CN106554797A - A kind of processing method of pyrolysis furnace with nichrome boiler tube - Google Patents
A kind of processing method of pyrolysis furnace with nichrome boiler tube Download PDFInfo
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Abstract
The present invention relates to pyrolysis furnace nichrome boiler tube field, discloses a kind of processing method of pyrolysis furnace nichrome boiler tube, the method includes：Under low oxygen partial pressure gas atmosphere, nichrome boiler tube is warming up to into 600-1100 DEG C with the programming rate less than 150 DEG C/h, and is incubated 5-100 hours；Wherein, enhanced heat transfer member is provided with the nichrome boiler tube.By using the pyrolysis furnace nichrome boiler tube that the inventive method process is obtained, can significantly extend the service cycle of pyrolysis furnace.
Description
Technical field
The present invention relates to a kind of processing method of pyrolysis furnace with nichrome boiler tube.
Background technology
Ethene is one of most important basic material of petroleum chemical industry.The method of ethene is produced at present to manage
Based on formula stove cracking technique, worldwide it is widely applied.But in the production process of ethene
In unavoidable difficult problem be cracker under arms during coking and carburizing.In cracking process
In coking boiler tube internal diameter can be made to diminish, tube drop increase, shorten pyrolysis furnace the cycle of operation；Work as pipe
When wall temperature reaches tolerance limit or pressure drop reaches to a certain degree, blowing out is needed to carry out coke cleaning operation.In boiler tube
Wall coking hinders being normally carried out for cracking reaction, affects yield of ethene, reduces production efficiency, and high temperature
Easily promote down boiler tube inwall carburizing, cause furnace tube material performance to weaken.
At present, it is the elevated temperature strength that ensures ethylene cracking tube, crack furnance radiation section furnace tube is usually nickel chromium triangle
Compo pipe, material used are mainly made up of elements such as Fe, Cr, Ni, simultaneously containing Mn, Si, Al,
The trace elements such as Nb, Ti, W, Mo.There are some researches show, at high temperature, Fe, Ni element is to carbon
Coking of the hydrogen compound on FeCrNi alloy cracking furnace pipes surface has notable catalytic action.In addition, compared with
The hydrocarbon raw material of weight is also accompanied by substantial amounts of Free radical coke and polycondensation coking in cracking process.Existing skill
In art, in order to reduce catalytic coking, researcher is attempted using multiple technologies in cracking furnace pipe inner wall surface system
Standby inert coatings, reduce hydro carbons contact with cracking furnace pipe inner surface Fe, Ni active component.
Canadian NOVA chemical companies disclose and a series of process cracking furnace pipe under low oxygen partial pressure atmosphere
Inner surface obtains the patent of chromium galaxite oxide-film, including US5630887, US6436202,
US6824883, US7156979, US7488392 etc..Open material shows, the technology with ethane,
The lighter hydrocarbons such as propane illustrate good suppression coking effect for the gas pyrolysis furnace of raw material, but former in liquid
In material cracking process, anti-coking effect is poor.Because the coking of gas pyrolysis furnace is based on catalytic coking, oxygen
Change film Fe, Ni element in boiler tube with catalytic coking activity can be isolated with hydro carbons coking source.And it is right
For the liquid cracking furnace with naphtha, diesel oil etc. as raw material, although its coking is also with catalytic coking
Based on, but polycondensation coking accounts for more than the 50% of total coking amount, and wherein polycondensation coking can completely by oxidation
Film is covered.Therefore, oxide-film is only on active service the initial stage effectively in boiler tube in liquid cracking furnace pipe, because at this moment
Oxide-film also do not covered by polycondensation coking, and work as pyrolysis furnace and run to the middle and later periods, oxide-film then can not
Play its effect.
The content of the invention
In order to solve produced problem in prior art, it is an object of the invention to provide one kind makes pyrolysis furnace
Processing method of the pyrolysis furnace that service cycle significantly extends with nichrome boiler tube.
The invention provides a kind of processing method of pyrolysis furnace with nichrome boiler tube, wherein, the method bag
Include：Under low oxygen partial pressure gas atmosphere, to be less than the programming rate of 150 DEG C/h by nichrome boiler tube liter
Temperature is to 600-1100 DEG C, and is incubated 5-100 hours；Wherein, it is provided with the nichrome boiler tube strong
Change heat transfer member.
The method according to the invention, by nichrome boiler tube is processed under low oxygen partial pressure gas atmosphere,
Its inner surface forms the inertia diaphragm with high thermal stability, suppresses or slow down catalytic coking phenomenon.
Meanwhile, enhanced heat transfer member is added inside boiler tube, changes fluid flow state, improve the coefficient of heat conduction,
Reduce Free radical coke and polycondensation coking.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Specific embodiment
Hereinafter the specific embodiment of the present invention is described in detail.It should be appreciated that this place is retouched
The specific embodiment stated is merely to illustrate and explains the present invention, is not limited to the present invention.
The processing method of the pyrolysis furnace nichrome boiler tube that the present invention is provided includes：In low oxygen partial pressure gas
Under atmosphere, nichrome boiler tube is warming up to into 600-1100 DEG C with the programming rate less than 150 DEG C/h, and
Insulation 5-100 hours；Wherein, enhanced heat transfer member is provided with the nichrome boiler tube.
According to the present invention, gently insulation is provided with enhanced heat transfer member in nichrome boiler tube to above-mentioned liter
Under the conditions of carry out.In low oxygen partial pressure gas treating process, by the presence of the enhanced heat transfer member
The gentle isothermal holding of above-mentioned liter is carried out, the flow regime of low oxygen partial pressure gas, low oxygen partial pressure gas is changed
The O of middle trace2Can be fully contacted with tube wall, make tube wall intact oxidised, the oxide-film of formation is covered
Rate is higher；In contrast, and carrying out low oxygen partial pressure gas treatment to the boiler tube without enhanced heat transfer member
When, gas is contacted with tube wall with laminar condition, the O in the middle of air-flow2Substantially it is not engaged in the oxygen of tube wall
Change reaction, tube wall can not be intact oxidised, so the oxide-film coverage rate for being formed is than relatively low.In addition, logical
The enhanced heat transfer member is crossed, in cracking process, enhanced heat transfer member will be close to the flowing of tube wall cracking gas
State becomes after turbulent flow from laminar flow, and the polycondensation coking of boiler tube inner surface is easy to cleaved airflow scouring and falls,
Because polycondensation coking is usually than more loose coke, weaker in the adhesive force of boiler tube inwall.Therefore,
Still based on catalytic coking, such hypoxemia divides the coke of the attachment of the boiler tube inwall containing enhanced heat transfer member
Swaging into oxide-film can just give full play to its effect, so as to significantly extend pyrolysis furnace service cycle.
In the present invention, as long as above-mentioned purpose can be reached as above-mentioned enhanced heat transfer member, for example
Can be at least one in twisted sheet, inner rib plate and inner fin.
In the present invention, the pyrolysis furnace nichrome boiler tube for being provided with enhanced heat transfer member can be by this
The conventional method in field is obtained.For example, pyrolysis furnace nichrome boiler tube generally adopts spun casting mode
Casting is formed, and the boiler tube for carrying enhanced heat transfer member in pipe then has different form processings, for example：Pipe
The interior boiler tube with twisted sheet or inner fin component is generally obtained using static casting mode block cast；And in managing
Boiler tube with internal-rib sheet element is by being formed in boiler tube interior welds fin.According to the length of boiler tube
And the difference of caliber equal-specification, enhanced heat transfer member pipe can be distributed in the difference of whole boiler tube with a determining deviation
Tube side.
In addition, the pyrolysis furnace nichrome boiler tube for being provided with enhanced heat transfer member can also be commercially available,
The plum tube (for the pipe of inner fin is provided with pipe) of such as Kellogg companies, the MERT of Kubota
The twisted slice tube of pipe (for the pipe of inner rib plate is provided with pipe) and Sinopec is (to be provided with torsion in pipe
The pipe of knee-piece) etc..
In the present invention, the low oxygen partial pressure gas atmosphere refers to a kind of reducing atmosphere, oxygen therein
Pressure is relatively low, so the oxidizing process for occurring is slowly, generates fine and close oxide-film beneficial in material surface.
The partial pressure of oxygen refers to the pressure present in atmosphere shared by oxygen, under low oxygen partial pressure atmosphere, gas
Oxygen in atmosphere is essentially from oxygenatedchemicals (such as H2O) decompose the oxygen for producing.
In the present invention, the low oxygen partial pressure gas is preferably water vapour (H2O) and selected from CO2、CO、
CH4、C2H6、C3H8、NH3、H2、N2, at least one in Ar and He；Or be water vapour
With at least one in air or cracking gas.
Preferably, the percentage by volume that water vapour accounts for low oxygen partial pressure gas is less than 7.5%；It is highly preferred that
It is 2-7.5%, more preferably 2-6% that water vapour accounts for the percentage by volume of low oxygen partial pressure gas.
Can preferably enumerate as above-mentioned low oxygen partial pressure gas：Water vapour and CH4Admixture of gas, water steam
Vapour and CO2Admixture of gas, water vapour and CO admixture of gas or water vapour and H2Gas
Mixture.
According to the present invention, need to be warming up to nichrome boiler tube with the programming rate less than 150 DEG C/h
600-1100 DEG C, and it is incubated 5-100 hours；In the case of preferred, the programming rate is 100 DEG C/h
Hereinafter, temperature retention time is 10-60 hours；In the case of preferred, the programming rate is 30-100 DEG C
/ h, temperature retention time are 15-50 hours.When the intensification being heat-treated in low oxygen partial pressure gas atmosphere processing procedure
When speed is 150 DEG C/more than h, as the heated fast expansion of boiler tube matrix is hardly formed tube skin
Stable oxide-film, and the oxide-film coverage rate that formed is relatively low and easily peels off.
Controlled within the above range by the condition for being gently incubated above-mentioned liter, can be former in boiler tube inner surface
The anti-coking of position formation, impervious carbon protective film, not only coverage rate is high, and is firmly combined with boiler tube matrix.
According to the present invention, the temperature that nichrome boiler tube is heated up is preferably 800-1000 DEG C.
According to the present invention, boiler tube matrix can adopt the common nichrome boiler tube of prior art, with weight hundred
Fraction meter, the boiler tube matrix composition include：Chromium 12-50%, nickel 20-50%, manganese 0.2-3%, silicon 0-3%,
The trace element of carbon 0-0.75%, 0-5% and trace element, balance of iron, the trace element are preferably
One or more in niobium, molybdenum, titanium, tungsten, aluminium, zirconium, rare earth, trace element are preferably sulphur and/or phosphorus.
According to the present invention, under above-mentioned treatment conditions, thickness is obtained for 1-10 μm (preferably 6-8 μm)
Oxide-film of the coverage rate for more than 85% (preferably more than 90%).
Hereinafter will be described the present invention by embodiment, but the present invention will be not limited in following realities
Apply example.
Embodiment 1
It is the industrial pyrolysis furnace radiation that same material print is placed with 35Cr45Ni and boiler tube to furnace tube material
Section boiler tube has carried out the process of low oxygen partial pressure gas atmosphere.The element of Tube alloys is consisted of：Cr：32.60、
Ni：42.44、Fe：21.13、Mn：1.01、Si：1.38、Nb:0.73、C：0.54th, other：0.17
(wt%).With spaced form in crack furnance radiation section furnace tube, axially disposed and boiler tube one
Twisted sheet made by body, it is a pitch that twisted sheet distorts 180 ° of axial length, two adjacent twisted sheets it
Between distance be 15 pitches.The low oxygen partial pressure gas for being adopted is for H2With the admixture of gas of water vapour,
The percentage by volume that wherein water vapour accounts for low oxygen partial pressure gas is 5.0%, low oxygen partial pressure gas treating process
The heating rate of middle heat-treatment furnace is 50 DEG C/h, and treatment temperature is 900 DEG C, and process time is 40 hours,
Then furnace temperature is down to room temperature naturally.After cooling, the print placed is taken out, ESEM is used in boiler tube
With its surface composition of energy spectrometer analysis, analysis shows print surface define comprising Cr, Mn, Ni,
The oxide-film of the oxide of Fe and Si elements, wherein, the thickness of oxide-film is 7.8 μm, and coverage rate is
90%.
Hydrocarbon vapours cracking reaction is carried out in the industrial pyrolysis furnace after the process of low oxygen partial pressure gas atmosphere, is split
Solution raw material is naphtha, and its physical property is：31.8～171.7 DEG C of boiling range, proportion D200.7169g/ml；Split
Solution condition is：825 DEG C of coil outlet temperature, water-oil factor is 0.55.The cycle of operation of pyrolysis furnace reaches 180
My god.
Embodiment 2
Same types pyrolysis furnace containing twisted sheet in radiant coil same as Example 1.Adopted
Low oxygen partial pressure gas be H2With the admixture of gas of water vapour, wherein water vapour accounts for low oxygen partial pressure gas
Percentage by volume be 3.2%, in low oxygen partial pressure gas treating process, the heating rate of heat-treatment furnace is
100 DEG C/h, treatment temperature is 950 DEG C, and process time is 30 hours, and then furnace temperature is down to room naturally
Temperature.With ESEM and energy spectrometer analysis print surface composition, analysis shows define bag on print surface
The oxide-film of the oxide containing Cr, Mn, Ni, Fe and Si element, wherein, the thickness of oxide-film is
6.4 μm, coverage rate is 85%.
Hydrocarbon vapours cracking reaction is carried out in the industrial pyrolysis furnace after the process of low oxygen partial pressure gas atmosphere, is split
Solution raw material is diesel oil, and its physical property is：211.5～408.7 DEG C of boiling range, proportion D200.8778g/ml, cracking
Condition is：795 DEG C of coil outlet temperature, water-oil factor is 0.75.The cycle of operation of pyrolysis furnace reaches 100
My god.
Embodiment 3
Same types pyrolysis furnace containing twisted sheet in radiant coil same as Example 1.Adopted
Low oxygen partial pressure gas be H2With the admixture of gas of water vapour, wherein water vapour accounts for low oxygen partial pressure gas
Percentage by volume be 2.2%, in low oxygen partial pressure gas treating process, the heating rate of heat-treatment furnace is
80 DEG C/h, treatment temperature is 850 DEG C, and process time is 45 hours, is then down to naturally furnace temperature
Room temperature.With ESEM and energy spectrometer analysis print surface composition, analysis shows are defined on print surface
The oxide-film of the oxide comprising Cr, Mn, Ni, Fe and Si element, wherein, the thickness of oxide-film is
6.2 μm, coverage rate is 87%.
Hydrocarbon vapours cracking reaction is carried out in the industrial pyrolysis furnace after the process of low oxygen partial pressure atmosphere, cracking is former
Expect for hydrogenation tail oil, its physical property is：170.1～342.0 DEG C of boiling range, proportion D200.8234g/ml, splits
Solution condition is：805 DEG C of coil outlet temperature, water-oil factor is 0.75.The cycle of operation of pyrolysis furnace reaches 120
My god.
Embodiment 4
HK40 lab scales boiler tube to managing and being placed with pipe same material print containing 1 section MERT carries out low
Partial pressure of oxygen gas atmosphere pre-oxidation treatment, the element of Tube alloys are consisted of：Cr：24.9、Ni：20.1、
Mn：0.98、Si：0.52、C：0.41st, p ＜ 0.03, S ＜ 0.03, balance of Fe (wt%).
Using CH4With the admixture of gas of water vapour as low oxygen partial pressure atmosphere processing gas, wherein water steams
It is 4.5% that vapour accounts for the percentage by volume of low oxygen partial pressure gas, and the flow velocity of low oxygen partial pressure gas is
400ml/min, the heating rate of heat-treatment furnace is 50 DEG C/h, and treatment temperature is 950 DEG C, and process time is
20 hours, then furnace temperature is down to room temperature naturally.The print placed in boiler tube is taken out, ESEM is used
With energy spectrometer analysis tube skin composition, analysis shows are defined comprising Cr, Mn and Si element in print
Oxide oxide-film, wherein, the thickness of oxide-film is 7.2 μm, and coverage rate is 88%.
Hydrocarbon vapours cracking reaction, cracking stock are carried out in the lab scale boiler tube after the process of low oxygen partial pressure atmosphere
For naphtha, its physical property is：32.8～173.8 DEG C of boiling range, proportion D200.7058g/ml；Cracking condition
For：845 DEG C of cracking temperature, water-oil factor is 0.5.The coking amount of the boiler tube of the present invention is not contained than prior art
The coking amount of enhanced heat transfer member and the HK40 boiler tubes for not carrying out low oxygen partial pressure process reduces 63.13%.
Embodiment 5
Enter to the 35Cr45Ni lab scale boiler tubes that same material print is placed with inner rib plate pipe and pipe are saved containing 1
Row low oxygen partial pressure pre-oxidation treatment, the element of Tube alloys are consisted of：Cr：34.5、Ni：44.6、Mn：
0.95、Si：1.23、C：0.49、Fe:16.55, other：1.68 (wt%).
Using the admixture of gas of CO and water vapour as low oxygen partial pressure atmosphere processing gas, wherein water steams
It is 5.5% that vapour accounts for the percentage by volume of low oxygen partial pressure gas, and the flow velocity of low oxygen partial pressure gas is
450ml/min, the heating rate of heat-treatment furnace is 30 DEG C/h, and treatment temperature is 950 DEG C, and process time is
20 hours, then furnace temperature is down to room temperature naturally.With ESEM and energy spectrometer analysis print surface composition,
Analysis shows define the oxide-film of the oxide comprising Cr, Mn and Si element on print surface, wherein,
The thickness of oxide-film is 8.0 μm, and coverage rate is 89%.
Hydrocarbon vapours cracking reaction, cracking stock are carried out in the lab scale boiler tube after the process of low oxygen partial pressure atmosphere
For naphtha, its physical property is：32.8～173.8 DEG C of boiling range, proportion D200.7058g/ml；Cracking condition
For：845 DEG C of cracking temperature, water-oil factor is 0.5.The coking amount of the boiler tube of the present invention is not contained than prior art
The coking amount of enhanced heat transfer member and the 35Cr45Ni boiler tubes for not carrying out low oxygen partial pressure process is reduced
73.29%.
Comparative example 1
Method according to embodiment 1 is carried out, and except for the difference that, twisted sheet is not contained in radiant coil, and
Low oxygen partial pressure gas atmosphere process is not carried out, the cycle of operation of pyrolysis furnace is 55 days.
Comparative example 2
Method according to embodiment 2 is carried out, and except for the difference that, twisted sheet is not contained in radiant coil, and
Low oxygen partial pressure gas atmosphere process is not carried out, the cycle of operation of pyrolysis furnace is 30 days.
Comparative example 3
Method according to embodiment 3 is carried out, and except for the difference that, twisted sheet is not contained in radiant coil, and
Low oxygen partial pressure gas atmosphere process is not carried out, the cycle of operation of pyrolysis furnace is 40 days.
Comparative example 4
Method according to embodiment 1 is carried out, and except for the difference that, does not carry out low oxygen partial pressure gas atmosphere process,
The cycle of operation of pyrolysis furnace is 100 days.
Comparative example 5
Method according to embodiment 2 is carried out, and except for the difference that, does not carry out low oxygen partial pressure gas atmosphere process,
The cycle of operation of pyrolysis furnace is 50 days.
Comparative example 6
Method according to embodiment 3 is carried out, and except for the difference that, does not carry out low oxygen partial pressure gas atmosphere process,
The cycle of operation of pyrolysis furnace is 70 days.
Comparative example 7
Be HP40 (Cr25Ni35) to furnace tube material, in radiant coil the industry containing twisted sheet split
Solution stove is carried out in low oxygen partial pressure atmosphere processing procedure, in boiler tube places same material print, and what is adopted is low
Partial pressure of oxygen gas is H2With the admixture of gas of water vapour, wherein water vapour accounts for low oxygen partial pressure atmosphere gas
Percentage by volume be 3.2%, in low oxygen partial pressure gas treating process, the heating rate of heat-treatment furnace is
155 DEG C/h, treatment temperature is 950 DEG C, and process time is 30 hours.Then furnace temperature is down to naturally
Room temperature.With ESEM and energy spectrometer analysis print surface composition, analysis shows print surface film oxide covers
Lid rate is less than 30%, and the oxide-film formed by print surface is easily peeled off.
Comparative example 8
Low oxygen partial pressure gas has been carried out to industrial crack furnace radiant coil of the furnace tube material for 35Cr45Ni
Atmosphere process.The element of Tube alloys is consisted of：Cr：32.59、Ni：43.04、Fe：20.60、Mn：
0.99、Si：1.36、Nb:0.76、C：0.48th, other：0.18 (wt%).
Boiler tube is allowed to be in H2、CH4In the atmosphere of water vapour, with the programming rate of 60 DEG C/h by boiler tube
Temperature rises to 600 DEG C, and the percentage by volume of temperature-rise period water vapour is 1.2%；Boiler tube is in 600 DEG C of constant temperature
6 hours, the percentage by volume of thermostatic process water vapour was 1.2%；With the programming rate of 30 DEG C/h by stove
Pipe temperature rises to 900 DEG C, and the percentage by volume of temperature-rise period water vapour is 0.6%；Boiler tube is permanent at 900 DEG C
Temperature 30 hours, the percentage by volume of thermostatic process water vapour is 0.6%；Then it is cooled to room temperature.
Hydrocarbon vapours cracking reaction is carried out in the industrial pyrolysis furnace after the process of low oxygen partial pressure gas atmosphere, is split
Solution raw material is naphtha, and its physical property is：33.5～170.7 DEG C of boiling range, proportion D200.7269g/ml；Split
Solution condition is：825 DEG C of coil outlet temperature, water-oil factor is 0.55.The cycle of operation of pyrolysis furnace reaches 80
My god.
By above-described embodiment and comparative example, the boiler tube obtained by method of the present invention process, energy
It is enough to form the moderate oxide-film of thickness in its inner surface, and coverage rate is also high.The boiler tube that the process is obtained
During for pyrolysis furnace, pyrolysis furnace significantly extends service cycle.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to above-mentioned reality
The detail in mode is applied, in the range of the technology design of the present invention, can be to the technical side of the present invention
Case carries out various simple variants, and these simple variants belong to protection scope of the present invention.
It is further to note that each particular technique described in above-mentioned specific embodiment is special
Levy, in the case of reconcilable, can be combined by any suitable means, in order to avoid need not
The repetition wanted, the present invention are no longer separately illustrated to various possible combinations.
Additionally, can also be combined between a variety of embodiments of the present invention, as long as its
Without prejudice to the thought of the present invention, which should equally be considered as content disclosed in this invention.
Claims (9)
1. processing method of a kind of pyrolysis furnace with nichrome boiler tube, it is characterised in that the method includes：
Under low oxygen partial pressure gas atmosphere, nichrome boiler tube is warming up to the programming rate less than 150 DEG C/h
600-1100 DEG C, and it is incubated 5-100 hours；Wherein, it is provided with reinforcing to pass in the nichrome boiler tube
Hot component.
2. method according to claim 1, wherein, the enhanced heat transfer member be twisted sheet,
At least one in inner rib plate and inner fin.
3. method according to claim 1, wherein, the low oxygen partial pressure gas be water vapour and
Selected from CO2、CO、CH4、C2H6、C3H8、NH3、H2、N2, at least one in Ar and He,
And water vapour accounts for the percentage by volume of low oxygen partial pressure gas below 7.5%.
4. method according to claim 3, wherein, the water vapour accounts for low oxygen partial pressure gas
Percentage by volume is 2-7.5%.
5. method according to claim 3, wherein, the low oxygen partial pressure gas be water vapour and
CH4Admixture of gas, water vapour and CO2Admixture of gas, water vapour and CO gas mixing
Thing or water vapour and H2Admixture of gas.
6. method according to claim 1, wherein, the programming rate is 100 DEG C/below h,
Temperature retention time is 10-60 hours.
7. method according to claim 6, wherein, the programming rate is 30-100 DEG C/h,
Temperature retention time is 15-50 hours.
8. the method according to any one in claim 1-7, wherein, by nichrome boiler tube
It is warming up to 800-1000 DEG C.
9. the method according to any one in claim 1-7, wherein, by weight percentage,
The matrix composition of the nichrome boiler tube includes：Chromium 12-50%, nickel 20-50%, manganese 0.2-3%, silicon
The trace element of 0-3%, carbon 0-0.75%, 0-5% and trace element, balance of iron；The trace element
For one or more in niobium, molybdenum, titanium, tungsten, aluminium, zirconium, rare earth, trace element is sulphur and/or phosphorus.
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| CN106554797B (en) | 2019-06-28 |
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