CN109666865A - Alloy and its preparation method and application with anticoking capability - Google Patents
Alloy and its preparation method and application with anticoking capability Download PDFInfo
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- CN109666865A CN109666865A CN201710963926.4A CN201710963926A CN109666865A CN 109666865 A CN109666865 A CN 109666865A CN 201710963926 A CN201710963926 A CN 201710963926A CN 109666865 A CN109666865 A CN 109666865A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/005—Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/22—Ferrous alloys, e.g. steel alloys containing chromium with molybdenum or tungsten
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/26—Ferrous alloys, e.g. steel alloys containing chromium with niobium or tantalum
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/28—Ferrous alloys, e.g. steel alloys containing chromium with titanium or zirconium
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention relates to field of alloy material, the alloy and its preparation method and application with anticoking capability is disclosed.The surface roughness of alloy is 0.2-10 μm, and on the basis of the total weight of alloy, the alloy contains Fe:96.5-99.3wt%；Cr:0-1.5wt%；Mn:0.3-0.8wt%；Si:0.1-0.4wt%；C:0.1-0.2wt%；Mo:0.2-0.6wt%；Microelement: 0-1wt%；The microelement is at least one of Al, Nb, Ti, W and rare earth element.The invention also discloses a kind of methods for preparing the alloy, including alloy raw material is carried out melting, obtain alloy after cooling.The invention also discloses above-mentioned alloys to apply in chemical process hydrocarbon device.Alloy material of the invention has the anticoking capability significantly improved.
Description
Technical field
The present invention relates to field of alloy material, and in particular, to alloy and preparation method thereof with anticoking capability and
Using.
Background technique
In ethylene cracker, quenching boiler, which is responsible for, to be cooled down cracking gas rapidly to terminate secondary response and utilize and split
The heat vented one's spleen generates the double action of high steam.Coking is that a protrusion in quenching boiler operational process is asked in heat exchanger tube
Topic.Especially, when cracking stock is mink cell focus (heavy AGO, VGO etc.), the coking of quenching boiler is more serious, and constitutes
The main restricting factor of cracker operation cycle.To guarantee the unimpeded of logistics, it has to so that pyrolysis furnace is irregularly stopped, with right
Quenching boiler carries out coke cleaning (mechanical or hydraulic decoking).This not only affects the utilization of capacity of pyrolysis furnace, and makes making for pyrolysis furnace
Use the lost of life.In addition, the coking of quenching boiler, increases its resistance drop, the hydrocarbon in the pressure rise radiating furnace tube of upstream point
Pressure rises, so that cracking furnace pipe be made to decline the selectivity of alkene, the yield of alkene is reduced；It is led again because burnt dirty in quenching boiler
Hot coefficient is very small, and the rising of quenching boiler outlet temperature not only reduces the yield of high-temperature position thermal energy, but also increases simultaneously
The thermic load for having added oil wash system brings difficulty to the balancing run of oil wash system.Therefore, how to inhibit or slow down quenching boiler
Coking just at a project in the urgent need to address.
US20030183248A1 discloses a kind of method for accelerating to burn reaction, i.e., to quenching boiler in burning process
Injection includes K on a small quantity2CrO4And K2Cr2O7Aqueous solution Deng I A or II A race chromate or bichromate and carbonate etc. is compound clear
Burnt promotor, not only accelerates coke-burning rate, also extends the boiler operatiopn period, because burning cleaner, residual coke layer change
It is thin.But the compound coke cleaning promotor used has strong oxidizing property, long-time service is larger to the corrosion of quenching boiler, moreover,
Additionally introducing compound coke cleaning promotor makes burning process more complicated, and K+Easily corrode boiler tube.
Summary of the invention
The purpose of the invention is to overcome the problems, such as the presence of the prior art, a kind of conjunction with anticoking capability is provided
Gold and its preparation method and application.
To achieve the goals above, one aspect of the present invention provides a kind of alloy with anticoking capability, the alloy
Surface roughness be 0.2-10 μm, on the basis of the total weight of alloy, the alloy contains following element:
Fe:96.5-99.3wt%；
Cr:0-1.5wt%；
Mn:0.3-0.8wt%；
Si:0.1-0.4wt%；
C:0.1-0.2wt%；
Mo:0.2-0.6wt%；
Microelement: 0-1wt%；
Wherein, the microelement is at least one of Al, Nb, Ti, W and rare earth element.
Second aspect of the present invention provides a kind of method for preparing the alloy, and this method includes melting alloy raw material
Refining obtains alloy after cooling.
Third aspect present invention provides above-mentioned alloy and applies in chemical process hydrocarbon device.
Through the above technical solutions, alloy material of the invention has the anticoking capability significantly improved, the present invention is used
The quenching boiler of alloy material preparation boiler itself also can effectively be prolonged with the coke cleaning reagent of corrosiveness without introducing
Long periods of time in order simplifies coke cleaning technique.
Specific embodiment
The present invention provides a kind of alloy with anticoking capability, the surface roughness of the alloy is 0.2-10 μm
(preferably 0.4-8 μm or 0.4-6.3 μm), on the basis of the total weight of alloy, the alloy contains following element:
Fe:96.5-99.3wt%；
Cr:0-1.5wt%；
Mn:0.3-0.8wt%；
Si:0.1-0.4wt%；
C:0.1-0.2wt%；
Mo:0.2-0.6wt%；
Microelement: 0-1wt%；
Wherein, the microelement is at least one of Al, Nb, Ti, W and rare earth element.Wherein, the rough surface
Degree with profile arithmetic average error Ra characterize, can be measured by comparing method, namely under the microscope by sample to be tested with indicate
Determine that the template of Ra numerical value relatively determines the Ra of sample to be tested；It can also be surveyed by tracer method by surfagauge
Obtain Ra.
Alloy according to the present invention can optionally contain Cr, this can be realized as long as controlling its dosage within the above range
The purpose of invention, but under preferable case, on the basis of the total weight of alloy, the content of Cr is 0.5-1.3wt%.
Alloy according to the present invention contains Mn, and mesh of the invention can be realized as long as controlling its dosage within the above range
, but under preferable case, on the basis of the total weight of alloy, the content of Mn is 0.45-0.75wt%.
Alloy according to the present invention contains Si, and mesh of the invention can be realized as long as controlling its dosage within the above range
, but under preferable case, on the basis of the total weight of alloy, the content of Si is 0.15-0.37wt%.
Alloy according to the present invention contains C, as long as control its dosage can be realized the purpose of the present invention within the above range,
But under preferable case, on the basis of the total weight of alloy, the content of C is 0.14-0.2wt%.
Alloy according to the present invention contains Mo, and mesh of the invention can be realized as long as controlling its dosage within the above range
, but under preferable case, on the basis of the total weight of alloy, the content of Mo is 0.21-0.55wt%.
Alloy according to the present invention contains microelement, dosage can control in 1wt% hereinafter, but under preferable case,
The content of microelement is 0.15-0.65wt%.
The main component of alloy according to the present invention is Fe, and content is within the above range or can be according to other elements
Content is calculated, that is, in a kind of special embodiment, alloy of the invention is in addition to containing above-mentioned element, surplus Fe.
The content for controlling each ingredient can further improve the anti-coking of alloy of the invention in above-mentioned preferred scope
Performance.
In the present invention, the rare earth element can be the common various rare earth elements in this field, as La, Ce, Pr, Nd, Pm,
At least one of Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y and Sc.A preferred embodiment of the invention,
The rare earth element is Y and/or Ce.
A kind of preferred embodiment according to the present invention, the microelement is Y, and the content of Y is 0.17-
0.19wt%.
The method provided by the invention for preparing the alloy includes that alloy raw material is carried out to melting, obtains alloy after cooling,
If its surface roughness not in aforementioned range of the invention, is handled it by additional mach mode.
Wherein, the composition of the alloy raw material is so that obtained alloy is formed with foregoing element.Select the group of alloy raw material
At to the method for obtaining the alloy with expected element composition and surface roughness be it is known in those skilled in the art, this
Text is no longer described in detail.
In the present invention, the method also includes casting obtained alloy, to obtain the alloy material of specific shape.
In the present invention, the method can also include being surface-treated to the alloy with particular surface roughness, with
Further increase its anticoking capability.According to the preferred embodiment of the present invention, using sulfur compound steam, vapor and reduction
The mixed gas of property gas is surface-treated alloy.Wish to illustrate, the element of alloy involved in the present invention
Element before composition is surface treatment forms.
In the preferred embodiment of the present invention, surface treatment is carried out to make alloy table to alloy using the mixed gas
The element in face is oxidized or vulcanizes, and is particularly conducive to improve the anticoking capability of alloy.To the content of each component in mixed gas
It is not particularly limited, but under preferable case, the volume ratio of sulphur vapor, vapor and reducibility gas is 0.1-3:0.1-
1000:1000, more preferably 0.2-2:50-1000:1000.In the present invention, in the absence of explanation to the contrary, the body of gas
Product refers to the volume under the status of criterion (0 DEG C, 101kPa).
In the preferred embodiment of the present invention, the type of the sulfide in the sulphur vapor is not limited particularly
It is fixed, inorganic sulphide and/or organic sulfur compound that can be common for this field, for example, the sulfide in the sulphur vapor
It can be H2S、SO2、SF6、COS、CS2、CH3SH、CH3CH2SH、CH3SCH3、CH3CH2SCH2CH3、CH3S-SCH3And CH3CH2S-
SCH2CH3At least one of.
In the preferred embodiment of the present invention, the reducibility gas can (partial pressure of oxygen be for various low oxygen partial pressure gases
Refer to pressure shared by oxygen present in gas), namely be difficult to decompose the gas for generating oxygen, be usually free of going back for oxygen element
Originality gas, preferably H2、CH4、C2H6、C3H8、C2H4、C3H6、C2H2、C3H4And NH3At least one of.
In the preferred embodiment of the present invention, the anti-of alloy can effectively improve in the higher situation of partial pressure of oxygen
Coking behavior.Therefore, the partial pressure of oxygen of the mixed gas can be greater than 10-16Pa, preferably 1.2 × 10-16Pa to 10-9Pa。
In the preferred embodiment of the present invention, the mixed gas can also contain non-active gas, it is preferable that described non-
The volume ratio of active gases and reducibility gas is 1-100:100.The non-active gas can be not susceptible to chemistry to be various
The gas of reaction, such as nitrogen and/or inert gas.The non-active gas is preferably at least one in nitrogen, argon gas and helium
Kind.
In the preferred embodiment of the present invention, to the acquisition pattern of the mixed gas, there is no particular limitation, such as can
Above-mentioned gas directly to be mixed to acquisition, reducibility gas (and optional non-active gas) can also be dissolved in by containing
The aqueous solution of the sulfide of water obtains, and reducibility gas (and optional non-active gas) can also be passed sequentially through liquid condition
Sulfide and water obtain.
In the preferred embodiment of the present invention, the condition of surface treatment is not required particularly.Preferably, mixed gas
The pressure of offer is 0.05-0.2MPa.Preferably, the temperature of the surface treatment is 600-1000 DEG C.Preferably, the surface
The time of processing is 5-100h, more preferably 10-60h.In the present invention, the pressure refers both to gauge pressure.
Alloy made from alloy or the method for the present invention of the invention has preferable anticoking capability, can replace existing material
Material prepares the devices such as quenching boiler, so as to improve the anti-coking of quenching boiler.Therefore, the present invention also provides foregoing
Alloy is applied in chemical process hydrocarbon device, especially the chemical process of reaction temperature higher (such as 450-750 DEG C)
Application in hydrocarbon device (such as cracking furnace pipe).
The present invention will be described in detail by way of examples below.
In following embodiment, surface roughness is by tracer method by surfagauge；Used (industry)
The physico-chemical parameter of naphtha is as shown in table 1:
Table 1
Embodiment 1-5 and comparative example 1-2
Alloyage raw material carries out melting, and the temperature of melting is 1500 DEG C, and cooling obtains alloy material, by gained alloy material
Expect that mechanical process at 5mm × 5mm × 3mm test piece with different surface roughness (Ra, μm, as shown in table 2), claims
Weight is formed with the element of X-ray energy Dispersive Spectroscopy (EDS) analysis test piece, the results are shown in Table 2 (on the basis of the total amount of alloy, with
Weight percent meter, surplus Fe).
Test piece coking experiment having a size ofBoiler tube in carry out: naphtha and water steam
Gas after 600 DEG C of preheater preheating, adopt by the lab scale cracking furnace tube for being 800mm into length, the length range of 0-600mm
850 DEG C are heated to resistance wire, and keeps constant temperature, is not heated in the length range of 600-800mm.Test piece hangs on 750mm's
Position (similar to the quenching boiler of industrial crack device), herein about 580 DEG C of temperature.Naphtha feed 100g/h, water-oil factor
0.5, pyrolysis time 4 hours, the physical property of used naphtha was as shown in table 1.
After cracking experiment, stop heating and charging, leads to N2Gas shielded is naturally cooling to room temperature.By test piece from boiler tube
Middle taking-up weighs and calculates coking amount (mg/cm2), to investigate the performance that it inhibits coking.Coking amount calculated result is shown in Table 2.
Table 2
The coking amount that can be seen that embodiment 1-5 from the data of table 2 is considerably less than comparative example, it is seen that alloy of the invention
Material has excellent anticoking capability, is particularly suitable as cracking furnace pipe use.
Test case 1-14
(1) alloyage raw material carries out melting, and the temperature of melting is 1500 DEG C, cooling, and mechanical process is different at having
Surface roughness (Ra, μm) 5mm × 5mm × 3mm test piece S1-S7, (element composition and Ra also distinguish analytical element composition
Shown in 1#-7# for table 2), and by its using sulfur compound steam, vapor and reducibility gas mixed gas to alloy into
Row surface treatment, then weighs the material after surface treatment, and carries out coking experiment using method same as described above,
Wherein, the gas used and surface treatment condition etc. are as follows:
S1: 600 DEG C of temperature, mixed gas H2S-H2O-H2-N2(volume ratio=0.2:1000:1000:100, the pressure provided
Power is 0.2MPa), time 10h；
S2: 700 DEG C of temperature, mixed gas SO2-H2O-CH4- Ar (volume ratio=0.64:600:1000:200, the pressure provided
Power is 0.2MPa), time 20h；
S3: 750 DEG C of temperature, mixed gas SF6-H2O-C2H6- He (volume ratio=1.1:400:1000:500, the pressure provided
Power is 0.05MPa), time 30h；
S4: 800 DEG C of temperature, mixed gas COS-H2O-C3H8-C2H4-N2- Ar (volume ratio=1.4:200:500:500:
500:500, the pressure provided are 0.1MPa), time 40h；
S5: 900 DEG C of temperature, mixed gas CS2-H2O-C3H6-C2H2-N2- He (volume ratio=1.8:100:200:800:5:
5, the pressure provided is 0.1MPa), time 50h；
S6: 1000 DEG C of temperature, mixed gas CH3SH-H2O-C3H4-NH3- Ar-He (volume ratio=2:50:500:500:5:
45, the pressure provided is 0.1MPa), time 60h；
S7: the gas used and surface treatment condition etc. are identical as S5；
The coking amount of S1-S7 is as shown in table 3.
(2) according to the method preparation test piece D2.1-D2.7 of step (1), (element composition and Ra are also respectively the 1#-7# of table 2
It is shown) and coking experiment is carried out, unlike, mixed gas is free of sulphur vapor.Coking amount is as shown in table 3.
Table 3
| Element composition | Test piece number | Coking amount | Test piece number | Coking amount |
| 1# | D2.1 | 35.7 | S1 | 24.8 |
| 2# | D2.2 | 23.5 | S2 | 20.2 |
| 3# | D2.3 | 17.6 | S3 | 14.1 |
| 4# | D2.4 | 10 | S4 | 8.3 |
| 5# | D2.5 | 11.3 | S5 | 8.6 |
| 6# | D2.6 | 14.1 | S6 | 9.9 |
| 7# | D2.7 | 36.2 | S7 | 26.9 |
The coking amount that can be seen that the modified alloy that the preferred process of the present invention obtains from the data of table 3 is considerably less than surface
The method of processing mode not in the preferred range, it is seen that alloy material can be made by preferred surface treatment method
With superior anticoking capability.Particularly, the element composition of S1 and S7 not within the scope of the invention, uses and S2-
The similar method of S6 is surface-treated, but the coking amount of the S2-S6 of element composition within the scope of the present invention is lower.
In addition, being shown by further Mechanics Performance Testing, alloy material excellent in mechanical performance of the invention, Neng Gouman
The requirement of sufficient chemical process hydrocarbon device (especially cracking furnace pipe).
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (9)
1. a kind of alloy with anticoking capability, which is characterized in that the surface roughness of the alloy is 0.2-10 μm, to close
On the basis of the total weight of gold, the alloy contains following element:
Fe:96.5-99.3wt%；
Cr:0-1.5wt%；
Mn:0.3-0.8wt%；
Si:0.1-0.4wt%；
C:0.1-0.2wt%；
Mo:0.2-0.6wt%；
Microelement: 0-1wt%；
Wherein, the microelement is at least one of Al, Nb, Ti, W and rare earth element.
2. alloy according to claim 1, wherein on the basis of the total weight of alloy, the alloy contains following element:
Cr:0.5-1.3wt%；
Mn:0.45-0.75wt%；
Si:0.15-0.37wt%；
C:0.14-0.2wt%；
Mo:0.21-0.55wt%；
Microelement: 0.15-0.65wt%；
Surplus is Fe.
3. alloy according to claim 1, wherein the surface roughness of the alloy is 0.4-8 μm.
4. alloy according to claim 1, wherein the surface roughness of the alloy is 0.4-6.3 μm.
5. alloy according to claim 1, wherein the rare earth element is Y and/or Ce.
6. alloy described in any one of -5 according to claim 1, wherein the microelement is Y, and the content of Y is
0.17-0.19wt%.
7. a kind of method for preparing alloy described in any one of claim 1-6, this method include carrying out alloy raw material
Melting obtains alloy after cooling.
8. according to the method described in claim 7, wherein, the method also includes casting obtained alloy.
9. alloy described in any one of claim 1-6 is applied in chemical process hydrocarbon device.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0734196A (en) * | 1993-07-15 | 1995-02-03 | Sumitomo Metal Ind Ltd | Ballast tank excellent in durability |
| CN101379362A (en) * | 2005-12-21 | 2009-03-04 | 埃克森美孚研究工程公司 | Corrosion resistant material for reduced fouling, heat transfer component with improved corrosion and fouling resistance, and method for reducing fouling |
| CN103469083A (en) * | 2013-09-18 | 2013-12-25 | 攀枝花学院 | Heat-resistant cast steel and application thereof |
| CN105200338A (en) * | 2014-05-30 | 2015-12-30 | 中国石油化工股份有限公司 | Anti-coking alloy material and use thereof |
-
2017
- 2017-10-17 CN CN201710963926.4A patent/CN109666865A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0734196A (en) * | 1993-07-15 | 1995-02-03 | Sumitomo Metal Ind Ltd | Ballast tank excellent in durability |
| CN101379362A (en) * | 2005-12-21 | 2009-03-04 | 埃克森美孚研究工程公司 | Corrosion resistant material for reduced fouling, heat transfer component with improved corrosion and fouling resistance, and method for reducing fouling |
| CN103469083A (en) * | 2013-09-18 | 2013-12-25 | 攀枝花学院 | Heat-resistant cast steel and application thereof |
| CN105200338A (en) * | 2014-05-30 | 2015-12-30 | 中国石油化工股份有限公司 | Anti-coking alloy material and use thereof |
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