CN100494492C - Stainless steel surface treatment technique for stainless steel chemical boat - Google Patents
Stainless steel surface treatment technique for stainless steel chemical boat Download PDFInfo
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- CN100494492C CN100494492C CNB2007100182141A CN200710018214A CN100494492C CN 100494492 C CN100494492 C CN 100494492C CN B2007100182141 A CNB2007100182141 A CN B2007100182141A CN 200710018214 A CN200710018214 A CN 200710018214A CN 100494492 C CN100494492 C CN 100494492C
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- stainless steel
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- polishing
- acid wash
- wash passivation
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/08—Iron or steel
- C23G1/086—Iron or steel solutions containing HF
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/08—Iron or steel
- C23G1/088—Iron or steel solutions containing organic acids
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Abstract
The present invention relates to stainless steel surface treating process for chemical cargo ship, and the process includes two parts of sectional polishing and spray pickling and deactivating. The process includes the following steps: welding stainless steel plates to form sections, polishing, healing up to form hull, polishing weld seams, pumping pickling and deactivating liquor with anticorrosive diaphragm pump into compartment, spraying pickling and deactivating liquor to each compartment, pumping out the used pickling and deactivating liquor, absorbing acid mist with alkali solution and washing the compartments with water. The treating process of the present invention can raise the anticorrosive capacity of the chemical cargo ship by over 20 times and increase the service life of chemical cargo ship greatly. The treating process has been performed practically.
Description
Technical field
The present invention relates to the shipbuilding field, relate in particular to the surface treatment technique for stainless steel of stainless steel chemistry product ship.
Background technology
Before 2005, the used steel of domestic construction chemical tanker are generally carbon steel, and the loading cabin will be brushed to paint to paste and is coated with maximum 3 years of its anticorrosion time limit.If the kind of chemical is transported in conversion, loading cabin internal layer also needs to paste again to be coated with, and not only expense height, time-consuming, and later maintenance expense is also very high, and to adopt stainless steel be main material more so build chemical tanker at present.
Stainless steel, particularly homemade stainless steel, there are defectives such as a large amount of pockmarks, pit in its surface irregularity, second-rate; And stainless steel also can bring surface and oil contaminant, scuffing, iron rust, impurity, low melting point metal pollutent, paint, welding slag, splash etc. in transportation, lifting, assembling, welding, welding inspection (, withstand voltage test painted as detecting a flaw) and the course of processing, and these materials have also influenced the stainless steel surface quality.If directly use without polished finish, then stainless steel surface is easy to corrosion; And after unsnatching chemical, cabin internal surface residual impurity is more, easy cleaning not, and these residues badly influence the purity of thing that next batch is freighted.
Stainless steel chemistry product transport-ship (being called for short " stainless steel chemistry product ship ") mainly is meant the boats and ships of the liquid chemical of delivery except that oil, processed oil and gas, mostly this shipment is inflammable, explosive or deleterious liquid chemical, in case therefore stainless steel surface is coarse, it is adsorbable a large amount of raffinate, be easy to volatilization in the cabin, fire, serious threat is to the safety of operation crewman and whole ship.Stainless steel chemistry product ship is one of the generally acknowledged hi-tech of the shipbuilding of the present world, shipping community, high added value ship type, and wherein stainless steel surface treatment technology (being that surface finish and acid wash passivation are handled) is a gordian technique that needs to be resolved hurrily.
Stainless corrosion resistance mainly is because surface coverage the fine and close passive film of one deck (about 1nm) as thin as a wafer, and this tunic is isolated corrosive medium, is the basic barrier of stainless steel protection.Passivation for stainless steel has behavioral characteristics: tend to destroy film usually when having reductive agent (as chlorion) in the environment, then can keep or repair membrane when existing at oxygenant (as air).Can slowly form oxide film though stainless steel is positioned in the air with oxygen, the protectiveness of this film is perfect inadequately.Usually to carry out thorough pickling earlier, use the oxygenant passivation again, could guarantee the integrity and stability of passive film.One of purpose of pickling is for Passivation Treatment creates favorable conditions, and guarantees to form the fine passive film.Because the thick one deck active iron of the average 10 μ m of stainless steel surface and the oxide compound of iron are corroded by pickling, the chemically reactive of acid solution makes that the dissolution rate at other position wants high on the dissolution rate specific surface of rejected region, therefore pickling can cause corrosive hidden danger to dispose some originally easily, made whole surface be tending towards uniform balance; Under the passivation of oxygenant, make stainless steel surface produce complete stable corrosion-resistant passive film then.But the more important thing is, make of the oxide compound optimum solvation of the oxide compound of iron and iron by acid wash passivation than chromium and chromium, removed poor chromium layer, form the enrichment of chromium at stainless steel surface, the current potential of this rich chromium passivation film can reach+1.0V (SCE), near the current potential of precious metal, improved erosion-resisting stability, make stainless steel can bring into play maximum erosion resistance.The stainless steel surface acid wash passivation except that improving to greatest extent the erosion resistance, prevents product contamination in addition and obtains effect attractive in appearance simultaneously.
Summary of the invention
Technical problem to be solved by this invention just provides and a kind ofly improves stainless steel chemistry product ship erosion resistance, prolongs boats and ships work-ing life, ensures the surface treatment technique for stainless steel of the chemical product ship of stainless steel of navigation safety.
For addressing the above problem, the surface treatment technique for stainless steel of a kind of stainless steel chemistry product ship of the present invention is characterized in that: comprise segmentation polishing and spray pickling passivation two portions; Described segmentation polishing comprises the steps: that 1. stainless steel plate becomes segmentation one by one through welding, assembling; 2. add polishing abrasive material palm fibre corundum, polish, polish with stainless steel integrated polishing machine; 3. weld seam was closed up in polishing after each segment folding became ship; Described spray pickling passivation comprises the steps: that (1) is with in the acid wash passivation liquid usefulness corrosion resisting diaphragm pump suction cabin; Wherein acid wash passivation liquid is for by 10～20% oxygenant of the long-pending per-cent of acid wash passivation liquid, 5～10% etching reagent, 0.6～1% inhibiter, 0.5%～1% complexing agent, 0.01%～0.02% tensio-active agent, and all the other waters replenish; Described oxygenant is the nitric acid of concentration 98%; Etching reagent is the hydrofluoric acid of concentration 40%; Inhibiter is the mixture of urotropine, aniline, potassium sulfocyanate and water, and its admixture ratio is counted urotropine 0.3%, aniline 0.2%, potassium sulfocyanate 0.1% by the weight ratio of 1kg water; Complexing agent is a citric acid; Tensio-active agent is a fatty alcohol-polyoxyethylene ether; Every m
2Treated side needs 2.5～3 liters of acid wash passivation liquid; (2) open liquid pump, from the ejection of corrosion-resistant diaphragm pump spray-head, the every cabin of rotary spray is 1.5～2 hours continuously with acid wash passivation liquid; (3) after reaction finishes, extract acid wash passivation liquid out with liquid pump; (4) absorb acid mist in the cabin with alkali lye, and use the tap water washing of tanks; Wherein alkali lye is the aqueous sodium hydroxide solution of concentration 8～10%.
Corrosion resisting diaphragm pump in the described spray pickling passivation step (1) is the pneumatic surge pump of stainless steel.
Described corrosion-resistant diaphragm pump spray-head is the tank washing machine special stainless steel shower nozzle that 360 degree can spin.
The present invention compared with prior art has the following advantages:
1, when adopting stainless material to do the loading cabin and carrying out surface finish and after acid wash passivation handled, its antiseptic power can improve more than 20 times, has prolonged the work-ing life of boats and ships, can reach 50 years needn't change; Even different chemical is transported in conversion, only need the cleaning of loading cabin is got final product; The chemical that loads when each cabin the phenomenon of chemical reaction can not occur producing because of mutual seepage not simultaneously yet, has improved shipping navigation safety greatly.
2, the whole polishing of the boat segmental among the present invention is first Application at home, does not also appear in the newspapers at present abroad.Because defective, scuffing, the splash on surface after polished finish, can be ground off in the loading cabin, make stainless steel surface as bright as a sixpence, greatly reduce surfaceness, surface quality improves a lot, and the unloading chemical does not almost have residual; After the unloading, get final product, safely, save trouble, save money and to save a large amount of quality time again with high pressure water washing.
3, because stainless steel chemistry product ship usually loads in mixture multiple different chemical, and the operation of use seawater (containing the corrodibility chlorion) washing of tanks is arranged, its acid wash passivation is indispensable especially.By stainless steel surface after the polishing and stainless steel pipeline are carried out the acid wash passivation processing, make stainless steel surface produce the passive film of one deck densification, itself and the chemical that loads are isolated, greatly improved stainless corrosion resistance nature, prolonged the work-ing life of chemical tanker.
4, since the present invention in application, with acid wash passivation liquid corrosion resisting diaphragm pump, by all stainless steel surface and continuous spray in the rotatable stainless steel shower nozzle directive of the 360 degree cabin, make the every nook and cranny in acid wash passivation liquid and stainless steel cabin all obtain abundant reaction, can produce stable, fine and close passive film, thereby reach corrosion resistant purpose.
5, because advanced spray mode has been adopted in the operation of the acid wash passivation among the present invention, it has replaced traditional cabin manual brushing processing mode of manually advancing, efficient is greatly improved: the ship with 3000 tonnages is an example, and the duration enters the cabin by original 20 workmans and constructs and shortened to 5 workmans in more than 20 day and finished in 3～4 days out of my cabin; Simultaneously, because volatile, the toxic and corrodibility of acid wash passivation liquid, when the workman advanced the cabin manual brushing, the danger of existing working aloft a large amount of inputs of labour protections such as acid-proof are arranged again, and quality was difficult to also guarantee.And adopt spray mode automatic spray, the workman need not carry out special protection, need not enter the cabin, have safety, continuously, the advantage of quick, efficient, environmental protection, and got rid of many human factors, guaranteed steady quality, evenly.
6, the present invention successful Application design voluntarily, make in China and utilize on first 3000 tonnes of stainless steels chemistry product ship " Ninghua 417 " that homemade stainless steel plate builds.After this ship was handed in 2006, quality has obtained the authoritative expert---China Classification Society and have the check empirical ship surveyor of Germanischer Lloyd and shipowner's consistent favorable comment, with the inspection of high score, and obtain to enter the admission card of international high-end market by international chemical conduct industry association (CDI).This invention now is applied in large enterprises such as the middleization world, long aviation fuel fortune, CNOOC, Cosco Group tens stainless steel chemistry product ship successively or just, and obtain extensive favorable comment, obtained good social benefit, promoted domestic shipbuilding striding forward to high-end market.
Embodiment
Subordinate Yang Yang company of embodiment 1 China long boat yangtze river in nanjing oil fortune group: 3000 tons of stainless steel chemistry product ships " Ninghua 417 " (first in China) (operation)
At first carry out the segmentation polishing by following step: 1. stainless steel plate becomes segmentation one by one through welding, assembling; 2. add polishing abrasive material palm fibre corundum, polish, polish with the flat electronic hand push polishing machine of 3.0KW.This flat electronic hand push polishing machine is to be rotated by the 3.0KW motor driving shaft, is equipped with the cloth wheel on the axle, and the cloth wheel is gone up and adhered to abrasive material palm fibre corundum, can grind when driving cloth wheel high speed rotating when axle rotates, the polishing stainless steel face; 3. weld seam was closed up in polishing after each segment folding became ship.
Carry out the spray pickling passivation then: in the pneumatic surge pump suction of the QBY-50 type stainless steel cabin that (1) already produces acid wash passivation liquid with the special pump of Shanghai handkerchief; (2) open liquid pump (ship carries), from the rotatable stainless steel shower nozzle ejection of 360 degree, the every cabin of rotary spray is 2 hours continuously with acid wash passivation liquid, makes all fully reactions of acid wash passivation liquid and every nook and cranny, stainless steel cabin; (3) after reaction finishes, extract acid wash passivation liquid out with liquid pump; (4) absorb acid mist in the cabin with the aqueous sodium hydroxide solution of 500 kilograms of concentration 8%, and with a large amount of tap water washings of tanks.This sodium hydroxide solution is that the solid sodium hydroxide with purity 99% adds the aqueous solution that 460 kg of water mix for 40 kilograms.
The acid wash passivation liquid formula that is adopted is: every m
2Treated side adds 2.5 liters of acid wash passivation liquid; Wherein 2.5 liters of acid wash passivation liquid is to be that hydrofluoric acid, 15ml inhibiter, 12.5ml citric acid (food grade), 0.5ml fatty alcohol-polyoxyethylene ether (analytical pure) and the 2097ml water of 98% nitric acid, 125ml concentration 40% is formulated by 250ml concentration.
The preparation of inhibiter: get 3 gram urotropines (analytical pure) respectively, 2 milliliters of aniline (analytical pure) and 1 restrain potassium sulfocyanate (analytical pure), put into 1000 milliliters volumetric flask, add tap water and are diluted to 1000ml and promptly obtain this inhibiter.
Embodiment 2 China long boat yangtze river in nanjing oil fortune groups: four 3000 tons of stainless steels chemistry product ships " Ninghua 418 " (operation), " Ninghua 419 " (operation), " Ninghua 420 " (building), " Ninghua 421 " (building)
The step of segmentation polishing and spray pickling passivation and the preparation of inhibiter are with embodiment 1, and the acid wash passivation liquid formula that is adopted is: every m
2Treated side adds 2.6 liters of acid wash passivation liquid, and wherein 2.6 liters of acid wash passivation liquid is formulated by hydrofluoric acid, 18ml inhibiter, 15.6ml citric acid (food grade), 0.4ml fatty alcohol-polyoxyethylene ether (analytical pure) and the 2059ml water of the nitric acid of 325ml concentration 98%, 182ml concentration 40%.
Aqueous sodium hydroxide solution with 500 kilograms of concentration 8.5% absorbs acid mist in the cabin.This sodium hydroxide solution is that the solid sodium hydroxide with purity 99% adds the aqueous solution that 457.5 kg of water mix for 42.5 kilograms.
Change international among the embodiment 3: 3450 tons of stainless steel chemistry product ships " winter jasmine " number (operation), 3600 tons " cuckoo " number (operation), 3600 tons " Milan " number (operation), 3600 tons " asparagus fern " number (building)
The step of segmentation polishing and spray pickling passivation and the preparation of inhibiter are with embodiment 1, and the acid wash passivation liquid formula that is adopted is: every m
2Treated side adds 2.7 liters of acid wash passivation liquid, and wherein 2.7 liters of acid wash passivation liquid is formulated by hydrofluoric acid, 21.6ml inhibiter, 18.9ml citric acid (food grade), 0.3ml fatty alcohol-polyoxyethylene ether (analytical pure) and the 2038.2ml water of the nitric acid of 405ml concentration 98%, 216ml concentration 40%.
Aqueous sodium hydroxide solution with 500 kilograms of concentration 9% absorbs acid mist in the cabin.This sodium hydroxide solution is that the solid sodium hydroxide with purity 99% adds the aqueous solution that 455 kg of water mix for 45 kilograms.
Embodiment 4 CNOOCs: 2300 tons of stainless steel chemistry product ships " marine oil 851 " number (first in Shandong, operation), 3500 tons " marine oil 852 " number (building)
The step of segmentation polishing and spray pickling passivation and the preparation of inhibiter are with embodiment 1, and the acid wash passivation liquid formula that is adopted is: every m
2Treated side adds 2.8 liters of acid wash passivation liquid, and wherein 2.8 liters of acid wash passivation liquid is formulated by hydrofluoric acid, 28ml inhibiter, 22.44ml citric acid (food grade), 0.56ml fatty alcohol-polyoxyethylene ether (analytical pure) and the 2007ml water of the nitric acid of 490ml concentration 98%, 252ml concentration 40%.
Aqueous sodium hydroxide solution with 500 kilograms of concentration 9% absorbs acid mist in the cabin.This sodium hydroxide solution is that the solid sodium hydroxide with purity 99% adds the aqueous solution that 455 kg of water mix for 45 kilograms.
Embodiment 5 Cosco Groups: 2400 tons of stainless steel chemistry product ships " are hoped extra large No. 1 " (first in Jiangsu is being built), " hoping the sea No. 2 " (building)
The step of segmentation polishing and spray pickling passivation and the preparation of inhibiter are with embodiment 1, and the acid wash passivation liquid formula that is adopted is: every m
2Treated side adds 3.0 liters of acid wash passivation liquid, and wherein 3.0 liters of acid wash passivation liquid is formulated by hydrofluoric acid, 30ml inhibiter, 30ml citric acid (food grade), 0.6ml fatty alcohol-polyoxyethylene ether (analytical pure) and the 2039.4ml water of the nitric acid of 600ml concentration 98%, 300ml concentration 40%.
Aqueous sodium hydroxide solution with 500 kilograms of concentration 10% absorbs acid mist in the cabin.This sodium hydroxide solution is that the solid sodium hydroxide with purity 99% adds the aqueous solution that 450 kg of water mix for 50 kilograms.
Claims (3)
1, a kind of surface treatment technique for stainless steel of stainless steel chemistry product ship is characterized in that: comprise segmentation polishing and spray pickling passivation two portions; Described segmentation polishing comprises the steps: that 1. stainless steel plate becomes segmentation one by one through welding, assembling; 2. add polishing abrasive material palm fibre corundum, polish, polish with stainless steel integrated polishing machine; 3. weld seam was closed up in polishing after each segment folding became ship; Described spray pickling passivation comprises the steps: that (1) is with in the acid wash passivation liquid usefulness corrosion resisting diaphragm pump suction cabin; Wherein acid wash passivation liquid is for by 10～20% oxygenant of the long-pending per-cent of acid wash passivation liquid, 5～10% etching reagent, 0.6～1% inhibiter, 0.5%～1% complexing agent, 0.01%～0.02% tensio-active agent, and all the other waters replenish; Described oxygenant is the nitric acid of concentration 98%; Etching reagent is the hydrofluoric acid of concentration 40%; Inhibiter is the mixture of urotropine, aniline, potassium sulfocyanate and water, and its admixture ratio is counted urotropine 0.3%, aniline 0.2%, potassium sulfocyanate 0.1% by the weight ratio of 1kg water; Complexing agent is a citric acid; Tensio-active agent is a fatty alcohol-polyoxyethylene ether; Every m
2Treated side needs 2.5～3 liters of acid wash passivation liquid; (2) open liquid pump, from the ejection of corrosion-resistant diaphragm pump spray-head, the every cabin of rotary spray is 1.5～2 hours continuously with acid wash passivation liquid; (3) after reaction finishes, extract acid wash passivation liquid out with liquid pump; (4) absorb acid mist in the cabin with alkali lye, and use the tap water washing of tanks; Wherein alkali lye is the aqueous sodium hydroxide solution of concentration 8～10%.
2, the surface treatment technique for stainless steel of a kind of stainless steel chemistry product ship as claimed in claim 1, it is characterized in that: the corrosion resisting diaphragm pump in the described spray pickling passivation step (1) is the pneumatic surge pump of stainless steel.
3, the surface treatment technique for stainless steel of a kind of stainless steel chemistry product ship as claimed in claim 2, it is characterized in that: described corrosion-resistant diaphragm pump spray-head is the tank washing machine special stainless steel shower nozzle that 360 degree can spin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CNB2007100182141A CN100494492C (en) | 2007-06-21 | 2007-06-21 | Stainless steel surface treatment technique for stainless steel chemical boat |
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| CNB2007100182141A CN100494492C (en) | 2007-06-21 | 2007-06-21 | Stainless steel surface treatment technique for stainless steel chemical boat |
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| CN100494492C true CN100494492C (en) | 2009-06-03 |
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| CN101804542A (en) * | 2010-04-09 | 2010-08-18 | 武昌船舶重工有限责任公司 | Regional stage surface treatment method for ship water ballast space |
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| CN103103515B (en) * | 2013-02-28 | 2016-05-11 | 杨东佑 | Passivation for stainless steel remover and preparation method thereof |
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| CN104087956B (en) * | 2014-07-22 | 2016-03-30 | 徐强 | The acid washing passivation technology of duplex stainless steel chemical tanker |
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| CN106756975A (en) * | 2016-11-25 | 2017-05-31 | 泸州北方化学工业有限公司 | A kind of surface treatment technique for stainless steel |
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| CN107268002A (en) * | 2017-08-04 | 2017-10-20 | 苏州吉利不锈钢制品有限公司 | A kind of 304 passivating agent for acid-washing stainless steel and preparation method thereof |
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| CN110182301B (en) * | 2019-04-22 | 2021-08-20 | 沪东中华造船(集团)有限公司 | Double-phase stainless steel sectional construction method for chemical tanker |
| CN113737187A (en) * | 2021-08-30 | 2021-12-03 | 西安石油大学 | Super 13Cr stainless steel surface pickling treatment method |
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2007
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