CN111809140A - Low-temperature carbon nitrogen oxygen co-cementation treating agent for improving hydrogen sulfide corrosion resistance of stainless steel - Google Patents
Low-temperature carbon nitrogen oxygen co-cementation treating agent for improving hydrogen sulfide corrosion resistance of stainless steel Download PDFInfo
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- CN111809140A CN111809140A CN202010671535.7A CN202010671535A CN111809140A CN 111809140 A CN111809140 A CN 111809140A CN 202010671535 A CN202010671535 A CN 202010671535A CN 111809140 A CN111809140 A CN 111809140A
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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
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/40—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using liquids, e.g. salt baths, liquid suspensions
- C23C8/52—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using liquids, e.g. salt baths, liquid suspensions more than one element being applied in one step
Abstract
The invention relates to a low-temperature carbon nitrogen oxygen co-permeation treating agent for improving hydrogen sulfide corrosion resistance of stainless steel, which comprises the following components in percentage by weight: KCNO 1-55%, NaCNO 1-55%, K2CO38 to 25 percent of (3), Na2CO38%~25%，Li2CO33%~25%，NaOH 5%~15%，KOH 5%~15%，La(OH)30.1%~5%,K2SO40.1%~2%,Na2SO40.1% -2%. The treatment temperature is 390-430 ℃ and the treatment time is 30-600 minutes. The treatment agent improves the thickness of the stainless steel infiltration layer and the performance of hydrogen sulfide corrosion resistance after treatment.
Description
Technical Field
The invention relates to a treating agent applied to low-temperature liquid carbon nitrogen oxygen co-cementation treatment of stainless steel, and after the stainless steel is subjected to low-temperature treatment by the treating agent, the corrosion resistance of a material, particularly the corrosion resistance in a hydrogen sulfide resistant environment, is greatly improved.
Background
The gas field in Chongqing area is an extra large gas field in China, and the reserve capacity is 3000 multiplied by 108m3Above all, about 67% of the detected are acid gas fields, and most of the gas fields belong to high-sulfur gas fields, such as the ferry river field H of Sichuan2S is 17% (v), CO28% (v), Rojiazhai gas field H2S is 10.49% (v), CO210.41% (v), iron mountain slope gas field H2S is 13% (v), CO27% (v) and an organic sulfur content of about 500 mg/m3The concentration of the acid gas far exceeds that of the acid gas in the gas field developed at home at present. In the gas collection and transportation equipment, a large number of stainless steel parts are used. The invention improves the application of stainless steel, especially austenitic stainless steel in high acid environment after low temperature carbon nitrogen oxygen treatment, has important functions for improving the corrosion resistance and the service life of key parts and reducing the cost, and has extremely wide application prospect.
The liquid carbon nitrogen oxygen treatment technology is also called as a soft nitriding process treatment technology, active nitrogen atoms generated by decomposing cyanate under the assistance of active substances are utilized to permeate into a workpiece, and an iron compound layer and a diffusion layer are formed on the surface of the workpiece, so that the wear resistance, the corrosion resistance and the fatigue resistance of the iron-based material are improved. Liquid tufftride treatment has therefore been widely used in production practice.
However, the liquid soft nitriding treatment technology applied to stainless steel at present has the following defects: generally, nitriding base salt is applicable at a high temperature generally between 520 ℃ and 650 ℃, and is not suitable for low-temperature treatment of stainless steel. Foreign authoritative research shows that (Dong Hansan. S-phase surface engineering of Fe-Cr, Co-Cr and Ni-Cr alloys [ J ]. International Materials Reviews, 2013, 55(2):65-98.), for corrosion resistant alloys such as stainless steel, etc., when the processing temperature is higher than 450 ℃, a nitrided layer can precipitate CrN, which leads to the reduction of the corrosion resistance of the material.
In addition, urea is generally used in the liquid soft nitriding treatment technology, and can generate a large amount of ammonia gas in the decomposition process, so that the environment is polluted, and the body of an operator is injured. For example, the invention of patent application No. 201010188211.4 provides a nitridizing salt for liquid nitriding, which consists of the following components in percentage by weight: CO (NH)2)230%~50%，Na2CO310%~20%，K2CO310%~20%，NaCl 20%~25%，K2SO31%~3%，CeCO31-3% of LiOH, 5-10% of LiOH. The treatment temperature is 580-650 ℃, the use temperature is 500-630 ℃, and the corrosion resistance of the material is reduced when the stainless steel is treated at the temperature. A large amount of ammonia gas is generated in the using process, and the environment is polluted.
Previous work by the inventors of the present patent application (wang, bear scale, fanghuan, a nitriding salt for low temperature salt bath nitriding of stainless steel, ZL 201110184878.1; wang, bear scale, zhangtaiping, a nitriding salt for low temperature salt bath nitriding, ZL 201110150084.3) showed that: the reasonable addition of proper substances makes the liquid soft nitriding salt formed according to a certain rule reduce the use temperature to the applicable temperature of stainless steel, but the treated infiltrated layer is thinner, after the treatment at 450 ℃ for 8h, the compound layer of 321 austenitic stainless steel is 10 mu m, the layer is thinner, and the material does not have the performance of being used in a high-sulfur environment.
The inventor of the patent application of the invention continuously optimizes the system on the basis, reduces the applicable temperature of the co-permeation treating agent and obviously increases the thickness of a permeation layer by literature research and analysis and combining a large number of tests, and can improve the corrosion resistance of the stainless steel while obviously improving the wear resistance of the stainless steel.
Disclosure of Invention
The invention aims to overcome the defect that the applicable temperature of nitriding base salt is higher in the liquid nitriding process of the stainless steel at present, and provides a low-temperature carbon-nitrogen-oxygen co-nitriding treating agent which can carry out low-temperature liquid nitriding treatment on the stainless steel, has a thicker carburized layer and is resistant to hydrogen sulfide corrosion.
The purpose of the invention is realized by the following steps: a low-temperature carbon nitrogen oxygen co-cementation treatment agent for improving hydrogen sulfide corrosion resistance of stainless steel comprises the following components in percentage by weight: the composition comprises the following components in percentage by weight: KCNO 1-55%, NaCNO 1-55%, K2CO38-25% of (A), Na2CO38-25%，Li2CO33-25%，NaOH 5-15%，KOH 5-15%，La(OH)30.1-5% , K2SO40.1-2%, Na2SO40.1-2% 。
The technical scheme adopted by the invention optimizes the formula of the co-permeation treating agent, obtains a basic formula through a large amount of tests and verifies, and reduces the treatment temperature. The reaction principle of the invention in the using process is as follows:
cyanate radical decomposition provides reactive nitrogen atoms: 4CNO-→ CO3 2-+ 2CN-+ CO + 2[N]
Nitriding reaction in the process of carbon nitrogen oxidation: (FeCr)Base body+ [N]→ （FeCr）Base body+[N]Gap
Nitriding reaction in the process of carbon nitrogen oxidation: (FeCr)Base body+ [C]→ （FeCr）Base body+[C]Gap
Nitriding reaction in the process of carbon nitrogen oxidation: (FeCr)Base body+ [N]→ （FeCr）xOy
Oxidation of cyanide by oxidizing components: CN-+ [O]→ CNO-
Wherein the cyanate provides cyanate ions; the reasonable collocation of the chloride and the hydroxide can improve the activity of the nitride and promote nitriding; and K2CO3、Na2CO3The reasonable matching of the components can effectively improve the activity and the fluidity of the nitrified salt and widen the application range of the treating agent. Under the working state, active nitrogen atoms generated by the decomposition of cyanate ions permeate into the surface of the corrosion-resistant iron-based material, and a hard and compact supersaturated solid solution layer is formed on the surface of the material, wherein the layer is thick. Thereby improving the wear resistance, corrosion resistance and fatigue resistance of the material. Due to CNO in the treating agent used in the present invention-Has stronger reduction potential, and the austenitic stainless steel can realize surface treatment without blunt pretreatment.
Proportioning, mixing, and melting at 480 deg.C. The low-temperature carbon-nitrogen-oxygen co-cementation treating agent for improving the hydrogen sulfide corrosion resistance of the stainless steel at 390-430 ℃ is prepared after melting.
The low-temperature carbon nitrogen oxygen co-cementation treatment agent for improving the hydrogen sulfide corrosion resistance of the stainless steel is introduced with the activating component and matched according to the reasonable proportion, so that the salt can keep a certain nitrogen potential at a lower temperature state, and the applicable temperature range of the soft nitriding salt is reduced to about 430 ℃. Taking austenitic stainless steel 316 as an example, the treatment by the soft nitriding salt can obtain a compound layer with the thickness of about 25 mu m, and the treated workpiece has good wear resistance and corrosion resistance.
Drawings
FIG. 1 shows the cross-section metallographic phase of 316 austenitic stainless steel treated by a treating agent at 430 ℃ for 8 h.
FIG. 2 is a graph of the corrosion rate of 316 austenitic stainless steel in NACEA saturated hydrogen sulfide solution for 720 hours.
Detailed Description
The low-temperature carbon for improving the hydrogen sulfide corrosion resistance of the stainless steel of the embodimentThe nitrogen-oxygen co-penetration treatment agent comprises the following components in percentage by weight: KCNO 35%, NaCNO 30%, K2CO39%，Na2CO38.5%，Li2CO33%，NaOH6%，KOH 4%, La(OH)33% ，Na2SO4 0.2%，K2SO40.3 percent. The embodiment is suitable for being used under the process condition of 430 ℃, and the using environment of the treating agent is stable. The cross-sectional metallographic results of the 316 austenitic stainless steel treated by the treating agent at 430 ℃ for 8h are shown in figure 1, the thickness of the white layer is 26.1 mu m, and the surface microhardness of the white layer reaches 1125HV 0.1.
FIG. 2 is a graph of the corrosion rate of 316 austenitic stainless steel in NACEA saturated hydrogen sulfide solution for 720 hours. It can be seen that the hydrogen sulfide corrosion resistance of the austenitic stainless steel is greatly improved after the austenitic stainless steel is treated by the low-temperature carbon nitrogen oxygen co-permeation treatment agent.
It should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the same; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (4)
1. A low-temperature carbon nitrogen oxygen co-cementation treatment agent for improving hydrogen sulfide corrosion resistance of stainless steel is characterized by comprising the following components in percentage by weight: KCNO 1-55%, NaCNO 1-55%, K2CO38%~25%，Na2CO38%~25%，Li2CO33%~25%，NaOH 5%~15%，KOH 5%~15%，La(OH)30.1%~5% , K2SO40.1%~2%, Na2SO40.1%~2%。
2. The low-temperature carbon nitrogen oxygen co-cementation treatment agent for improving the hydrogen sulfide corrosion resistance of stainless steel according to claim 1 is characterized by comprising the following components in percentage by weight: KCNO 35%, NaCNO 30%,K2CO39%，Na2CO38.5%，Li2CO33%，NaOH 6%，KOH 4%, La(OH)33% ,Na2SO4 0.2%, K2SO40.3%。
3. the low-temperature carbonitriding agent as claimed in claim 1, wherein the low-temperature carbonitriding treatment temperature is 390-430 ℃ for 30-600 min.
4. The low-temperature carbonitriding treatment agent for improving the resistance of stainless steel to hydrogen sulfide corrosion according to claims 1-3, characterized in that after the low-temperature carbonitriding treatment, the low-temperature strengthening layer of austenitic stainless steel is larger than 25 μm, and the microhardness and the resistance to hydrogen sulfide corrosion are significantly improved.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022245554A1 (en) * | 2021-05-20 | 2022-11-24 | Refined Technologies, Inc. | Compositions for preventing polythionic acid (pta) stress corrosion cracking on 300 series stainless steel and methods of using the same |
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| CN1488007A (en) * | 2000-11-29 | 2004-04-07 | 帕克热处理工业株式会社 | Method of salt bath nitriding for producing iron member having improved corrosion resistance and iron parts |
| US20040159372A1 (en) * | 2001-11-02 | 2004-08-19 | Kolene Corporation | Low temperature nitrocarburizing salt and method of use |
| CN101871088A (en) * | 2009-04-21 | 2010-10-27 | 上海江凯金属表面处理技术有限公司 | Salt bath formula for treating stainless air conditioning compressor blade by salt bath nitriding treatment and treatment method |
| CN102899604A (en) * | 2012-09-27 | 2013-01-30 | 南车戚墅堰机车车辆工艺研究所有限公司 | Metal surface salt bath nitrocarburizing method |
| CN102943234A (en) * | 2012-11-20 | 2013-02-27 | 四川大学 | Low-temperature salt bath nitriding process for Austenitic stainless steel workpiece |
| CN106967945A (en) * | 2016-01-14 | 2017-07-21 | 杭州巨星科技股份有限公司 | Rare earth-sulfide for stainless steel urges the QPQ techniques for oozing low temperature QPQ compositions and stainless steel knife altogether |
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2020
- 2020-07-13 CN CN202010671535.7A patent/CN111809140A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1488007A (en) * | 2000-11-29 | 2004-04-07 | 帕克热处理工业株式会社 | Method of salt bath nitriding for producing iron member having improved corrosion resistance and iron parts |
| US20040159372A1 (en) * | 2001-11-02 | 2004-08-19 | Kolene Corporation | Low temperature nitrocarburizing salt and method of use |
| CN101871088A (en) * | 2009-04-21 | 2010-10-27 | 上海江凯金属表面处理技术有限公司 | Salt bath formula for treating stainless air conditioning compressor blade by salt bath nitriding treatment and treatment method |
| CN102899604A (en) * | 2012-09-27 | 2013-01-30 | 南车戚墅堰机车车辆工艺研究所有限公司 | Metal surface salt bath nitrocarburizing method |
| CN102943234A (en) * | 2012-11-20 | 2013-02-27 | 四川大学 | Low-temperature salt bath nitriding process for Austenitic stainless steel workpiece |
| CN106967945A (en) * | 2016-01-14 | 2017-07-21 | 杭州巨星科技股份有限公司 | Rare earth-sulfide for stainless steel urges the QPQ techniques for oozing low temperature QPQ compositions and stainless steel knife altogether |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022245554A1 (en) * | 2021-05-20 | 2022-11-24 | Refined Technologies, Inc. | Compositions for preventing polythionic acid (pta) stress corrosion cracking on 300 series stainless steel and methods of using the same |
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