CN104762628A - Combustion gas steel cylinder and storage tank anticorrosion method - Google Patents

Combustion gas steel cylinder and storage tank anticorrosion method Download PDF

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Publication number
CN104762628A
CN104762628A CN201410004071.9A CN201410004071A CN104762628A CN 104762628 A CN104762628 A CN 104762628A CN 201410004071 A CN201410004071 A CN 201410004071A CN 104762628 A CN104762628 A CN 104762628A
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metal
gas
combustion gas
steel cylinder
pressure
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CN201410004071.9A
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王正天
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王正天
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Abstract

The invention relates to a combustion gas steel cylinder and storage tank anticorrosion method, and especially relates to a method for solving corrosion of hydrogen sulfide in compressed combustion gas and liquefied combustion gas to a high pressure metal container and reducing the SO2 discharging concentration after combustion of the combustion gas containing sulfur-containing components. Combustion gas steel cylinder steel cylinder and storage tanks have a hydrogen sulfide corrosion inhibition function through plating the high pressure metal container with a metal coating containing at least one of Zn, Sn, Cu and Pb, or adding metal powder containing at least one of Zn, Sn, Cu and Pb, or combining coating with the addition of the metal powder, and the characteristic of easy adsorption of mercaptan and other sulfides to the Zn, Sn, Cu and Pb metal components is used to greatly reduce the sulfur-containing components in the combustion gas entering a combustion apparatus and reduce SO2 pollution. The method has the advantages of simplicity, easy implementation, low cost and convenient enforcement.

Description

The anti-corrosion method of a kind of gas cylinder, storage tank
Technical field
Disclosed in this invention is the anti-corrosion method of a kind of gas cylinder, storage tank, refers to that solving hydrogen sulfide in compressed gas, liquefaction gas to the burn into belonging to container more than high pressure reduces sulfur component in combustion gas discharge SO after fuel gas buring especially 2the method of concentration, belongs to material technology category.
Background technology
Hydrogen sulfide is a kind of objectionable constituent in liquefaction gas, in petroleum refining process, particularly hydrocracking technique, sulphur in crude oil is reduced into thinization hydrogen, pass through fractionation, reside in liquefied petroleum gas (LPG), just can with pressurized liquefied and become the part of liquefied petroleum gas (LPG) if do not add alkali washing process before as finished product, alkali cleaning sometimes does not thoroughly also have partial vulcanization hydrogen and is present in liquefied petroleum gas (LPG).
In recent years, in a line city, due to popularizing of pipe natural gas, the market of liquefaction gas is in compression; But in tier 2 cities, small towns, liquefied petroleum gas (LPG) obtains increasingly extensive application in industry and people's lives, steel cylinder, the storage tank of storage liquid liquefied oil gas constantly increase, the contained thinization hydrogen-type corrosion medium of liquefied petroleum aerogenesis, warehousing and transportation facilities is caused to the phenomenon of stress corrosion crack, cause attention and the concern of people.The mechanical damage that stress corrosion is different from general corrosion and causes, neither the big area alkali of whole storage tank thin, but local produce in tank body one region, it follows following rule: latent period, and---the crackle apparition---crack propagation phase---is until the destructive process that breaks, this destruction is with larger emergentness, more difficult prediction, often brings loss of life and personal injury.
Also there is hydrogen sulfide in compressed natural gas, especially the Sweet natural gas that coastal in South East Asia (as Thailand, Burma etc.) find, have higher hydrogen sulfide content, and their desulfurization technology is lower, natural gas line is universal few, uses compressed natural gas mode in a large number.
No matter be that (people are usually simply referred to as liquefied gas to accumulating liquefaction gas, comprise liquefied petroleum gas (LPG) and natural gas liquids) or compressed gas, all the other belong to high pressure vessel, what capacity was little is commonly referred to as liquefaction gas steel cylinder or compressed gas steel cylinder, capacious have liquefaction gas storage tank or compressed natural gas storage tank, its housing and the position such as weld seam, adapter thereof certainly exist stress, contact, easily produce corrosion with the thinization hydrogen in liquefaction gas or compressed natural gas:
H 2S+Fe=FeS+H 2(1)
If contain liquid phase water in liquefaction gas or compressed natural gas, and H 2s concentration is higher, and stress corrosion speed is just very fast, the steel cylinder that more may cause or metal tank tank rupture; Although, corrosion produce iron sulphide when pH is higher (during pH>6, corresponding to S 2-concentration is higher, and FeS is more stable), proceeding of corrosion can be delayed as protective membrane; But in liquefaction gas or compressed natural gas, practical situation are generally containing a small amount of water, and pH<6, the FeS that corrosion produces is relatively unstable, and etch ratio is very fast, and high pressure vessel easily stress corrosion cracking occurs.
As far back as early 1950s, the U.S. just begins one's study H 2the stress corrosion problem of S, through the exploration of decades, NACE (NACE) proposes, the petroleum gas liquefied, when there being liquid phase water, H 2during the gaseous phase partial pressure >0.00035MPa of S, just there is H 2the corrosion of S to equipment and the danger of destruction; Japan also began one's study in 1962, through 20 years of researches and practice, was solving the H of high-strength steel 2s stress corrosion aspect achieves certain success, and worked out " high-strength steel use standard ", and this standard clear stipulaties in various degree steel grade of rank allows to store H 2the limit value of S concentration.China's research in this respect there has also been larger progress, and China Petroleum Chemicals Corporation is for avoiding H 2s to conveying and the stress corrosion of storage facilities, to the H in liquefied petroleum gas (LPG) 2s content is defined as below 10ppm.But, the situation current according to China, most without refining in oil field light hydrocarbon, H 2the content of S and water is general higher.The crackle found in many storage tanks in succession open tank inspection in recent years, wherein has a considerable amount of crackle to belong to H 2the stress corrosion cracking that S causes.
Market has and adopts ZARE coating to reduce H 2the method of the stress corrosion that S causes, ZARE contains sacrificial anode metal composition and adds the compositions such as rare earth element (being called for short ZARE coating), and rare earth element can improve the activity of metal alloy greatly, thus effectively prevents H 2s stress corrosion crack; But rare earth resources belongs to scarce resource, there is the restriction of cost factor in the application in this field.
At present mainly through to manufacture gaseous-pressure container steel material and add the method such as alloying elements cr, Mo, V, Ti, B and prevent H 2s stress corrosion; Easy, effectively cannot realize the suppression of the stress corrosion to hydrogen sulfide, the thinization hydrogen that also cannot effectively reduce in combustion gas produces the phenomenon of sulfur dioxide pollution air after burning.
The sulfur-bearing standard max of China's civil natural gas: a class gas is little equals 100mg/ cubic meter, two class gas are little equals 200mg/ cubic meter, and three class gas are little equals 460mg/ cubic meter; The sulfurous gas discharged after 1 cubic metre of combustion of natural gas mostly is (460mg/32) x64=920mg most, and minimum is 200mg sulfurous gas.China is 1300 billion cubic meters at the consumption of 2011, and the Natural Gas Demand of China may double in these 5 years at 2011-2015; According to International Energy Agency prediction, the year two thousand thirty Natural Gas In China consumption will reach about 3310 billion cubic meters, become second-biggest-in-the-world natural gas consumption state, account for 7% of world's total amount consumed.Huge gas consumption, also means and has a large amount of sulfur dioxide gas to discharge, can infer that the sulfurous gas of discharging for 2011 is at least 2.6 ten thousand tons, may reach 120,000 tons at most from gas consumption this respect data; If do not taken measures, increase by more than 3 times to the year two thousand thirty river.
In order to solve the problem, suppress compressed gas, hydrogen sulfide in liquefaction gas to the corrosion of high-pressure metal container, and significantly reduce sulfur component in combustion gas discharge SO after fuel gas buring 2concentration is to reduce atmospheric pollution, and spy completes the present invention.
Summary of the invention
The object of this invention is to provide a kind of method suppressing the hydrogen sulfide in compressed gas and liquefaction gas the burn into of high-pressure metal container also significantly to be reduced to sulfur component in combustion gas, reduce fuel gas buring and produce SO 2the atmospheric pollution caused.
In order to achieve the above object, the technical solution used in the present invention is:
Add at least containing a kind of Metal Zn in these high-pressure metal containers, Sn, Cu, the metal component of Pb, as sacrificial anode component and the absorption carrier to sulfur component in combustion gas, can by plating at least containing a kind of Metal Zn in the inside of these high-pressure metal containers, Sn, Cu, the metal plating of Pb, or belong in container more than these high pressure and add at least containing a kind of remaining genus Zn, Sn, Cu, the metal-powder of Pb, also can adopt coating and add the remaining method belonging to powder combinations, it is made to possess to suppress hydrogen sulfide in compressed gas and liquefied gas to the function of high-pressure metal container corrosion, and significantly can reduce sulfur component in combustion gas and enter combustion unit, avoid burnedly being oxidized to SO 2pollute.
In such scheme, at least containing a kind of remaining coating belonging to Zn, Sn, Cu, Pb in high-pressure metal container, or the metal-powder at least containing a kind of Metal Zn, Sn, Cu, Pb, these remaining genus components can be reacted to generate with hydrogen sulfide and be dredged compound and hydrogen, play a protective role to metal vessel; In addition, also have in compressed gas and liquefied gas and dredge alcohol sulfides, easily adsorb on the surface of Zn, Sn, Cu, Pb, sulfide can be reduced and enter that burner is burned is oxidized to SO 2the phenomenon polluted; The ratio of Zn, Sn, Cu, Pb is great, can not reduce make a significant impact volume of a container.
From the solubility product of slightly soluble compound, remaining genus Zn, Sn, Cu, Pb have than Fe more preferably with H 2s reaction generates the tendency of sulfide:
Ksp(FeS)=6×10 -18(2)
Ksp(ZnS)=6×10 -24(3)
Ksp(SnS)=1×10 -25(4)
Ksp(CuS)=6×10 -36(5)
Ksp(Cu 2S)=2×10 -48(6)
Ksp(PbS)=1×10 -28(7)
It suppresses H 2the mechanism of action that S corrodes steel cylinder, is equal to the metal-powder of interpolation or metal plating as sacrificial anode.
For freshly prepd high-pressure metal container, plating or the remaining method belonging to coating of electroless plating can be adopted, implement more convenient; For belonging to container more than the high pressure used, can adopt and add the remaining method belonging to powder, convenient operation; In the Sweet natural gas producing region that thinization hydrogen richness is higher, the method for the two combination can be adopted, high-pressure metal internal tank is plated metal plating, adds appropriate remaining genus powder simultaneously, to ensure anti-hydrogen sulfide corrosion and to reduce sulfurous gas air-polluting effect.
In sum, core technology of the present invention is: at accumulating compressed gas, in the high-pressure metal container of liquefied gas, introduce easier and hydrogen sulfide reacting metal coating, the method of metal-powder or their combination, utilize Zn, Sn, Cu, Pb metal component easily and hydrogen sulfide react and generate sulfide and protect high-pressure metal container not cure hydrogen-type corrosion, utilize Zn, Sn, Cu, Pb metal component easily adsorbs the thin compounds such as mercaptan, reduce contracting combustion gas, the sulfide of liquefied gas enters the burned oxidation of burner, reduce atmospheric pollution, method is simple, be convenient to implement, with low cost.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described:
The different methods that table 1, embodiment are corresponding
Employing volume is that the cylinder for liquefied gas of the carbon steel material of 35.5L is done experiment: the plating of new interior of steel bottle or electroless plating completed before producer's cylinder valve handling machinery assembling cylinder valve, and adding metal-powder is also completed before cylinder valve handling machinery assembling cylinder valve; Used cylinder for liquefied gas, before opening cylinder valve, is soaked bottle with hot water barrel and the residual combustion gas that can volatilize is finished using by gas-cooker as far as possible, on cylinder valve handling machinery, then open cylinder valve add metal-powder, be loaded on cylinder valve.
Table 1 is listed the different methods of disposal corresponding to embodiment, by steel cylinder corresponding in table 1 after same gas station filling liquefied gas is placed three days, the content of sulfurous Anhydride in gas after test burning, find that the content of sulfur dioxide of steel cylinder is after treatment generally lower than the content of sulfur dioxide of control sample, with embodiment 6 zinc-plated+content of sulfur dioxide for the treatment of process of adding zinc powder is minimum, low by 50%. than control sample
It should be pointed out that the above embodiment can make the present invention of those skilled in the art's comprehend, but do not limit the present invention in any way.Therefore, although this specification sheets embodiment is to present invention has been detailed description, it will be appreciated by those skilled in the art that and still can modify to the present invention or equivalent replacement; And all do not depart from technical scheme and the improvement thereof of the spirit and scope of the present invention, it all should be encompassed in the middle of the protection domain of patent of the present invention.

Claims (1)

1. an anti-corrosion method for gas cylinder, storage tank, refers to that solving compressed gas, thinization hydrogen in liquefaction gas to the burn into of high-pressure metal container reduces sulfur component in combustion gas discharge SO after fuel gas buring especially 2the method of concentration, it is characterized in that adding the metal component at least containing a kind of Metal Zn, Sn, Cu, Pb in these high-pressure metal containers, its addition means can be:
(1) metal plating at least containing a kind of Metal Zn, Sn, Cu, Pb, in the inside of high-pressure metal container is plated,
(2), in these high-pressure metal containers, the metal-powder at least containing a kind of Metal Zn, Sn, Cu, Pb is added,
(3) combination of coating and interpolation metal-powder, is adopted.
CN201410004071.9A 2014-01-06 2014-01-06 Combustion gas steel cylinder and storage tank anticorrosion method Pending CN104762628A (en)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101928944A (en) * 2010-03-12 2010-12-29 邹积强 Alloy sacrificial anode film preventing stress corrosion cracking and preparation method thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101928944A (en) * 2010-03-12 2010-12-29 邹积强 Alloy sacrificial anode film preventing stress corrosion cracking and preparation method thereof

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