2012-07-24 2012-10-31 嘉兴科菲冶金科技股份有限公司 Special anode in cyclone electrolyzer

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1313298A (en) * 1969-06-27 1973-04-11 Ici Ltd Anode assembly for electrolytic cells
CN2097209U (en) * 1991-08-19 1992-02-26 郑州市华中环保科技开发研究所 Electrolytic tube of generator for sodium hypochlorite
CN2196125Y (en) * 1994-04-13 1995-05-03 北京夏洋科贸公司 Gas state strong oxidant generator
CN2430432Y (en) * 2000-05-12 2001-05-16 戴继岚 Automatic control static flow processor
CN2760012Y (en) * 2004-01-14 2006-02-22 上海劲钻实业公司 Special-purpose combined anode for cylinder form water electrolysis apparatus
CN201121211Y (en) * 2007-07-25 2008-09-24 飞鹏环境工程有限公司 Card insertion type diaphragm electrolysis apparatus
CN101440633A (en) * 2008-12-22 2009-05-27 李瓯 Method and apparatus for electrochemically cleaning urinous scale
CN202099386U (en) * 2011-05-11 2012-01-04 宝鸡新城钛管股份公司 Titanium anode tube
CN202175581U (en) * 2011-07-27 2012-03-28 金川集团有限公司 Treating device for waste copper sulfate electrolyte liquid
CN102758215A (en) * 2012-07-24 2012-10-31 嘉兴科菲冶金科技股份有限公司 Special anode in cyclone electrolyzer

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106367779A (en) * 2016-11-07 2017-02-01 南昌专腾科技有限公司 Titanium-based porous electrode material and preparation method thereof

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Effective date of registration: 20180510

Address after: 710003 room 2, unit 11, 11 commercial plaza, 275 Fenghe Road, Lianhu District, Xi'an, Shaanxi.

Patentee after: SHAANXI RUIKAI ENVIRONMENTAL PROTECTION & TECHNOLOGY CO., LTD.

Address before: 710075 room 2508, block B, two hi tech three road Fortune Center, Xi'an, Shaanxi.

Patentee before: Xi'an Rui Kai Power Tech Corp. Inc.

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