CN107881393A - A kind of anti-coking alloy material and preparation method thereof and a kind of anti-coking cracking furnace pipe - Google Patents
A kind of anti-coking alloy material and preparation method thereof and a kind of anti-coking cracking furnace pipe Download PDFInfo
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- CN107881393A CN107881393A CN201610868506.3A CN201610868506A CN107881393A CN 107881393 A CN107881393 A CN 107881393A CN 201610868506 A CN201610868506 A CN 201610868506A CN 107881393 A CN107881393 A CN 107881393A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C30/00—Alloys containing less than 50% by weight of each constituent
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G9/14—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils in pipes or coils with or without auxiliary means, e.g. digesters, soaking drums, expansion means
- C10G9/16—Preventing or removing incrustation
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G9/14—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils in pipes or coils with or without auxiliary means, e.g. digesters, soaking drums, expansion means
- C10G9/18—Apparatus
- C10G9/20—Tube furnaces
- C10G9/203—Tube furnaces chemical composition of the tubes
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- 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
- C22C38/04—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
- C22C38/06—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
- C22C38/34—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of 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
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel 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
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/48—Ferrous alloys, e.g. steel alloys containing chromium with nickel 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
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/50—Ferrous alloys, e.g. steel alloys containing chromium with nickel with titanium or zirconium
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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
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/58—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of manganese
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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
- C23C8/06—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 gases
- C23C8/28—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 gases more than one element being applied in one step
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Abstract
The present invention relates to anti-coking field, in particular it relates to a kind of anti-coking alloy material, a kind of method for preparing the anti-coking alloy material and a kind of anti-coking cracking furnace pipe.The anti-coking alloy material includes alloy material matrix and the coat coated on the alloy material matrix surface, contain the metal oxide and metal sulfide of metallic element in the alloy material matrix in the coat, relative to the volume of the coat, the content of the metal oxide is 75.1 85 volume %, and the content of the metal sulfide is 15 24.9 volume %.The anti-coking alloy material of the present invention can effectively suppress coking and the long period can keep anticoking capability.
Description
Technical field
The present invention relates to anti-coking field, in particular it relates to a kind of anti-coking alloy material, one kind prepares anti-coking conjunction
The method of golden material and a kind of anti-coking cracking furnace pipe.
Background technology
In ethylene production, cracking furnace pipe inwall inevitably produces surface coking and metallic matrix carburizing, its
Two kinds of adverse consequences can be caused.On the one hand, coking can cause boiler tube internal diameter to diminish, and pressure drop increase, unit capacity is reduced and led
Wall resistance increase is caused, furnace tube heat transfer coefficient reduces, energy consumption increase.Therefore, pyrolysis furnace generally has to stop every 30-60 days
Production once carries out coke cleaning treatment.This frequently coke cleaning treatment seriously reduces production efficiency, adds production cost.The opposing party
Face, the carbon that tube skin is deposited can be diffused into metallic matrix and form carbide, increase the fragility of material, and and then can cause gold
Belong to powdered.These material damages caused by carburizing can interact with the thermal cycle during coke cleaning treatment, greatly shorten
The life-span of cracking furnace pipe.Therefore, tube coking problem is the problem urgently solved in ethylene production.
In past 50 years, people suppress the coking of crack furnance radiation section furnace tube using various ways.Such as
Change the process conditions (low hydrocarbon partial pressure, short residence time etc.) of hydrocarbon pyrolysis, (hydrogenation, virtue are pre-processed to cracking stock
Hydrocarbon extracting etc.), enhanced heat transfer member (outer ailhead, enhanced heat transfer member etc.) is imported in radiant coil, is added into raw material
Coking inhibitor, these methods improve the Coking of radiant coil to a certain extent.
Furthermore it is also possible to using the method pre-oxidized to cracking furnace pipe, this method is typically by low oxygen partial pressure oxygen
The mode of change obtains manganese picotite MnCr in boiler tube inner surface2O4Protective layer, but its anti-coking performance and unstable, wherein
One major reason is that manganese picotite oxide layer completely can not cover Fe, Ni element of inner surface.Moreover, for stone brain
For oil, diesel oil is the liquid cracking furnaces of raw material, although its coking is also based on catalytic coking, polycondensation coking accounts for always
More than the 50% of coking amount, wherein polycondensation coking completely can will cover oxide-film.Therefore, oxide-film is in liquid cracking furnace pipe
Can only be effective initial stage in boiler tube military service, because oxide-film at this moment is not covered also by polycondensation coking, and when pyrolysis furnace is run to
Middle and later periods, the effect of oxide-film can not play it.
The content of the invention
The purpose of the present invention be the anti-coking alloy material generally existing for overcoming prior art anticoking capability deficiency and/
Or the shortcomings that falling short of anti-coking time, there is provided a kind of anti-coking alloy material, a kind of side for preparing the anti-coking alloy material
Method and a kind of anti-coking cracking furnace pipe.The anti-coking alloy material of the present invention can effectively suppress coking and can be longer
Time keeps anticoking capability.
The coat of existing anti-coking material it is generally desirable to containing manganese picotite oxide as much as possible, but this
The inventor of invention has found that alloy material matrix surface always can not form manganese picotite oxide in some region, because
Can be constantly from the crystal boundary or crystal defect on top layer to table for Cr, Mn element in the cracking furnace pipe matrix alloy in oxidizing process
Face migrate, but crystal boundary and crystal defect distribution and it is uneven, in some crystal boundaries or the less region of crystal defect, Cr,
For Mn elements to the seldom of surface migration, the manganese picotite oxide of formation can not be completely by alloy material matrix surface
Fe, Ni element cover, serious so as to result in this subregion catalytic coking.Thus, it was found by the inventors of the present invention that by
Part sulfide is formed in coat, this partial vulcanization thing is just mainly that Fe, Ni on alloy material base inner surface are formed
FeS and NiS, so as to ensure that alloy material matrix surface substantially all can be capped, so as to significantly reduce pyrolysis furnace
The catalytic coking activity of pipe.
First aspect present invention provides a kind of anti-coking alloy material, and the anti-coking alloy material includes alloy material base
Body and the coat coated on the alloy material matrix surface, metal member in the alloy material matrix is contained in the coat
The metal oxide and metal sulfide of element, relative to the volume of the coat, the content of the metal oxide is 75.1-
85 volume %, the content of the metal sulfide is 15-24.9 volumes %.
Second aspect of the present invention provides a kind of anti-coking cracking furnace pipe, it is characterised in that the anti-coking cracking furnace pipe
Tube wall is made up of the anti-coking alloy material of the present invention, wherein the coat is located at the interior of the tube wall of the anti-coking cracking furnace pipe
Side.
Third aspect present invention provides a kind of method for the anti-coking alloy material for preparing the present invention, it is characterised in that
Methods described includes, and the coat is prepared by the following：At a high temperature of more than 500 DEG C, by coating gas with it is described
The inner surface contact of alloy material matrix reacts to form coat so as to the inner surface in the alloy material matrix, its
In, the coating gas contains sulfide gas, vapor and carrier gas, with the total volume meter of the coating gas, the vulcanization
The content of thing gas is 0.01-0.1 volumes %, and the content of the vapor is 0.001-2 volumes %, and the content of the carrier gas is
97.9-99.989 volume %.
Anti-coking alloy material provided by the invention can effectively suppress coking and the long period can keep resistive connection
Burnt performance.Method technique provided by the invention is simple, and the oxide-film and sulfide film of formation can effectively cover cracking furnace pipe inwall
Fe, Ni element, so as to reduce the coking of its running, extend the cycle of operation of pyrolysis furnace.The anti-coking alloy of the present invention
Material is particularly suited for use on cracking furnace pipe.The coke deposited in cracking furnace pipe inwall can be reduced using the method for the present invention
More than 50% even more than 70%.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The end points of disclosed scope and any value are not limited to the accurate scope or value herein, these scopes or
Value should be understood to comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, respectively
It can be combined with each other between the endpoint value of individual scope and single point value, and individually between point value and obtain one or more
New number range, these number ranges should be considered as specific open herein.
First aspect present invention provides a kind of anti-coking alloy material, and the anti-coking alloy material includes alloy material base
Body and the coat coated on the alloy material matrix surface, metal member in the alloy material matrix is contained in the coat
The metal oxide and metal sulfide of element, relative to the volume of the coat, the content of the metal oxide is 75.1-
85 volume %, the content of the metal sulfide is 15-24.9 volumes %.
The coat of the present invention meets that mentioned component requirement can realize preferable anti-coking effect, it is preferable that relative
In the weight of the coat, the content of the metal oxide is 78-82 volumes %, and the content of the metal sulfide is
18-22 volumes %.
In the present invention, the composition of the metal sulfide in the coat does not limit specifically, is in alloy material
The metal sulfide that contained metal is formed in vulcanization reaction, therefore the metal sulfide in the coat may contain
The sulfide of the metallic element of sulfide can be formed in various alloy materials, such as FeS, NiS, MnS and Cr can be included2S3
In one or more.Preferably, FeS and NiS accounts for more than the 90 weight % of the metal sulfide in coat, more preferably 95 weights
Measure more than %.
In the present invention, the composition of the metal oxide in the coat does not limit specifically, is in alloy material
The metal oxide that contained metal is formed in the oxidation reaction, therefore the metal oxide in the coat may contain
The oxide of the metallic element of oxide can be formed in various alloy materials, such as MnO, Cr can be included2O3、MnxCr3-xO4
(manganese picotite) etc., it is preferable that wherein MnxCr3-xO4More than the 90 weight % of the metal oxide in the coat are accounted for, more
It is preferred that more than 95 weight %；Wherein x is 0.5-2, preferably 1-2, and x value is usually 1,1.5 and 2, i.e. Mn1Cr2O4、
Mn1.5Cr1.5O4And Mn2Cr1O4。
In the present invention, the thickness of the coat can be 0.5-5 μm, preferably 1-4 μm, more preferably 2-3 μm.
In the present invention, the alloy material matrix element composition there is no particular limitation, such as can include Fe,
Cr, Ni, Mn, Si and C and trace element and trace element, it is preferable that wherein Mn and Si weight percentage meets formula
(1), under conditions of the Mn and Si of the present invention constituent content, continuous coating is more readily formed in alloy material matrix surface
Layer, and whole coverings can be ensured as much as possible,
It is highly preferred that Mn and Si weight percentage meets formula (2),
In the present invention, the cracking furnace pipe can be various cracking furnace pipes commonly used in the art, be preferably used for cracking
The cracking furnace pipe of Hydrocarbon Organic.Preferably, the chromium content in the cracking furnace pipe is 13-44 weight %, and nickel element contains
It is 0.2-3 weight % to measure as 16-44 weight %, manganese element content, and silicon content is 0-3 weight %, carbon element content 0-
The total content of 0.75 weight %, trace element and trace element is 0-5 weight %, and the content of ferro element is 0.25-70.8 weights
Measure %；It is highly preferred that the chromium content in the cracking furnace pipe is 30-40 weight %, nickel element content is 30-42 weights
% is measured, manganese element content is 1.6-2 weight %, and silicon content is 1.5-3 weight %, and carbon element content is 0.2-0.6 weights
% is measured, the total content of trace element and trace element is 0-2 weight %, and the content of ferro element is 10.4-36.7 weight %.This hair
The bright trace element for example, at least one of Al, Nb, Ti, W, Mo, La, Ce, Y, Nd, Pr, Gd, Dy, Sm, the trace
Secondary element is, for example, sulphur and/or phosphorus.
Second aspect of the present invention provides a kind of anti-coking cracking furnace pipe, wherein, the tube wall of the anti-coking cracking furnace pipe by
The anti-coking alloy material of the present invention is made, wherein the coat is located at the inner side of the tube wall of the anti-coking cracking furnace pipe.
In the present invention, the anti-coking cracking furnace pipe also include inside the anti-coking cracking furnace pipe and with tube wall inwall
The enhanced heat transfer member to connect.The enhanced heat transfer member can change cracking gas flow regime, primarily serve two effects：(1)
Change the flow regime of coating, the O of trace in gas2And sulfide can be contacted sufficiently with tube wall, the coat of formation
Coverage rate is higher；(2) in cracking process, enhanced heat transfer member by the flow regime of cracking gas after laminar flow becomes turbulent flow, stove
The polycondensation coking of pipe internal surface, which is easy to be cleaved airflow scouring, to be fallen, because polycondensation coking is typically all than more loose coke,
It is weaker in the adhesive force of boiler tube inwall.Therefore, the coke of the boiler tube inwall attachment containing enhanced heat transfer member is still with catalysis
Based on coking, such coat is with regard to that can give full play to its effect.
In the present invention, there is no particular limitation for the enhanced heat transfer member, such as can be twisted sheet.The twisted sheet
Number can be 1-10, the length of each twisted sheet can be 20-30cm.The mounting means of the twisted sheet for example distorts
The axis of piece overlaps with the axis of cracking furnace pipe, and the edge of the twisted sheet connects with the inwall of cracking furnace pipe, so as to close
The inside of golden material matrix is divided into two parts.
Third aspect present invention provides a kind of method for the anti-coking alloy material for preparing the present invention, wherein, the side
Method includes, and the coat is prepared by the following：At a high temperature of more than 500 DEG C, by coating gas and the alloy material
The surface of material matrix is contacted so as to react to form coat on the surface of the alloy material matrix, wherein, the coating
Gas contains sulfide gas, vapor and carrier gas, with the total volume meter of the coating gas, the content of the sulfide gas
For 0.01-0.1 volumes %, the content of the vapor is 0.001-2 volumes %, and the content of the carrier gas is 97.9-99.989
Volume %.
In the present invention, in the presence of the anti-coking alloy material is in the form of anti-coking cracking furnace pipe, methods described
Including the coat is prepared by the following：At a high temperature of more than 500 DEG C, the coating gas is passed through pyrolysis furnace
Pipe, reacted by the inner surface of the coating gas and the cracking furnace pipe so as in the inner surface shape of the cracking furnace pipe
Into coat.
In the present invention, in the coating gas content of sulfide gas and vapor when meeting above range
Preferably coating effect and anti-coking effect are realized, it is in a more preferred case, described with the total volume meter of the coating gas
The content of sulfide gas is 0.02-0.08 volumes %, and the content of the vapor is 0.2-1.8 volumes %, the carrier gas
Content is 98.12-99.78 volumes %；It is further preferred that the content of the sulfide is 0.02-0.04 volumes %, the water
The content of steam is 0.5-1.5 volumes %, and the content of the carrier gas is 98.46-99.48 volumes %.
In the present invention, described sulfide can be gas in itself, itself can also still exist for liquid at room temperature
The carrier gas that can be passed at room temperature or in a heated condition is swept along and entered in gas.Described sulfide can for example select
From H2S、SO2、SF6、COS、CS2、CH3SH、CH3CH2SH、CH3SCH3、CH3CH2SCH2CH3、CH3S-SCH3And CH3CH2S-
SCH2CH3In one or more, preferably H2S、SF6、CH3SH、CH3SCH3And CH3S-SCH3In one or more.
In the present invention, the carrier gas can be the conventional carrier gas in this area, such as can be selected from H2、N2, in Ar and He
One or more, most preferably H2.Because industrial pure above-mentioned gas are costly and more unobtainable, therefore can make
By the use of caused byproduct gas in industrial running as carrier gas, so as to which other impurity gas can also be contained in the carrier gas
Body, the foreign gas for example can be hydrocarbon cracking gas, the hydrocarbon cracking gas such as CH4、C2H6、C3H8、C2H4、C3H6、
C2H2And C3H4In one or more.The foreign gas can account for below the 50 volume % of carrier gas, preferably 40 volume % with
Under, more preferably below 30 volume %.
There is no particular limitation for acquisition pattern of the present invention to the coating gas, such as can be steamed with sulfide gas, water
Gas and carrier gas directly mix acquisition, can also obtain carrier gas by the aqueous solution containing water-soluble sulfide, can be with
Carrier gas is passed sequentially through into the sulfide of liquid condition and water obtains.
The present invention is to using the admixture of gas containing sulfide gas, vapor and low oxygen partial pressure gas to cracking furnace pipe
There is no particular limitation for the condition that inner surface is handled, as long as enabling to form oxide and sulfide in boiler tube inner surface
Coat film, so as to be advantageous to suppress or slow down the coking of cracking furnace pipe, for example, the condition of the processing generally includes to locate
It can be 800-1200 DEG C to manage temperature, and processing time can be 5-200 hours.In addition, although by treatment temperature and processing time
Control can obtain meeting expected oxide and sulfide within the above range, but coverage rate is higher, resistive connection in order to obtain
Burnt better oxide-film and sulfide film, it is preferable that the treatment temperature is 850-1150 DEG C, and the processing time is 10-
100h, more preferably 20-60 hours.
In the present invention, the presence of the carrier gas can substantially reduce the content of vapor, so as to form low oxygen partial pressure
Environment.Low oxygen partial pressure environment is a kind of reproducibility environment, and partial pressure of oxygen therein is relatively low, so the oxidizing process occurred is very slow
Slowly, the coat film in the fine and close oxide of material surface generation and sulfide is advantageous to.The pressure of the low oxygen partial pressure gas can
Think 0-0.3MPa, preferably 0.05-0.2MPa；Partial pressure of oxygen therein can be 1.1 × 10-15~1 × 10-9Pa, it is preferably
1.1×10-15~1 × 10-13Pa.In the present invention, the partial pressure of oxygen refers to shared by oxygen present in the low oxygen partial pressure gas
Pressure, the oxygen in low oxygen partial pressure environment is essentially from oxygenatedchemicals (such as H2O oxygen caused by) decomposing.
When the mixed gas using only vapor and carrier gas carries out high temperature oxidation process to alloy material, inner surface is always
Some region can not form manganese picotite oxide, because Cr in oxidizing process in cracking furnace pipe matrix alloy,
Mn elements can be constantly from the crystal boundary or crystal defect on top layer to surface migration, but crystal boundary and crystal defect distribution are simultaneously uneven
Even, in some crystal boundaries or the less region of crystal defect, Cr, Mn element are sharp to the seldom of surface migration, the manganese chromium of formation
Spar oxide completely can not cover Fe, Ni element on cracking furnace pipe inner surface (because in low oxygen partial pressure condition
Lower Fe, Ni are difficult to be oxidized), which results in this subregion catalytic coking is serious.Also contain in the coating gas of the present invention
Sulfide, Fe, Ni vulcanization generation FeS and NiS that sulfide will can be not covered with, so as to significantly alleviate the knot of cracking furnace pipe
Burnt phenomenon.
Relatively low, higher with the water vapour content coating gas phase of the content of vapor that the method for the present invention uses
Be advantageous to generate the manganese picotite of higher amount than, coating gas used in method of the invention, but temperature in industrial operation
More difficult control, easy temperature runaway, therefore be generally not used for coating online.
The coat that the method for the present invention obtains is due to the ion formed containing substantial amounts of oxygen, sulphur and boiler tube inner surface metal
Key is not allowed easily peelable so as to combine than stronger under the huge souring of cracked gas stream yet.And the coat of the present invention
It is consistent with the main component of matrix alloy therefore very close with the thermal coefficient of expansion of matrix, the caused thermal stress between matrix
It is small, the long-term use of requirement of hydrocarbon cracking boiler tube can be met.
The present invention will be described in detail by way of examples below.
Embodiment 1
The present embodiment is 5 × 5 × 2mm to size, element forms 35Cr45Ni alloy materials lacing film as shown in table 1 and carried out
Experiment.Record initial weight of weighing is carried out to lacing film first.Then weighted metal lacing film is hung in boiler tube, to boiler tube
Inside it is passed through coating gas to be coated lacing film, the CH containing 2 volume % in coating gas4, 1 volume % H2O, 0.02 body
Product % H2S and 96.98 volume %H2, flow velocity 200ml/min, treatment temperature is 950 DEG C, processing time 30h.Coated
The lacing film of completion, is designated as I1.
Embodiment 2
The present embodiment is 5 × 5 × 2mm to size, element forms 35Cr45Ni alloy materials lacing film as shown in table 1 and carried out
Experiment.Record initial weight of weighing is carried out to lacing film first.Then weighted metal lacing film is hung in boiler tube, to boiler tube
Inside it is passed through coating gas to be coated lacing film, 20 volume %C is contained in coating gas3H8, 0.5 volume %H2O, 0.08 body
Product %CH3SH and 79.42 volume %N2, flow velocity 200ml/min, treatment temperature is 1050 DEG C, processing time 40h.Coated
The lacing film of completion, is designated as I2.
Embodiment 3
The present embodiment is 5 × 5 × 2mm to size, element forms 35Cr45Ni alloy materials lacing film as shown in table 1 and carried out
Experiment.Record initial weight of weighing is carried out to lacing film first.Then weighted metal lacing film is hung in boiler tube, to boiler tube
Inside it is passed through coating gas to be coated lacing film, 8 volume %C is contained in coating gas2H4, 1.5 volume %H2O, 0.03 volume %
CS2With 90.47 volume %Ar, flow velocity 200ml/min, treatment temperature is 850 DEG C, processing time 60h.Obtain what coating was completed
Lacing film, it is designated as I3.
Embodiment 4
Carried out according to the method for embodiment 1, except that, different scraping blades as shown in table 1 are formed using element.Most
The cracking furnace pipe that coating is completed is obtained eventually, is designated as I4.
Comparative example 1
Carried out according to the method for embodiment 1, except that, H is not contained in coating gas2Contain in S, i.e. coating gas
2 volume % CH4, 1 volume % H2O and 97 volume % H2.The lacing film that coating is completed is finally given, is designated as D1.
Comparative example 2
Carried out according to the method for embodiment 1, except that, the CH containing 2 volume % in the coating gas4, 3 volume %
H2O, 0.02 volume % H2S and 94.98 volume % H2.The cracking furnace pipe that coating is completed is finally given, is designated as D2.
Table 1
Test case
(1) embodiment 1-4 and comparative example 1-2 are observed respectively under the XL-30 type Flied emission environmental scanning electronic microscopes of FEI Co.
The coat for the cracking furnace pipe I1~I4 and D1~D2 surfaces coating that the coating of gained is completed, metal oxide is in crystalline substance under Electronic Speculum
Palpiform looks, sheet-like morphology is presented in metal sulfide, it is possible thereby to estimate the volume content of metal oxide and metal sulfide, often
The coat of individual boiler tube takes ten visuals field to be estimated, and averages, by the metal oxide of gained and metal sulfide
Volume content accounting is remembered in table 2.
Table 2
| Metal sulfide (%) | Metal oxide (%) | It is not covered with (%) | ||
| Embodiment 1 | I1 | 18 | 82 | 0 |
| Embodiment 2 | I2 | 22 | 78 | 0 |
| Embodiment 3 | I3 | 19 | 81 | 0 |
| Embodiment 4 | I4 | 16 | 80 | 4 |
| Comparative example 1 | D1 | - | 88 | 12 |
| Comparative example 2 | D2 | 31 | 69 | 0 |
(2) coking is tested
Reference examples are set first：Tested using lacing film same as Example 1.Record of weighing is carried out to lacing film first
Initial weight.Then weighted metal lacing film is hung in boiler tube and carries out cracking coking experiment, the mistake of cracking coking experiment
Journey includes：Started to warm up after being passed through He gas shieldeds, being raised to time of 860 DEG C of cracking reaction temperature from starting ambient temperature is
90min.After temperature is raised to cracking temperature, stopping is passed through He gas, while by 2%C2H6+ 98%N2Gas is through 20 DEG C of water-bath saturation waters
Reaction boiler tube is passed through after steam cracking reaction occurs, crack coking reaction time 20h.After cracking coking experiment terminates, stop adding
Heat and charging, lead to He gas shieldeds, are naturally cooling to room temperature.Metal material lacing film is taken out from boiler tube, weighed, by gained weight
Subtract initial weight and coking amount is calculated, the coking amount data are remembered in table 3.
According to the lacing film completed respectively to the coating obtained by embodiment 1-4 and comparative example 1-2 with reference examples identical method
I1~I4 and D1~D2 carries out above-mentioned coking experiment, and the coking amount data of gained are remembered in table 3.
Table 3
| Lacing film | Reference examples | I1 | I2 | I3 | I4 | D1 | D2 |
| Coking amount (g) | 4.7273 | 0.4653 | 0.5269 | 0.4417 | 0.6042 | 1.1280 | 0.4829 |
As can be seen from Table 3, the cracking furnace pipe that the method according to the invention is coated to obtain is first in coking experiment
The coking amount of secondary coking is generally at below 1g (most below 0.55g), and coking amount reduces more than 80% compared with reference examples, card
Bright coat of the invention can effectively suppress tube coking.And the coking amount of the first time coking of comparative example 1 is up to 1.1g,
Far above the coking amount of the present invention, it was demonstrated that the anti-coking of gained boiler tube when not containing the method for sulfide using prior art
Can be far below the present invention；Although the coking amount of comparative example 2 is also less, because water vapour content is higher in coating gas, so as to raw
Into manganese picotite is relatively fewer and testing sulphide to more, it is relatively short so as to the life-span of anti-coking.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.It is further to note that described in above-mentioned embodiment
Each particular technique feature, in the case of reconcilable, can be combined by any suitable means, in order to avoid not
Necessary repetition, the present invention no longer separately illustrate to various combinations of possible ways.In addition, a variety of implementations of the present invention
It can also be combined between mode, as long as it without prejudice to the thought of the present invention, it is public that it should equally be considered as institute of the invention
The content opened.
Claims (11)
1. a kind of anti-coking alloy material, it is characterised in that the anti-coking alloy material includes alloy material matrix and is coated on
The coat of the alloy material matrix surface, the metal oxygen of metallic element in the alloy material matrix is contained in the coat
Compound and metal sulfide, relative to the volume of the coat, the content of the metal oxide is 75.1-85 volume %,
The content of the metal sulfide is 15-24.9 volumes %.
2. anti-coking alloy material according to claim 1, wherein, the metal sulfide in the coat include FeS,
NiS, MnS and Cr2S3In one or more.
3. anti-coking alloy material according to claim 1 or 2, wherein, contain in the metal oxide in the coat
There is Mn more than 90 weight %xCr3-xO4, x 0.5-2.
4. anti-coking alloy material according to claim 1, wherein, the element composition of the alloy material matrix includes
Fe, Cr, Ni, Mn, Si and C, wherein Mn and Si weight percentage meet formula (1),
Preferably, Mn and Si weight percentage meets formula (2),
5. the anti-coking alloy material according to claim 1 or 4, wherein, the chromium content in the alloy material is
13-44 weight %, nickel element content are 16-44 weight %, and manganese element content is 0.2-3 weight %, and silicon content is 0-3 weights
% is measured, carbon element content is 0-0.75 weight %, and the total content of trace element and trace element is 0-5 weight %, ferro element
Content is 0.25-70.8 weight %；The trace element is at least one of niobium, titanium, tungsten, aluminium and rare earth, and the trace is first
Element is sulphur and/or phosphorus.
6. a kind of anti-coking cracking furnace pipe, it is characterised in that the tube wall of the anti-coking cracking furnace pipe is by any in claim 1-5
Anti-coking alloy material described in one is made, wherein the coat is located at the inner side of the tube wall of the anti-coking cracking furnace pipe.
7. anti-coking cracking furnace pipe according to claim 6, wherein, the anti-coking cracking furnace pipe also includes being located at resistive connection
The enhanced heat transfer member to connect inside burnt cracking furnace pipe and with tube wall inwall；
Preferably, the enhanced heat transfer member is twisted sheet.
A kind of 8. method for preparing the anti-coking alloy material in claim 1-5 described in any one, it is characterised in that described
Method includes, and the coat is prepared by the following：At a high temperature of more than 500 DEG C, by coating gas and the alloy
The surface of material matrix is contacted so as to react to form coat on the surface of the alloy material matrix, wherein, the painting
Cover gas and contain sulfide gas, vapor and carrier gas, with the total volume meter of the coating gas, the sulfide gas contains
Measure as 0.01-0.1 volumes %, the content of the vapor is 0.001-2 volumes %, and the content of the carrier gas is 97.9-
99.989 volume %.
9. the method according to claim 11, wherein, with the total volume meter of the coating gas, the sulfide gas
Content is 0.02-0.08 volumes %, and the content of the vapor is 0.2-1.8 volumes %, and the content of the carrier gas is 98.12-
99.78 volume %.
10. according to the method for claim 8, wherein, the partial pressure of oxygen in the coating gas is 1.1 × 10-13~1 × 10- 9Pa。
11. anti-coking alloy material according to claim 8, wherein, the sulfide gas is selected from H2S、SO2、SF6、
COS、CS2、CH3SH、CH3CH2SH、CH3SCH3、CH3CH2SCH2CH3、CH3S-SCH3And CH3CH2S-SCH2CH3In one kind or
It is a variety of, it is preferably selected from H2S、SF6、CH3SH、CH3SCH3And CH3S-SCH3In one or more；
Preferably, the carrier gas is selected from H2、N2, one or more in Ar and He.
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| CN112725722A (en) * | 2019-10-28 | 2021-04-30 | 中国石油化工股份有限公司 | Method for treating inner surface of quenching boiler tube |
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