CN115852280A - Heat treatment method of Coriolis mass flowmeter for high-pressure hydrogen - Google Patents
Heat treatment method of Coriolis mass flowmeter for high-pressure hydrogen Download PDFInfo
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 239000001257 hydrogen Substances 0.000 title claims abstract description 84
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 84
- 238000010438 heat treatment Methods 0.000 title claims abstract description 73
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 238000001816 cooling Methods 0.000 claims description 19
- 238000004321 preservation Methods 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 239000010963 304 stainless steel Substances 0.000 claims description 3
- 229910000589 SAE 304 stainless steel Inorganic materials 0.000 claims description 3
- 230000035945 sensitivity Effects 0.000 abstract description 21
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- 150000002431 hydrogen Chemical class 0.000 abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 80
- 229910052759 nickel Inorganic materials 0.000 description 40
- 230000000694 effects Effects 0.000 description 20
- 206010070834 Sensitisation Diseases 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
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- 229910001566 austenite Inorganic materials 0.000 description 10
- 239000012071 phase Substances 0.000 description 10
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention provides a heat treatment method of a Coriolis mass flowmeter for high-pressure hydrogen, which comprises the following steps of: a) Selecting HC-22 as a liquid receiving material of the Coriolis mass flowmeter; b) Assembling a heat treatment assembly of the Coriolis mass flowmeter; c) Respectively laying brazing materials BNi-5 on the vibration isolation sheet and the measuring pipe as well as the measuring pipe and the flow divider; d) Installing a wind scooper; e) And (4) sending the mixture into a vacuum gas quenching furnace, vacuumizing and executing a heat treatment process. According to the invention, a more appropriate material is selected, and a brand-new heat treatment overall process is adopted, so that the hydrogen removal thoroughness of the liquid receiving part is improved, the uniformity of the material of the liquid receiving part is improved, the material defect of the liquid receiving part is reduced, the stress concentration of the liquid receiving part is reduced, the hydrogen embrittlement sensitivity of the liquid receiving part is reduced, and the risk of hydrogen embrittlement of the liquid receiving part is reduced; the brazing is ensured to be firm, uniform and full, and the strength and consistency of a welding joint are improved; the stress removal of the liquid receiving part is thorough, and the precision and the repeatability of the Coriolis mass flowmeter are improved.
Description
Technical Field
The invention relates to the technical field of heat treatment, in particular to a heat treatment method of a Coriolis mass flowmeter for high-pressure hydrogen.
Background
The liquid receiving material of the existing Coriolis mass flowmeter is 316L stainless steel, the nickel content of the 316L stainless steel is 10-14%, the lower limit is generally 10%, the nickel equivalent is 25.188-31.468%, and the national standard GB50516-2010 requires that the nickel content is more than 12% and the nickel equivalent is more than 28.5% when the austenitic stainless steel is used for a hydrogen pipeline. Under critical conditions, which is a requirement for hydrogen pipelines, the measuring tube for mass flowmeters generally has a small wall thickness, so that materials with higher nickel content and nickel equivalent are required.
When the small-specification Coriolis mass flowmeter is used for brazing heat treatment, the situations of incomplete and uneven brazed parts and insufficient strength often occur, and the analysis reason is that when the conventional Coriolis mass flowmeter assembly is used for brazing heat treatment, a brazing filler metal is laid on the assembly and then directly placed into a vacuum gas quenching furnace for brazing heat treatment, but after the highest temperature heat preservation is finished, a large amount of low-temperature nitrogen needs to be flushed for cooling, but under the working condition, the brazing filler metal is still in a liquid phase, the high-pressure hydrogen flowmeter is generally in a small specification, brazed parts are extremely small, the brazing filler metal is extremely rarely laid, the brazing filler metal which is still in the liquid phase can be blown away by instantaneous high-pressure air flow, so that the brazing is not firm and uneven, and the welding seam of the brazed part is not full. Meanwhile, when the current Coriolis mass flowmeter assembly is brazed, BNi-1 (BNi 74 CrSiB) brazing material is selected, the brazing material contains too high iron and carbon components, and the content of chromium is low, so that the brazing material is not suitable for nickel-based single-phase austenitic alloy applied to a high-pressure hydrogen flowmeter.
More importantly, the current coriolis force mass flowmeter for high-pressure hydrogen gas needs to be subjected to dehydrogenation heat treatment, brazing heat treatment, stress relief heat treatment and solution heat treatment, but the existing brazing and heat treatment process scheme has poor process effects, i.e. hydrogen absorbed in a liquid receiving component cannot be thoroughly removed; secondly, the residual stress of the equipment is large, so that the accuracy and the repeatability of the Coriolis mass flowmeter for the high-pressure hydrogen are poor, and the liquid metering accuracy can only reach 0.15 percent generally; thirdly, the problems of uneven material, defects, stress concentration and martensite phase transformation cannot be effectively solved, the hydrogen embrittlement sensitivity is high, and the hydrogen embrittlement phenomenon easily occurs under the working condition of high pressure and hydrogen containing after long-time work.
Disclosure of Invention
In view of the above, in order to prevent the liquid receiving material of the coriolis force mass flowmeter from being hydrogen brittle in a high-pressure hydrogen environment, which causes damage to the liquid receiving metal and hydrogen leakage, the high-pressure hydrogen coriolis force mass flowmeter selects a single-phase austenitic alloy with high nickel content and nickel equivalent as the liquid receiving material, on the basis, the invention selects a more appropriate material and adopts a brand-new heat treatment overall process, so that the hydrogen removal thoroughness of the liquid receiving part is improved, the material uniformity of the liquid receiving part is improved, the material defects of the liquid receiving part are reduced, the stress concentration of the liquid receiving part is reduced, the hydrogen brittle sensitivity of the liquid receiving part is reduced, and the risk of hydrogen embrittlement of the liquid receiving part is reduced; the brazing is ensured to be firm, uniform and full, and the strength and consistency of a welding joint are improved; the stress removal of the liquid receiving part is thorough, and the precision and the repeatability of the Coriolis mass flowmeter are improved.
Hydrogen embrittlement: the hydrogen embrittlement of the metal material refers to the phenomenon that after hydrogen enters the metal, when the local hydrogen concentration reaches saturation, the plasticity of the metal is reduced, cracks are induced or hysteresis fracture is generated, and the hydrogen embrittlement can be divided into internal hydrogen embrittlement and environmental hydrogen embrittlement, wherein the former is caused by excessive hydrogen absorbed by the metal material in the smelting and processing processes (such as acid washing, electroplating, cold processing and the like); the latter means that in hydrogen-containing environments such as hydrogen gas, hydrogen enters the metal to cause performance loss. The present invention refers primarily to the former for hydrogen removal. The hydrogen embrittlement prevention can reduce the material unevenness, defects, stress and martensite phase transformation generated in the original material neutralization cold processing (such as bending and the like) process by removing hydrogen and heat treatment, and reduce the hydrogen embrittlement sensitivity.
The invention provides a heat treatment method of a Coriolis mass flowmeter for high-pressure hydrogen, which comprises the following steps of:
a) Selecting HC-22 as a liquid receiving material of the Coriolis mass flowmeter; b) Assembling a heat treatment assembly of the Coriolis mass flowmeter; c) Respectively laying brazing materials BNi-5 on the vibration isolation sheet and the measuring pipe as well as the measuring pipe and the flow divider; d) Installing a wind scooper; e) Sending the mixture into a vacuum gas quenching furnace, vacuumizing, and executing a heat treatment process:
a: firstly, the temperature is raised to 260 ℃ for 30 min;
b: the application time is 60min, and the temperature is kept at 260 ℃;
c: the application time is 30min, and the temperature is raised to 420 ℃;
d: it is administered for 20min, and maintained at 420 deg.C;
e: the application time is 30min, and the temperature is raised to 600 ℃;
f: the application time is 50min, and the temperature is raised to 1030 ℃;
g: taking 25min, and keeping the temperature at 1030 deg.C;
h: the application time is 50min, and the temperature is raised to 1170 ℃;
i: it is administered for 40min, and heat preservation is carried out at 1170 deg.C;
j: introducing low temperature liquid nitrogen, and rapidly cooling to room temperature for 50min; and finishing the heat treatment of the Coriolis mass flowmeter.
In the present invention, the nickel content of HC-22 in step A) is preferably 50% or more, and the nickel equivalent is preferably 77% or more. The invention adopts HC-22 as the liquid receiving material, can solve the technical problem that the prior art selects 316L stainless steel meeting the upper limit of national standard or 904L stainless steel, in particular: the 316L is selected as the defect that even if the 316L is selected according to the upper limit of national standard Ni, cr and Mo, the nickel content is 14 percent, the nickel equivalent is 31.5 percent, and is only a little higher than 12 percent and 28.5 percent of the national standard, but the nickel content is the standard of the national standard for hydrogen pipelines, generally, a measuring tube used by the Coriolis force mass flowmeter uses a thin-walled tube to ensure the Coriolis force effect, so the requirement is stricter than the national standard, and the 316L is not suitable for serving as the liquid receiving material of the mass flowmeter for high-pressure hydrogen; while 904L (nickel content is 23% -28%, nickel equivalent is 50.5%) is superior to 316L in material composition, but it has two problems, firstly, its nickel content and nickel equivalent are lower than HC-22 (nickel content is more than 50%, nickel equivalent is more than 77%), secondly, the yield strength and allowable stress of 904L are respectively 216MPa and 115MPa, and the yield strength and allowable stress of HC-22 are respectively 310MPa and 206MPa, especially the allowable stress is almost twice as much as 904L, which means that it is desired to bear the same pressure, the wall thickness of 904L measuring tube is about twice as much as HC-22, but the increase of wall thickness will greatly reduce the Coriolis effect of Coriolis mass flowmeter, and reduce the precision of the device; 904L is also not suitable.
In the present invention, the assembly of step B) preferably comprises:
the device comprises a supporting plate, a flow divider, a measuring tube, a vibration isolation sheet, brazing solder and a coil magnet bracket; wherein, the measuring pipe is respectively contacted with the flow divider and the vibration isolation sheet.
In the present invention, the BNi-5 in step C) does not contain Fe, contains C preferably at most 0.06 and Cr preferably at most 18.5-19.5%. The invention adopts BNi-5 as brazing filler metal, can solve the technical problems existing in the prior art of selecting BNi-2 as brazing material, and particularly comprises the following steps: BNi-2 is selected, and the components are as follows:
| Ni | Cr | B | Si | Fe | C | S | P | |
| BNi-2 | the remainder (about 82%) | 6～8 | 2.75～3.5 | 4.0～5.0 | 2.5～3.5 | ≤0.06 | ≤0.02 | ≤0.02 |
Compared with BNi-1, the content of Fe and C is greatly reduced, the content of Ni is increased, and the alloy is more suitable for welding stainless steel, but the Cr content is lower, the brazing temperature is lower (1010 ℃ -1177 ℃), and the alloy is not suitable for single-phase austenitic alloy with high nickel content and nickel equivalent.
In the present invention, the brazing material is preferably laid in step C) with a width of 1mm to 1.5mm, and a full weld of 360 ° is required.
In the present invention, the material of the wind scooper in the step D) is preferably 304 stainless steel.
In the present invention, the process of installing the wind scooper in step D) is preferably as follows:
the heat treatment components of each set of Coriolis mass flowmeter are provided with the air guide covers, then the air guide covers are fixed on the fixed bottom plate, and the fixed bottom plate can be provided with a plurality of sets of heat treatment components at the same time.
In the present invention, the principle of arranging the wind scoopers in step D) is preferably as follows:
(1) The arrangement of the air guide opening is symmetrical on two sides according to a central line; (2) The total area of the air guide opening occupies 25 to 35 percent of the area of the plane; (3) The arrangement of the air guide port must avoid the position where the brazing material is laid by at least 15mm; (4) an air guide port is required to be arranged at the elbow of the measuring pipe; (5) an air guide opening is required to be arranged in the center; and (6) the bottom edge is provided with a wind guide opening.
In the prior art, furnace cooling is adopted, or the assembly is integrally wrapped, or a large amount of brazing solder is coated, so that the rest can meet the strength requirement of a welding joint; in order to prevent the brazing filler metal in the liquid phase from being blown away by wind formed by low-temperature nitrogen, some manufacturers choose to cool the brazing filler metal to 850 ℃ along with the furnace; or directly furnace-cooled to a lower temperature, such as 400 ℃; both methods firstly increase the heat treatment duration, resulting in increased costs and reduced efficiency, especially with direct furnace cooling to lower temperatures; the sensitization temperature of the second stainless steel is 450-850 ℃, and the stainless steel is subjected to intergranular corrosion for a long time in the temperature range, so that the method is not suitable; thirdly, the whole assembly is wrapped, so that the air in the assembly cannot be completely separated out, oxidation occurs in the heat treatment process, meanwhile, because the whole assembly is wrapped, the temperature rise and heat dissipation of the assembly are greatly influenced, the heat treatment cannot be carried out according to the designed temperature gradient, the temperature of the assembly is uneven, and the solid solution and stress removal effects are influenced; the brazing material is not fully melted, so that the brazing effect is influenced, and the brazing is not firm, uneven and not full, welding slag is left and the like; the temperature is slowly reduced, so that the film is in a sensitization temperature section for a long time, and intergranular corrosion is caused. The air guide cover is adopted, so that firm and full brazing is ensured.
In the present invention, the degree of vacuum of the evacuation in step E) is preferably 1X 10 -2 Pa～3×10 -2 Pa, more preferably 2X 10 -2 Pa。
In the present invention, the degree of vacuum is preferably maintained at 1X 10 throughout the heat treatment process in step E) -2 Pa～3×10 - 2 PaMore preferably at 2X 10 -2 Pa。
Aiming at the heat treatment process, various heat treatment processes can be formulated by various manufacturers, but the current heat treatment processes are not ideal in effect and cannot meet the requirement of a high-precision Coriolis mass flowmeter for the working condition of high-pressure hydrogen; the heat treatment process of the traditional Coriolis flowmeter generally has the following problems: the temperature gradient is unreasonable, and the heat preservation time is not set at the temperature point, so that the flow meter component cannot be heated uniformly; the highest temperature value and the heat preservation time are unreasonable, the stress in the assembly cannot be effectively removed, the accuracy and the repeatability of the flowmeter are low, meanwhile, the nonuniformity, the defects, the stress concentration and the martensite phase transformation in the material cannot be effectively eliminated, so that hydrogen can more easily enter a weak area in the material in the later use of high-pressure hydrogen, and the hydrogen brittleness sensitivity of the material is increased; the final cooling section is unreasonable in arrangement, the stainless steel can be in a sensitization temperature range for a long time along with furnace cooling, intergranular corrosion of the stainless steel is caused, the hydrogen brittleness sensitivity of the material is increased, the service life of equipment is shortened, and the risks of damage of a liquid receiving part and hydrogen leakage are increased. The invention adopts an advanced heat treatment process, which specifically comprises the following steps:
a: firstly, the temperature is raised to 260 ℃ for 30 min;
b: the application time is 60min, and the temperature is kept at 260 ℃;
c: the application time is 30min, and the temperature is raised to 420 ℃;
d: it is administered for 20min, and maintained at 420 deg.C;
e: the application time is 30min, and the temperature is raised to 600 ℃;
f: the application time is 50min, and the temperature is raised to 1030 ℃;
g: the application time is 25min, and the temperature is kept at 1030 ℃;
h: the application time is 50min, and the temperature is raised to 1170 ℃;
i: taking 40min, and keeping the temperature at 1170 deg.C;
j: introducing low temperature liquid nitrogen, and rapidly cooling to room temperature for 50min.
Including a temperature section for dehydrogenation; a heat-insulating section for making the temperature of the assembly uniform; avoiding the temperature section setting of the sensitization temperature interval; the stress removing, brazing and solid solution effects are facilitated, the unevenness, the defects and the stress concentration of the material of the liquid receiving part are facilitated to be reduced, the hydrogen embrittlement sensitivity of the liquid receiving part is reduced, and the high-temperature section setting of the risk of hydrogen embrittlement of the liquid receiving part is reduced; the method is favorable for avoiding sensitization temperature, improving solid solution effect and avoiding the design of a cooling section for absorbing hydrogen during cooling.
The invention provides a heat treatment method of a Coriolis mass flowmeter for high-pressure hydrogen, which adopts the following basic scheme: selecting HC-22 as a liquid receiving material of the flowmeter; BNi-5 is selected as nickel-based brazing filler metal for brazing; assembling a brazing filler metal protective cover before the bare tube enters a vacuum gas quenching furnace; more reasonable heat treatment temperature gradient, heat preservation time and vacuum degree are set.
Has the following beneficial effects:
(1) Selecting HC-22 as a raw material, wherein the nickel content and the nickel equivalent of the HC-22 are far beyond the national standard, and meanwhile, the HC-22 is also a nickel-based single-phase austenitic alloy; the hydrogen embrittlement sensitivity of the material is reduced along with the increase of the nickel content and the nickel equivalent, the hydrogen embrittlement sensitivity of the material is reduced along with the increase of the proportion of austenite in the material, the nickel content of the HC-22 material is more than 50 percent, the nickel equivalent of the HC-22 material is more than 77 percent, and the single-phase austenite composition ensures that the hydrogen embrittlement sensitivity of the material is extremely low, and the hydrogen embrittlement prevention is ensured from the material aspect; meanwhile, the yield strength of HC-22 is 310MPa, the allowable stress is 206MPa, and the allowable stress is far more than 172MPa and 115MPa of 316L, so that the pressure-bearing capacity is ensured, the wall thickness of the pipe is reduced to the maximum extent, the Coriolis effect is improved, and the precision and the repeatability of equipment are improved.
(2) Due to the design of the air guide cover, the low-temperature liquid nitrogen can be selected for rapid cooling in the heat treatment, so that the problems that the brazing is not firm, the welding line is not uniform and the durability and the performance of equipment are reduced due to the fact that the liquid phase brazing material is blown away by the strong wind of the low-temperature liquid nitrogen are avoided; the long-time sensitization temperature section and low production efficiency caused by furnace cooling are avoided; the uneven heating and slow heat dissipation caused by full wrapping are avoided; the wind scooper is innovatively used in the heat treatment process, so that the firmness and uniformity of brazing can be guaranteed to the maximum extent, and the stress removal and solid solution effects of the assembly can be improved to the maximum extent.
(3) The BNi-5 brazing material is selected, so that the heat treatment temperature of 1170 ℃ can be met, meanwhile, the BNi-5 does not contain Fe, contains little C and high Cr, is more suitable for brazing of HC-22, and avoids the increase of hydrogen brittleness sensitivity caused by the formation of martensite in the brazing process.
(4) The innovative heat treatment process flow has the specific functions of temperature gradient setting and time setting:
a: firstly, the use time is 30min, and the temperature is raised to 260 ℃;
b: the application time is 60min, and the temperature is kept at 260 ℃;
the material is heated to 260 ℃ and is kept warm for 1 hour, and the activity of hydrogen is greatly enhanced at the temperature of more than 200 ℃ and the hydrogen can be separated out from the metal material, so that the hydrogen content in the material composition can be reduced to the maximum extent; the hydrogen embrittlement sensitivity of the liquid receiving part is reduced; meanwhile, the arrangement can fully volatilize the adhesive in the brazing material;
c: the application time is 30min, and the temperature is raised to 420 ℃;
d: taking 20min, and keeping the temperature at 420 deg.C;
the arrangement of the heat preservation section avoids a sensitization temperature section (450-850 ℃), and meanwhile, the heat preservation section is added and arranged at a proper place, so that the temperature uniformity of the assembly can be improved, and the solid solution effect of heat treatment can be improved;
e: the application time is 30min, and the temperature is raised to 600 ℃;
f: the application time is 50min, and the temperature is raised to 1030 ℃;
g: the application time is 25min, and the temperature is kept at 1030 ℃;
the temperature rising section is arranged in the sensitization temperature range, and the heat preservation section is not arranged, so that intergranular corrosion is avoided; the temperature is raised to the temperature point and kept, so that the internal stress of the part can be fully eliminated;
h: the application time is 50min, and the temperature is raised to 1170 ℃;
i: it is administered for 40min, and heat preservation is carried out at 1170 deg.C;
the setting of the temperature point and the setting of the heat preservation time period 1 can eliminate the residual stress in the material to the maximum extent, improve the consistency of the material, and effectively improve the zero stability of the mass flowmeter, thereby improving the precision of the equipment; 2. the solid solution effect is fully ensured, so that austenite and martensite in a metastable state are completely converted into supersaturated austenite, and the tissue unevenness and the microscopic defects in the material are eliminated; the reduction of stress in the material, the reduction of metastable austenite and martensite, the improvement of the structural uniformity and the reduction of defects can reduce the hydrogen embrittlement sensitivity of the material; therefore, the process can reduce the hydrogen brittleness sensitivity of the material to the maximum extent; 3. the melting temperature of the brazing solder is taken into consideration, so that the brazing solder can be melted and infiltrated fully, and firm welding is realized;
j: introducing low temperature liquid nitrogen, rapidly cooling to room temperature, and taking 50min;
the rapid cooling section ensures that the heat treatment assembly is not in a sensitization temperature range, avoids intergranular corrosion, ensures the performance of the material, simultaneously directly draws the material to room temperature, avoids hydrogen from entering the material again in the process, and ensures the dehydrogenation effect of the material to the maximum extent.
Drawings
FIG. 1 is an assembly view of a thermal management assembly of a Coriolis mass flowmeter in an embodiment of the present invention;
FIGS. 2 to 3 are schematic views showing brazing materials applied to the vibration isolating sheet and the measuring tube and the flow divider in the embodiment of the present invention;
FIG. 4 is a schematic view of an embodiment of the present invention illustrating installation of a wind scooper;
FIG. 5 is a schematic view of an embodiment of the present invention illustrating an air guiding opening;
FIG. 6 is a temperature profile of a heat treatment process in an embodiment of the present invention;
fig. 7 is a process flow diagram of a heat treatment method of the coriolis force mass flowmeter for high-pressure hydrogen gas according to the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Examples
(1) HC-22 was selected as the liquid receiving material of the flowmeter, and the composition thereof is shown in Table 1 below.
TABLE 1 ingredient table (mass percent) of HC-22 material
Wherein, the nickel content is more than 50 percent, and the nickel equivalent is more than 77 percent.
(2) The coriolis mass flowmeter completes the assembly of the heat treated components, as shown in fig. 1; FIG. 1 is an assembly drawing of a heat treatment assembly of a Coriolis mass flowmeter in an embodiment of the present invention, wherein 1 is a support plate, 2 is a flow divider, 3 is a measurement tube, 4 is a vibration isolation plate, 5 is a brazing material, 6 is a coil magnet holder.
(3) Brazing materials BNi-5 are laid at the positions of the vibration isolation sheets and the measuring pipe as well as the measuring pipe and the flow divider, and the components of the brazing materials are shown in the following table 2; and requiring to be fully laid, and requiring to form A:1mm to 1.5mm; b: the laying width of 1 mm-1.5 mm requires that a full weld joint is laid by 360 degrees, which is shown in figures 2-3.
TABLE 2BNi-5 Material composition ingredient Table (in percentage by mass)
| Ni | Cr | B | Si | C | S | P | |
| BNi-5 | The remainder (about 71%) | 18.5～19.5 | ≤0.03 | 9.75～10.5 | ≤0.06 | ≤0.02 | ≤0.02 |
(4) Installing an air guide cover, wherein the air guide cover is made of 304 stainless steel, each set of flow meter heat treatment assembly is provided with the air guide cover, then the air guide cover is fixed on a fixed bottom plate, and a plurality of sets of heat treatment assemblies can be simultaneously installed on the fixed bottom plate; referring to FIG. 4, FIG. 4 is a schematic view of an embodiment of the present invention showing a wind scooper, wherein 1 is a wind scooper, 2 is a fixed base plate, 3 is a fixed bolt, and 4 is a heat treatment assembly.
The arrangement of the air guiding openings follows the following principles: 1. the arrangement of the air guide opening is symmetrical on two sides according to a central line; 2. the total area of the air guide opening occupies 25 to 35 percent of the area of the plane; 3. the arrangement of the air guide port must avoid the position where the brazing material is laid by at least 15mm; 4. an air guide port is required to be arranged at the elbow of the measuring pipe; 5. the center is provided with an air guide opening; 6. the bottom edge is provided with a wind guide opening; fig. 5 shows a schematic view of arranging the air guide opening in the embodiment of the invention.
(5) After the air guide port is arranged, the mixture is sent into a vacuum gas quenching furnace for vacuum pumping, and the vacuum degree is kept at 2.0 multiplied by 10 -2 Pa, performing a heat treatment process (see fig. 6):
a: firstly, the temperature is raised to 260 ℃ for 30 min;
b: the application time is 60min, and the temperature is kept at 260 ℃;
c: the application time is 30min, and the temperature is raised to 420 ℃;
d: it is administered for 20min, and maintained at 420 deg.C;
e: the application time is 30min, and the temperature is raised to 600 ℃;
f: the application time is 50min, and the temperature is raised to 1030 ℃;
g: the application time is 25min, and the temperature is kept at 1030 ℃;
h: the application time is 50min, and the temperature is raised to 1170 ℃;
i: it takes 40min, and keeps the temperature at 1170 ℃.
j: introducing low temperature liquid nitrogen, and rapidly cooling to room temperature for 50min.
The heat treatment process is finished, and the vacuum degree is kept at 2.0 multiplied by 10 in the whole process -2 Pa。
The process flow chart of the heat treatment method of the Coriolis mass flowmeter for high-pressure hydrogen provided by the invention is shown in figure 7.
After the heat treatment process is used for treatment, the performance of the flowmeter is greatly improved, the precision of the flowmeter reaches the level of 0.05%, and the repeatability of the flowmeter reaches the level of 0.02%. A set of prototype processed by the heat treatment process is randomly selected for 20:1 range ratio experiment, wherein the flow rate range is (26.5-530) kg/h, detection flow rate points and detection times are set according to JJG1038-2008 Coriolis mass flowmeter measurement verification regulations, the detection flow rate points and the detection times are respectively at qmax, 0.5qmax, 0.2qmax, qmin and qmax, the 5 flow rate points are verified, and each flow rate point is verified for 6 times; the detection precision is 0.04%, and the repeatability is 0.02%; the advanced nature of the heat treatment process is reflected, and the experimental data are shown in the following table 3.
TABLE 3 Experimental data for experiments using the flowmeter after the heat treatment method provided by the present invention
In conclusion, the heat treatment method of the Coriolis mass flowmeter for high-pressure hydrogen provided by the invention has the following beneficial effects:
(1) Selecting HC-22 as a raw material, wherein the nickel content and the nickel equivalent of the HC-22 are far beyond the national standard, and meanwhile, the HC-22 is also a nickel-based single-phase austenitic alloy; the hydrogen embrittlement sensitivity of the material is reduced along with the increase of the nickel content and the nickel equivalent, the hydrogen embrittlement sensitivity of the material is reduced along with the increase of the proportion of austenite in the material, the nickel content of the HC-22 material is more than 50 percent, the nickel equivalent of the HC-22 material is more than 77 percent, and the single-phase austenite composition ensures that the hydrogen embrittlement sensitivity of the material is extremely low, and the hydrogen embrittlement prevention is ensured from the material aspect; meanwhile, the yield strength of HC-22 is 310MPa, the allowable stress is 206MPa, and the allowable stress is far more than 172MPa and 115MPa of 316L, so that the pressure-bearing capacity is ensured, the wall thickness of the pipe is reduced to the maximum extent, the Coriolis effect is improved, and the precision and the repeatability of equipment are improved.
(2) Due to the design of the air guide cover, the low-temperature liquid nitrogen can be selected for rapid cooling in the heat treatment, so that the problems that the brazing is not firm, the welding line is not uniform and the durability and the performance of equipment are reduced due to the fact that the liquid phase brazing material is blown away by the strong wind of the low-temperature liquid nitrogen are avoided; the long-time sensitization temperature section and low production efficiency caused by furnace cooling are avoided; the uneven heating and slow heat dissipation caused by full wrapping are avoided; the wind scooper is innovatively used in the heat treatment process, so that the firmness and uniformity of brazing can be guaranteed to the maximum extent, and the stress removal and solid solution effects of the assembly can be improved to the maximum extent.
(3) The BNi-5 brazing material is selected, so that the heat treatment temperature of 1170 ℃ can be met, meanwhile, the BNi-5 does not contain Fe, contains little C and high Cr, is more suitable for brazing of HC-22, and avoids the increase of hydrogen brittleness sensitivity caused by the formation of martensite in the brazing process.
(4) The innovative heat treatment process flow has the specific functions of temperature gradient setting and time setting:
a: firstly, the use time is 30min, and the temperature is raised to 260 ℃;
b: the application time is 60min, and the temperature is kept at 260 ℃;
the material is heated to 260 ℃ and is kept warm for 1 hour, and the activity of hydrogen is greatly enhanced at the temperature of more than 200 ℃ and the hydrogen can be separated out from the metal material, so that the hydrogen content in the material composition can be reduced to the maximum extent; the hydrogen embrittlement sensitivity of the liquid receiving part is reduced; meanwhile, the arrangement can fully volatilize the adhesive in the brazing material;
c: the application time is 30min, and the temperature is raised to 420 ℃;
d: it is administered for 20min, and maintained at 420 deg.C;
the arrangement of the heat preservation section avoids a sensitization temperature section (450-850 ℃), and meanwhile, the heat preservation section is added and arranged at a proper place, so that the temperature uniformity of the assembly can be improved, and the solid solution effect of heat treatment can be improved;
e: the application time is 30min, and the temperature is raised to 600 ℃;
f: the application time is 50min, and the temperature is raised to 1030 ℃;
g: the application time is 25min, and the temperature is kept at 1030 ℃;
the temperature rising section is arranged in the sensitization temperature interval, and the heat preservation section is not arranged, so that intergranular corrosion is avoided; the temperature is raised to the temperature point and is kept, so that the internal stress of the part can be fully eliminated;
h: the application time is 50min, and the temperature is raised to 1170 ℃;
i: it is administered for 40min, and heat preservation is carried out at 1170 deg.C;
the setting of the temperature point and the setting of the heat preservation time interval 1 can eliminate the residual stress in the material to the maximum extent, improve the consistency of the material, and effectively improve the zero stability of the mass flowmeter, thereby improving the precision of the equipment; 2. the solid solution effect is fully ensured, so that austenite and martensite in a metastable state are completely converted into supersaturated austenite, and the tissue unevenness and the microscopic defects in the material are eliminated; the reduction of stress in the material, the reduction of metastable austenite and martensite, the improvement of the structural uniformity and the reduction of defects can reduce the hydrogen brittleness sensitivity of the material; therefore, the process can reduce the hydrogen brittleness sensitivity of the material to the maximum extent; 3. the melting temperature of the brazing solder is taken into consideration, so that the brazing solder can be melted and infiltrated fully, and firm welding is realized;
j: introducing low temperature liquid nitrogen, rapidly cooling to room temperature, and taking 50min;
the rapid cooling section ensures that the heat treatment assembly is not in a sensitization temperature range, avoids intergranular corrosion, ensures the performance of the material, simultaneously directly draws the material to room temperature, avoids hydrogen from entering the material again in the process, and ensures the dehydrogenation effect of the material to the maximum extent.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A heat treatment method of a Coriolis mass flowmeter for high-pressure hydrogen comprises the following steps:
a) Selecting HC-22 as a liquid receiving material of the Coriolis mass flowmeter; b) Assembling a heat treatment component of the Coriolis mass flowmeter; c) Respectively laying brazing materials BNi-5 on the vibration isolation sheet and the measuring pipe as well as the measuring pipe and the flow divider; d) Installing a wind scooper; e) Sending the mixture into a vacuum gas quenching furnace, vacuumizing, and executing a heat treatment process:
a: firstly, the temperature is raised to 260 ℃ for 30 min;
b: the application time is 60min, and the temperature is kept at 260 ℃;
c: the application time is 30min, and the temperature is raised to 420 ℃;
d: it is administered for 20min, and maintained at 420 deg.C;
e: the application time is 30min, and the temperature is raised to 600 ℃;
f: the application time is 50min, and the temperature is raised to 1030 ℃;
g: the application time is 25min, and the temperature is kept at 1030 ℃;
h: the application time is 50min, and the temperature is raised to 1170 ℃;
i: it is administered for 40min, and heat preservation is carried out at 1170 deg.C;
j: introducing low temperature liquid nitrogen, and rapidly cooling to room temperature for 50min; and finishing the heat treatment of the Coriolis mass flowmeter.
2. The method for heat-treating a high-pressure hydrogen coriolis force mass flowmeter as set forth in claim 1, wherein the ni content of the HC-22 in the step a) is 50% or more and the ni equivalent is 77% or more.
3. The method for heat-treating a coriolis force mass flowmeter for high-pressure hydrogen of claim 1 wherein said assembled components of step B) comprise:
the coil magnet support comprises a support plate, a flow divider, a measuring pipe, a vibration isolation sheet, a brazing material and a coil magnet support; wherein, the measuring pipe is respectively contacted with the flow divider and the vibration isolation sheet.
4. The method for heat-treating a coriolis force mass flowmeter for high-pressure hydrogen as set forth in claim 1, wherein said BNi-5 in said step C) contains no Fe, 0.06 or less in C content, and 18.5 to 19.5% in Cr content.
5. The method for heat-treating a coriolis force mass flowmeter for high-pressure hydrogen as set forth in claim 1, wherein said applying of said brazing material in step C) is required to form an application width of 1mm to 1.5mm, and is required to apply a full weld of 360 °.
6. The method as set forth in claim 1, wherein the material of the wind scooper in step D) is 304 stainless steel.
7. The heat treatment method of the coriolis force mass flowmeter for high-pressure hydrogen gas according to claim 1, characterized in that the process of installing the wind scooper in step D) is specifically:
the heat treatment components of each set of Coriolis mass flowmeter are provided with the air guide covers, then the air guide covers are fixed on the fixed bottom plate, and the fixed bottom plate can be provided with a plurality of sets of heat treatment components at the same time.
8. The heat treatment method of the coriolis force mass flowmeter for high-pressure hydrogen as set forth in claim 1, wherein the air guide ports of said air guide cover in step D) are arranged in accordance with the following principle:
(1) The arrangement of the air guide opening is symmetrical on two sides according to a central line; (2) The total area of the air guide opening occupies 25 to 35 percent of the area of the plane; (3) The arrangement of the air guide port must avoid the position where the brazing material is laid by at least 15mm; (4) an air guide port is required to be arranged at the elbow of the measuring pipe; (5) an air guide opening is required to be arranged in the center; and (6) the bottom edge is provided with a wind guide opening.
9. The method for heat-treating a coriolis force mass flowmeter for high-pressure hydrogen as set forth in claim 1, wherein a degree of vacuum of 1 x 10 is applied to said evacuation in step E) -2 Pa～3×10 -2 Pa。
10. The heat treatment method of a coriolis force mass flowmeter for high-pressure hydrogen as set forth in claim 1, wherein the degree of vacuum is maintained at 1 x 10 throughout the heat treatment process in step E) -2 Pa～3×10 -2 Pa。
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2222466A1 (en) * | 1997-11-25 | 1999-05-25 | Jacques Montagnon | Nickel-chrome-iron-based alloy compound |
| US20030049155A1 (en) * | 2001-06-28 | 2003-03-13 | Pike Lee M. | Two step aging treatment for Ni-Cr-Mo alloys |
| JP2008144237A (en) * | 2006-12-12 | 2008-06-26 | Hitachi Ltd | gamma' PHASE STRENGTHENED FeNi BASED ALLOY |
| WO2016131702A1 (en) * | 2015-02-17 | 2016-08-25 | Höganäs Ab (Publ) | Nickel based alloy with high melting range suitable for brazing super austenitic steel |
| JP2018104793A (en) * | 2016-12-28 | 2018-07-05 | 新日鐵住金株式会社 | Ni steel for liquid hydrogen |
| TW201901809A (en) * | 2017-05-17 | 2019-01-01 | 日商斯庫林集團股份有限公司 | Heat treatment device and heat treatment method |
| CN113637929A (en) * | 2021-07-14 | 2021-11-12 | 北京科技大学 | Heat treatment process for improving room temperature strength of nickel-based high-temperature alloy |
| CN113681103A (en) * | 2021-07-16 | 2021-11-23 | 北京科技大学 | Multi-brazing and heat treatment process for maintaining strength of nickel-based high-temperature alloy |
| CN114107630A (en) * | 2021-11-19 | 2022-03-01 | 北京科技大学 | Heat treatment method for improving hydrogen embrittlement resistance of martensitic stainless steel, stainless steel and application |
-
2022
- 2022-11-21 CN CN202211455235.0A patent/CN115852280B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2222466A1 (en) * | 1997-11-25 | 1999-05-25 | Jacques Montagnon | Nickel-chrome-iron-based alloy compound |
| US20030049155A1 (en) * | 2001-06-28 | 2003-03-13 | Pike Lee M. | Two step aging treatment for Ni-Cr-Mo alloys |
| JP2008144237A (en) * | 2006-12-12 | 2008-06-26 | Hitachi Ltd | gamma' PHASE STRENGTHENED FeNi BASED ALLOY |
| WO2016131702A1 (en) * | 2015-02-17 | 2016-08-25 | Höganäs Ab (Publ) | Nickel based alloy with high melting range suitable for brazing super austenitic steel |
| JP2018104793A (en) * | 2016-12-28 | 2018-07-05 | 新日鐵住金株式会社 | Ni steel for liquid hydrogen |
| TW201901809A (en) * | 2017-05-17 | 2019-01-01 | 日商斯庫林集團股份有限公司 | Heat treatment device and heat treatment method |
| CN113637929A (en) * | 2021-07-14 | 2021-11-12 | 北京科技大学 | Heat treatment process for improving room temperature strength of nickel-based high-temperature alloy |
| CN113681103A (en) * | 2021-07-16 | 2021-11-23 | 北京科技大学 | Multi-brazing and heat treatment process for maintaining strength of nickel-based high-temperature alloy |
| CN114107630A (en) * | 2021-11-19 | 2022-03-01 | 北京科技大学 | Heat treatment method for improving hydrogen embrittlement resistance of martensitic stainless steel, stainless steel and application |
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