CN100588736C - Oil and bushing low-temperature powder embedding aluminizing agent for petroleum - Google Patents
Oil and bushing low-temperature powder embedding aluminizing agent for petroleum Download PDFInfo
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- CN100588736C CN100588736C CN200610113859A CN200610113859A CN100588736C CN 100588736 C CN100588736 C CN 100588736C CN 200610113859 A CN200610113859 A CN 200610113859A CN 200610113859 A CN200610113859 A CN 200610113859A CN 100588736 C CN100588736 C CN 100588736C
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Abstract
The low temperature quick aluminizing agent specially for petroleum pipe and casing consists of metal source, activator, catalyst and stuffing. The metal source consists of 150-mesh Al powder in 10-20wt% of the aluminizing agent, 120-mesh Zn powder in 10-25 wt%, 150-mesh Zn-Fe alloy powder in 10-20 wt% and/or 150-mesh Fe-Al alloy powder in 10-15 wt%. The activator consists of ammonium chloride, aluminum chloride, sodium fluoride and/or potassium bifluoride. The catalyst consists of 100-mesh Mo powder in 0-3 wt% and La and Os 0-3 wt%, with La and Os in the weight ratio of 1 to 1. The stuffingis 100-mesh alumina powder. The aluminizing agent is applied at 380-500 deg.c to obtain aluminized layer.
Description
Technical field
The present invention relates to metal conditioner, the quick aluminizing medium of particularly a kind of oil special oil bushing low-temperature.
Background technology
After oil and gas pipes is corroded, can cause enormous economic loss to oil-gas field, even cause catastrophic failure and environmental pollution and abominable social influence, in the China Petroleum, the etching problem that height contains under H2S, CO2 and the High Temperature High Pressure coupling operating mode is on the rise at present.Be head it off, adopt methods such as surperficial coating, inner liner stainless steel, Glass Steel Tube and input sustained release dosage both at home and abroad usually.The surface coating process is simple, but poor with basal body binding force, easily comes off; Inner liner stainless steel complex process, poor stability, cost height; Glass Steel Tube antiseptic property excellence, but that its production technology, support equipment require is high, and production cost increases substantially; And the input inhibiter, effectively protection period is short, the cumulative cost height, and ground adaptability is relatively poor.Therefore, it is remarkable to explore the aseptic technic meaning with high performance-price ratio.
Contain for 8% Al atomic time in the steel substrate, the surface can form the Al of densification, anti-corrosion, resistance to high temperature oxidation
2O
3Film, but matrix fragility increases, and only both can guarantee center toughness in alitizing, can improve surface property again.Aluminizing technology is under certain condition, make that penetration enhancer and workpiece interface priming reaction are carried out, produce active A l atom, and replace by rapid diffusion passages such as room and crystal boundary, dislocation in the workpiece dot matrix and iron atom, form sosoloid and the intermetallic compound of aluminium in steel, thereby improved the upper layer microstructure and property.Because the high-performance upper layer that obtained is that support modification produces with the original upper layer of workpiece, therefore be higher than the general technology that is coated with, plates, brushes or the like far away with substrate combinating strength.
Medium and high temperature (700-1100 ℃) aluminizing technology has obtained great success, anti-H at parts such as small-sized component, crude oil refinery parts, aircraft turbine blades aspect anticorrosion
2S, CO
2, and corrosive nature such as atmosphere, seawater even exceeded the 1Cr18Ni9Ti stainless steel, can match in excellence or beauty with 316 stainless steels, and stable processing technique, comprehensive price ratio significantly improve.Patent documentation " a kind of pack aluminizing agent and pack cementation aluminizing method " (CN1207431C) discloses conventional aluminising penetration enhancer and has consisted of: aluminium powder, iron powder, ammonia chloride, aluminum oxide, these compositions are formations the most basic in the aluminising, wherein only ammonia chloride belongs to activator, utilizes this prescription can only be under high temperature (＞700 ℃) condition, utilize the hot activation effect to realize aluminising, and rely on these basic comprisings even mechanically adjust component content, interfacial activity Al atom can't obtain enough intensity of activation at low temperatures, and the infiltration process can not realize.
Patent documentation " rare earth-urge aluminising " has been mentioned rare earth element in (CN1051765A), be ytterbium, hafnium, tantalum etc., its effect only limits to the pretreatment technology of hot-dip aluminizing using (mollerizing method), to actual aluminising critical process, process is infiltrated in the activation that is active A L atom, does not have direct significance.
Patent documentation " have the protection slip applies and the aluminizing method and the equipment of Frequency Induction Heating " (CN1007735B) described in " slip coating+induction heating " aluminizing technology between mollerizing and powder aluminising; the patent protection content is pre-treatment (being coating processes) and induction heating technology; utilize common slip penetration enhancer to realize that essence aluminising temperature is more than 900 ℃.
Patent documentation " aluminium coating process " (Aluminum coating process) (GB791502) belongs to the coating processes that contains the aluminium anti-corrosion coating, and wherein related aluminising treatment temp is up to 1500 ℃.
Patent documentation " employing electrically contacts heating method obtains aluminized coating at steel pipe internal-surface method " is a kind of principle of the quick aluminising of pipe fitting (CN1587433A), and the aluminising temperature is between 850-1300 ℃.Source metal is aluminium and Al alloy powder in its penetration enhancer, and effect only provides aluminium atom source.
The needed temperature drift of common aluminizing technology is the maximum bottleneck problem that restriction oil application tube is used.General aluminising workpiece all is to carry out 700-1100 ℃ of medium and high temperature, its process object is mainly plain carbon stool, as 20 steel, and perhaps some low alloy steel parts, the core structure of these parts and performance change before and after the aluminising little, perhaps change more greatly but do not influence use properties.Yet oil, sleeve pipe belong to oil pipes, alloying level is higher, its matrix microtexture, mechanical performance index are subjected to the strict restriction of relevant criterion, be higher than the aluminising of its annealing temperature (about 560 ℃), to significantly change its microstructure and property, make the workpiece performance degradation, can't satisfy the oil-gas field scene to oil, the requirement of telescopic mechanical property, thereby bring a series of serious problems, therefore, how guaranteeing that matrix does not have under the condition of considerable change, promptly cold condition realizes that down the oil pipe alitizing is the technical problem underlying that must solve.In addition, oil, telescopic geometric buckling also have certain influence to the infiltration process of active A l atom.
Summary of the invention
Oil special oil, cover alloying degree are higher, and general is that the aluminising penetration enhancer of object can't be handled the oil application tube with soft steel; The oil application tube belongs to " quenching+tempering " tissue simultaneously, tempering temperature is between 500-660 ℃, if adopt the temperature aluminising between 500-650 ℃ of conventional penetration enhancer, oil pipe will produce drawing effect, material softening, performance degradation, will no longer be fit to the oil gas well and utilize, it is useless that oil pipe becomes.Temperature is higher than 660 ℃, and austenitizing will take place material structure, and original " quenching+tempering " tissue will be eliminated fully, and the oil pipe performance is poorer, must return factory's thermal treatment again.For overcoming the above problems, the present invention has developed a kind of oil special oil, bushing low-temperature powder pack cementation aluminizing penetration enhancer of being suitable for.Purport of the present invention is exactly under low temperature (380-500 ℃) condition, utilizes various activation mechanisms, promotes active A l atom to infiltrate matrix, realizes tubular member upper layer aluminising modification, improves anti-H
2S, CO
2Deng antiseptic property.
A kind of oil special oil, cover low-temperature powder pack cementation aluminizing penetration enhancer, by source metal, activator, catalyzer and weighting agent are formed, wherein, source metal is by the 150 order aluminium powders that account for penetration enhancer weight percent 10-20%, the 120 order zinc powders of 10-25%, one or more compositions of the 150 order aluminium zinc powder of 10-20% or the 150 order ferro-aluminium powder of 10-15%, activator is by ammonia chloride, aluminum chloride, one or more compositions of Sodium Fluoride or potassium hydrogen fluoride, catalyzer is by the 100 order molybdenum powders that account for penetration enhancer weight percent 0-3%, the rare-earth elements of lanthanum of 0-3% and osmium constitute, wherein lanthanum and osmium weight percent are 1: 1, and weighting agent is 100 purpose aluminum oxide powders.In the aluminium zinc powder, the weight percent of aluminium content is 58.5%, and aluminium content is 25% in the ferro-aluminium powder.
The weight percent of aluminising penetration enhancer consists of, the 150 order aluminium powders of 10-20%, the 120 order zinc powders of 10-25%, the activator of 0-10%, the 100 order molybdenum powders of 0-3%, the rare-earth elements of lanthanum of 0-3% and osmium constitute, and wherein lanthanum and osmium weight percent are 1: 1, and all the other are 100 purpose aluminum oxide powders.Described activator is made up of one or more of ammonia chloride, aluminum chloride, Sodium Fluoride or potassium hydrogen fluoride.
The weight percent of aluminising penetration enhancer consists of, the 150 order aluminium zinc powder of the 150 order aluminium powders of 10-20%, the 120 order zinc powders of 10-25%, 10-20%, the 150 order ferro-aluminium powder of 10-15%, the activator of 0-10%, the 100 order molybdenum powders of 0-3%, the rare-earth elements of lanthanum of 0-3% and osmium constitute, wherein lanthanum and osmium weight percent are 1: 1, and all the other are 100 purpose aluminum oxide powders.Described activator is made up of one or more of ammonia chloride, aluminum chloride, Sodium Fluoride or potassium hydrogen fluoride.
Catalyzer is a rare earth element in the penetration enhancer of the present invention, its oxide compound, muriate decompose in middle temperature, discharge active rare earth atom, adsorbed by workpiece, rare earth atom can enter matrix by reducing behind the absorption workpiece, and its radius causes bigger distortion district after recovering, and makes room, dislocation desity improve, increased the rapid diffusion passage of metal active atom A l, Zn, thereby realized that active A L atomic diffusion enters metallic matrix.After temperature reduces, rare earth atom will break away from matrix and reply original form, therefore, show as the effect of oozing of urging.Another effect of rare earth element is that its active compound can stretch into matrix along crystal boundary, and aluminum oxide is had " bolt is carved " effect, has increased aluminum oxide film and high base strength greatly.Wherein the adding of molybdenum element has significantly promoted the rare earth catalytic cementation process, does not have molybdenum to participate in, and the rare earth element effect is little.
Penetration enhancer comprises aluminium powder, zinc powder, aluminium zinc and ferro-aluminium powder, and aluminium powder only provides the aluminium atom.The effect of zinc powder is that zinc atom is easy to diffuse into workpiece surface (because the fusing point of zinc own significantly is lower than the fusing point of aluminium under the aluminising temperature, be easy to activate), produce distortion, because zinc atom is close with the aluminium atomic radius, therefore can for as yet fully activated aluminium atom diffusion admittance is provided, have the effect of oozing of urging.The zinc-aluminium master alloy has simultaneously to be provided the Al atom and urges the effect of oozing.It is wetting property and the avidity that improves active A l atom and iron-base workpiece surface that the iron aluminium intermediate alloy mainly acts on, suppressing impedance dielectrics such as both interface adhesions, caking, slagging scorification under the rate of heating conditions of higher occurs, guarantee that the active aluminum atom enters workpiece substrate smoothly, finishes the aluminising process.
The granularity problem that penetration enhancer is formed, many patents have all been mentioned, and all are scope, are not concrete granularity sizes.Preamble is stated, and the aluminising key is that the Al atom activates, activates, diffuses into matrix.Different penetration enhancer granularities have directly determined the shared void ratio of diffusion admittance of Al atom, this void ratio is when a certain threshold value is following, the Al atom is can't activated, urges the effect of oozing even add rare earth, molybdenum powder, zinc powder and ferro-aluminium etc., and the aluminising effect is also not obvious.In other words, the granularity that is limited in this patent diffusion agent formulation is free to matrix surface and infiltrate matrix and play an important role by the space for the active aluminum atom, after adjusting a little is to obtain expecting the aluminising effect.
The aluminising temperature that adopts penetration enhancer of the present invention to need is low, can obtain outer rich aluminium, the rich zinc of internal layer, compact bilayer structure co-penetration layer between 380-500 ℃, this infiltration layer has utilized zinc coat, the normal temperature corrosion resistance nature of aluminized coating and the wear resistance and the high temperature oxidation resistance of aluminized coating simultaneously; Also can obtain single aluminized coating, comprising aluminium, zinc sosoloid and the zinc-aluminium, iron aluminide in steel.In the outside surface aluminized coating sosoloid of aluminium in steel can workpiece surface produce with matrix bond closely, to external agency such as H
2S, CO
2Oxide film Deng not having selectivity, densification with matrix and isolated from outer medium, has significant corrosion resistance nature.The oxide film fusing point surpasses 2000 ℃, has good high temperature oxidation resistance.Iron aluminide has higher hardness in the aluminized coating, thereby has increased the wear resisting property of infiltration layer, has improved anti-current body scouring capability greatly.When some sharp-pointed grinding pebble destroyed oxide film, oxide film was repaired on the spontaneous surface of moving to of aluminium atom meeting in the sosoloid, makes this oxide film have good self-reparing capability.
Oil special oil provided by the invention, bushing low-temperature pack aluminizing penetration enhancer, the aluminized coating that is obtained has excellent corrosion-resistant, wear-resisting, erosion resistance in harsh oil gas well delivery medium, and have the good high-temperature resistance of oxidation, and oil, sleeve pipe matrix and performance do not have considerable change.
Description of drawings
Fig. 1: infiltration layer pattern and matrix
Fig. 2: aluminized coating preservative effect comparison diagram
Embodiment
Embodiment one to six:
The N80 oil pipe that one section 400mm is long (new pipe) adopts chamber type electric resistance furnace to carry out pack aluminizing at 450 ℃ behind pickling, the applying protecting coat, be incubated after 8 hours, and obtaining internal layer on oil pipe inside and outside wall surface is the sosoloid of zinc in iron, and skin is FeAl
2, FeAl, aluminium sosoloid coexistence in steel aluminized coating, behind the furnace cooling, supercoat peels off naturally, the oil pipe surface keeps clean and tidy, oozes back each phase size of oil pipe and is in the allowed band, considerable change does not take place in matrix, still satisfies the industry standard requirement.
The foregoing description diffusion agent formulation such as following table:
Each penetration enhancer component per distribution ratio table of table 1: embodiment, %
| 150 order aluminium powders | 120 order zinc powders | 150 order aluminium zinc powder ※ | 150 order ferro-aluminium powder ※ | Activator and per-cent | 100 order molybdenum powders | Rare earth element | 100 purpose aluminum | |
| Embodiment | ||||||||
| 1 | 10 | 25 | 10 ammonia chlorides | 3 | 0.1 | Clout | ||
| Embodiment 2 | 20 | 10 | 7 aluminum chloride | 0.1 | 3 | Clout | ||
| Embodiment 3 | 15 | 20 | 10 | 15 | 4 Sodium Fluorides | 0.1 | 0.1 | Clout |
| Embodiment 4 | 12 | 15 | 20 | 10 | 2.5 ammonia chloride, 2.5 aluminum chloride | 3 | 3 | |
| Embodiment | ||||||||
| 5 | 10 | 25 | 15 | 12 | 4 potassium hydrogen fluorides | 1.5 | 1.5 | Clout |
| Embodiment 6 | 20 | 10 | 13 | 13 | 8 ammonia chlorides, 4 Sodium Fluorides | 2 | 2 | Clout |
Wherein in the aluminium zinc powder, the weight percent of aluminium content is 58.5% to ※, and aluminium content is 25% in the ferro-aluminium powder.
The about 0.21mm of embodiment 3 tube inner wall infiltration layers is followed successively by aluminium sosoloid in steel, FeAl, FeAl from outside to inside
2, Fe
2Al
5, the sosoloid of zinc in iron, ooze back oil pipe each size and be in the allowed band.Infiltration layer interface rule, good with matrix bond, considerable change does not all take place in matrix and mechanical property, the institute infiltration layer pattern that obtains and ooze the back matrix shown in Fig. 1 (b).Embodiment 4～6 aluminising effects are with embodiment 3.
Above-mentioned 2,6 two embodiment gained oil pipe samples are utilized pottery (wherein an end leaves aperture), and after closed at both ends, each injects 10%H
2S+3%NaCl solution carries out anti-corrosion test after the sealing, simultaneously with the 1Cr18Ni9Ti stainless steel tube of same size specification and not the aluminising oil pipe adopt and carry out corrosion-resistant simultaneous test with quadrat method, the result is as shown in Figure 2.From Fig. 1, Fig. 2 as can be seen, after employing this patent invention penetration enhancer carries out aluminising, under cold condition, obtained ideal aluminising effect.Gained infiltration layer erosion resistance difference in above-mentioned etchant solution is little, but all is significantly higher than not aluminising N80 oil pipe, and is suitable with the 1Cr18Ni9Ti stainless steel.The oil pipe matrix does not change after the aluminising, and considerable change does not take place the mechanical performance index of API standard code, and workpiece deformation is also very little, can satisfy the requirement of oil gas site work.
Claims (1)
1, a kind of oil special oil bushing low-temperature powder pack cementation aluminizing penetration enhancer, it is characterized in that: described by weight percentage aluminising penetration enhancer is by 15% 150 order aluminium powders, 20% 120 order zinc powders, 10% 150 order aluminium zinc powder, 15% 150 order ferro-aluminium powder, 4% Sodium Fluoride, 0.1% 100 order molybdenum powders, 0.1% lanthanum osmium, and wherein lanthanum and osmium weight percent are that 1: 1 and surplus are that 100 order aluminum oxide powders constitute;
Or described penetration enhancer is by 12% 150 order aluminium powders, 15% 120 order zinc powders, 20% 150 order aluminium zinc powder, 10% 150 order ferro-aluminium powder, 2.5% ammonium chloride, 2.5% aluminum chloride, 3% 100 order molybdenum powders, 3% lanthanum osmium, and wherein lanthanum and osmium weight percent are that 1: 1 and surplus are that 100 order aluminum oxide powders constitute;
Or described penetration enhancer is by 10% 150 order aluminium powders, 25% 120 order zinc powders, 15% 150 order aluminium zinc powder, 12% 150 order ferro-aluminium powder, 4% potassium hydrogen fluoride, 1.5% 100 order aluminium powders, 1.5% lanthanum osmium, and wherein lanthanum and osmium weight percent are that 1: 1 and surplus are that 100 order aluminum oxide powders constitute;
Or described penetration enhancer is by 20% 150 order aluminium powders, 10% 120 order zinc powders, 13% 150 order aluminium zinc powder, 13% 150 order ferro-aluminium powder, 8% ammonium chloride, 4% Sodium Fluoride, 2% 100 order molybdenum powders, 2% lanthanum osmium, and wherein lanthanum and osmium weight percent are that 1: 1 and surplus are that 100 order aluminum oxide powders constitute;
In the described aluminium zinc powder, the weight percent of aluminium content is 58.5%, and aluminium content is 25% in the ferro-aluminium powder.
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| CN200610113859A CN100588736C (en) | 2006-10-20 | 2006-10-20 | Oil and bushing low-temperature powder embedding aluminizing agent for petroleum |
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| CN200610113859A CN100588736C (en) | 2006-10-20 | 2006-10-20 | Oil and bushing low-temperature powder embedding aluminizing agent for petroleum |
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| CN101665901B (en) * | 2009-10-14 | 2011-09-28 | 北京中路大成科技发展有限公司 | Method for preparing ZnAlTi multi-component alloy anticorrosive coating on workpiece surface |
| CN101665900B (en) * | 2009-10-14 | 2011-11-02 | 北京中路大成科技发展有限公司 | Method for preparing ZnAlMg multi-component alloy anticorrosive coating on workpiece surface |
| CN101985731B (en) * | 2010-09-25 | 2014-01-01 | 杭州浙锚预应力有限公司 | Steel plate multicomponent alloy co-cementation method |
| CN102021511A (en) * | 2011-01-09 | 2011-04-20 | 南昌航空大学 | Low-temperature powder embedding aluminum-rich penetrating agent for stainless steel |
| CN102127732B (en) * | 2011-03-02 | 2012-10-10 | 安徽天通达克罗涂复科技有限公司 | Complex alloy permeation agent and method for preparing permeation layer |
| CN102534468B (en) * | 2012-02-29 | 2014-08-13 | 西安石油大学 | Preparation technology for steel-surface in-situ ceramic layer used in low-temperature aluminizing petroleum pipeline |
| CN103375657B (en) * | 2012-04-17 | 2016-08-17 | 新兴铸管股份有限公司 | A kind of iron-based pipeline containing corrosion-inhibiting coating |
| CN103484816A (en) * | 2012-06-13 | 2014-01-01 | 常州兰翔机械有限责任公司 | Calorizing impregnation agent for K4648 alloy and preparation method thereof, and calorizing method |
| CN102758169B (en) * | 2012-07-31 | 2014-09-03 | 西北工业大学 | Process method for embedding cementation of Al-Si-Y on TiAl on alloy surface |
| CN102766840B (en) * | 2012-08-08 | 2014-05-14 | 中国石油化工股份有限公司 | Surface modification zinc-aluminum rare earth joint-seeping method of steel heat exchanger tube bunch and seeping agent thereof |
| CN103014615B (en) * | 2012-12-31 | 2015-07-08 | 淄博万昌化工设备有限公司 | Method for preparing aluminum-molybdenum surface alloying coating on surface of steel |
| CN103266298B (en) * | 2013-06-04 | 2015-11-18 | 南昌航空大学 | Stainless steel low-temperature powder embedding Fe-Al permeation penetration enhancer and pack cementation processing method |
| CA2882788C (en) * | 2014-02-26 | 2019-01-22 | Endurance Technologies, Inc. | Coating compositions, methods and articles produced thereby |
| CN104498868A (en) * | 2014-12-29 | 2015-04-08 | 国家电网公司 | Multi-element alloy zinc-impregnation method |
| US10822710B2 (en) | 2016-07-06 | 2020-11-03 | The Board Of Trustees Of The University Of Illinois | Aluminized metallic scaffold for high temperature applications and method of making an aluminized metallic scaffold |
| CN107893210A (en) * | 2017-11-20 | 2018-04-10 | 中国石油大学(华东) | A kind of ferrous materials low temperature zinc-aluminium agent for co-cementation and co-infiltrating method |
| CN108118285A (en) * | 2017-12-29 | 2018-06-05 | 东方电气集团东方锅炉股份有限公司 | Improve low temperature aluminizing agent, method and the material of high temperature resistance steam oxidation performance |
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| CN112159954B (en) * | 2020-10-29 | 2022-10-18 | 中国航发南方工业有限公司 | Aluminizing agent and application thereof |
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