CN103788986B - A kind of hydrocarbon cracking boiler tube suppressing coking and preparation method thereof - Google Patents
A kind of hydrocarbon cracking boiler tube suppressing coking and preparation method thereof Download PDFInfo
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- CN103788986B CN103788986B CN201210426321.9A CN201210426321A CN103788986B CN 103788986 B CN103788986 B CN 103788986B CN 201210426321 A CN201210426321 A CN 201210426321A CN 103788986 B CN103788986 B CN 103788986B
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Abstract
Hydrocarbon cracking boiler tube that the invention provides a kind of anti-coking and preparation method thereof.First using cracking furnace pipe as barrel-shaped negative electrode, the mixture of simple substance manganese or manganese aluminium, form mn ion or mn ion, aluminum ions mixture by glow discharge principle, at high temperature infiltrate boiler tube internal skin fast along lattice defect, form the pervious course of manganese element or manganese, aluminium element; Then containing H
2carry out high-temperature heat treatment with under the low oxygen partial pressure atmosphere of water vapour, form manganese picotite or manganese-aluminium spinelle coating at the internal surface of cracking furnace pipe.This coating can reduce coking and the carburizing of cracking furnace pipe, extends the cycle of operation and the work-ing life of boiler tube.
Description
Technical field
The present invention relates to petrochemical industry, particularly relate to and a kind of there is the hydrocarbon cracking boiler tube and preparation method thereof suppressing coking behavior.
Background technology
The triolefin (ethene, propylene, divinyl) that ethylene unit is produced and triphen (benzene,toluene,xylene) are the basic materials of petrochemical industry.The output of ethene, industrial scale and technology indicate the developmental level of a national oil chemical industry.The method of current production ethene is based on pyrolysis in tubular furnace technology, and it is worldwide widely applied.
The coking of pyrolysis in tubular furnace furnace radiant coil is a large technical barrier of long-standing problem ethylene production, and coking can increase boiler tube thermal resistance, reduces heat transfer coefficient, wall temperature is caused to raise, fuel consumption increases, and occurs boiler tube carburizing and local superheating phenomenon, makes the boiler tube lost of life; Coking can shorten the cycle of operation of pyrolyzer, reduces effective production time, and lot of energy is used for burning simultaneously; Coking layer can make fluid-pressure drop increase, and olefin yields reduces, and boiler tube internal diameter diminishes, and ethylene producing device treatment capacity reduces, and can block boiler tube when coking is serious, makes ethylene unit be forced to stop.
Mainly take following several method to suppress the coking of cracking furnace pipe at present: (1) adds coking inhibitor in cracking stock; (2) in the metallurgical coating of cracking furnace pipe internal surface coating anti-coking; (3) cracking furnace pipe applies pre-treatment online.
The more representational patent of coking inhibitor is US4900426, the US4551227 of Phillips Petroleum Co. of chemical company of nail (unit of length) section, the US4680421 of Bates research company, the CN1247887 of Beijing Chemical Research Institute, the CN1367225 of Yangzi Petrochemical Co., Ltd.In cracking stock or dilution steam generation the coking inhibitor added containing the element such as sulphur, phosphorus, basic metal, alkaline-earth metal, boride have simple to operate, without the need to changing Production Flow Chart, advantage with low cost.Its principle makes tube skin passivation, shields the catalytic coking effect of iron, nickel etc. on the surface; Change free radical reaction course, suppress homogeneous reaction coking; Catalytic steam and coke carry out gasification reaction, constantly generate CO, CO
2; Change the physical aspect of burnt dirt, make it loose, be easy to remove.But, coking inhibitor may cause corrosion to boiler tube metal, the olefin product in downstream is polluted, and from the situation that domestic and international coking inhibitor is applied at full scale plant, it is relatively applicable to the single light hydrocarbon feedstocks of the components such as ethane, and for the domestic cracking stock based on petroleum naphtha, coking inhibitor extends few to the pyrolyzer cycle of operation, add the shortcoming itself with corrodibility and contaminative, coking inhibitor does not have large-scale industrial application so far.
The more representational patent of metallurgical coating is the US6585864 of Canadian Westaim company, the US6579628 of industrial company of Japanese Datong District, the US6537388 of Alon sufacing company of the U.S., the CN1580316 of Research Institute of Petro-Chemical Engineering, the CN1546609 of Luoyang petroleum chemical engineering company.Apply anti-scorch coating at cracking furnace pipe internal surface and form one or more layers mechanical property and all good protective layer of thermal stability, as Al mainly through plasma spraying, method such as heat sputtering, high temperature sintering etc. at boiler tube internal surface
2o
3, Cr
2o
3, SiO
2deng, this coating reduces the catalytic activity of boiler tube inwall Fe, Ni, and its frictional coefficient is lower, can effective the sticking of slagging prevention precursor, and slows down whole coking process.Coating technology is applied to hydrocarbon cracking boiler tube, extend the cycle of operation to a certain extent, but coating processes is complicated, cost is high, and coating life is limited, and coating processes is larger on the composition profiles of whole boiler tube, weave construction impact, and boiler tube must just can apply in dismounting, boiler tube after coating due to welding reason, makes weld become the position suppressing coking the weakest, so coating technology is not adopted by ethylene production business so far on a large scale in assembling process.
The more representational patent of online coating pre-treatment is CN100497529C, the US6514563 of SK company of Korea S, the CN1399670 of French Atofina company of East China University of Science.The metallurgical coating technology of coking inhibitor and anti-coking industrially applies himself limitation, so people wish a kind of method finding suppression coking both inhibitor and coating advantages can got up, namely without the need to changing the flow process of existing cracker, online anti-coking coating is formed and coating can the processing method of online updating.The principle that the online precoating of cracking furnace pipe forms coating is exactly allow in the atmosphere of the water vapour in boiler tube of the compound containing elements such as Si, B, S, P, Cr, Ca, Al decompose, the oxidate produced, boiler tube inwall (wherein S, P and matrix metal effect form metallic sulfide, metal phosphide), forms one or more layers anti-coking coating.The fatal shortcoming of online coating one is exactly the huge souring that coating is unable to bear cracked gas stream, easily peels off, and therefore this technology fails industrialization.
For suppressing the coking of hydrocarbon cracking process, the actually operating of factory utilizes high-temperature vapor to cracking furnace pipe preoxidation for some time, and boiler tube internal surface just can form Cr
2o
3oxide film protection layer, boiler tube use the initial stage, this protective layer can play certain effect preventing surface catalysis coking, carburizing, but be through for some time circulation cracking and after burning, Cr
2o
3zone of oxidation turns the Cr gradually becoming fragility
xc
ycarbide, anti-coking effect was lost efficacy.
From 1997 to 2006, Canadian Nova company disclosed a collection of at cracking furnace pipe inwall formation manganese picotite MnCr
2o
4the patent of protective layer, comprises US5630887, US6824883, US7156979, US6436202, US2004265604, US2005077210, US2006086431.Within 2005,8 ethylene production plant of this technology in the U.S., Europe, Asia, the Middle East are promoted by Nova, the cycle of operation reaches more than 400 day, within 2007, this technology is improved by Nova further, and the cycle of operation on the joffre full scale plant of Alberta reaches 700 days.Chinese Petroleum Univ. in 2009 also discloses two sections and forms manganese picotite MnCr at cracking furnace pipe inwall
2o
4the patent of protective layer, CN101565807, CN101565808.Nova and China University Of Petroleum Beijing are all that the low oxygen partial pressure gas at high temperature formed by the mixed gas of hydrogen and water vapour is carried out process to new boiler tube inwall and obtains manganese picotite, and their difference is lower than University of Petroleum of water vapour content in the low oxygen partial pressure gas in Nova technology.From the effect of the patent of Nova and China University Of Petroleum Beijing and industrial application, we can infer, MnCr
2o
4spinel protective layer is very fine and close, has excellent anti-coking, anti-carburizing energy, can reduce coking and the carburizing of industrial crack boiler tube.
But, utilize the manganese picotite MnCr that the mode of this low oxygen partial pressure is formed at cracking furnace pipe inwall
2o
4protective layer also has following shortcoming: (1) can only apply this technology in new boiler tube, can not be used for old boiler tube; (2) the manganese picotite MnCr formed
2o
4protective layer is after air-steam burns, and its anti-coking, anti-carbon potential decline obviously, and the life-span of coating can not be oversize.
Summary of the invention
For the shortcoming utilizing low oxygen partial pressure mode to exist at the spinel protective layer that cracking furnace pipe inwall is formed in prior art; the invention provides a kind of hydrocarbon cracking boiler tube containing manganese picotite, manganese-aluminium spinelle coating and preparation method thereof; in hydrocarbon cracking process; coke significantly reduces in the deposition of this boiler tube internal surface; the cycle of operation of boiler tube obviously extends, and can apply in old cracking furnace pipe.
An object of the present invention is to provide a kind of hydrocarbon cracking boiler tube of anti-coking, it is characterized in that:
The internal surface of described cracking furnace pipe has manganese picotite or manganese-aluminium spinelle coating; Described manganese picotite coating contains Mn
xcr
3-xo
4, MnO, SiO
2, Fe and Ni; Described manganese-aluminium spinelle coating contains Mn
xal
3-xo
4, Al
2o
3, SiO
2, Fe and Ni;
Described spinel coating, it is the mixture by simple substance manganese or simple substance manganese and pure aluminum, utilize glow discharge principle, generate high-octane mn ion and aluminum ion, be splashed to stove cracking furnace pipe internal surface fast, and at 800 DEG C-1000 DEG C, the internal skin of described cracking furnace pipe is infiltrated fast along lattice defect, form the pervious course of manganese element or manganese, the change of aluminium element concentration in gradient; Then containing H
2with under the low oxygen partial pressure gas of water vapour, one or two stage high-temperature heat treatment are carried out to the cracking furnace pipe containing manganese element or manganese, aluminium element pervious course, is formed at the internal surface of described cracking furnace pipe.
In the specific implementation, by weight percentage, the composition of described cracking furnace pipe matrix is: chromium 12 ~ 50%, nickel 20 ~ 50%, manganese 0.2 ~ 3%, silicon 0 ~ 3%, the trace element of carbon < 0.75%, 0 ~ 5% and trace elements, and surplus is iron; Described trace element is one or more in niobium, titanium, tungsten, aluminium, rare earth element, and described trace elements is that sulphur is or/and phosphorus.
In the specific implementation, in described manganese picotite coating, described Mn
xcr
3-xo
4molar fraction be 30-99.6%, the molar fraction of described MnO is 0.1-30%, described SiO
2molar fraction be 0.1-20%, the molar fraction of described Fe is 0.1-10%, and the molar fraction of described Ni is 0.1-10%; In described manganese-aluminium spinelle coating, described Mn
xal
3-xo
4molar fraction be 30-99.6%, described Al
2o
3molar fraction be 0.1-30%, described SiO
2molar fraction be 0.1-20%, the molar fraction of described Fe is 0.1-10%, and the molar fraction of described Ni is 0.1-10%.
In the specific implementation, the structural formula of described manganese picotite is Mn
xcr
3-xo
4, in formula, the numerical value of x is 0.5 ~ 1.5; The structural formula of described manganese-aluminium spinelle is Mn
xal
3-xo
4, in formula, the numerical value of x is 0.5 ~ 1.5.
Another object of the present invention is to provide a kind of preparation method of hydrocarbon cracking boiler tube of anti-coking, and the preparation method of described cracking furnace pipe comprises the following steps:
(1) using cracking furnace pipe as barrel-shaped negative electrode, simple substance manganese or manganese aluminium mixture are placed in described barrel-shaped negative electrode, by glow discharge principle in the rough vacuum argon shield atmosphere of 0.1 ~ 30Pa, produce high-octane mn ion or mn ion, aluminum ions mixture, be splashed to boiler tube internal surface fast, high-energy metals ion infiltrates the internal skin of described cracking furnace pipe fast at 800 DEG C-1000 DEG C along lattice defect, form the pervious course of manganese element or manganese, the change of aluminium element concentration in gradient;
(2) in certain low oxygen partial pressure atmosphere, one or two stage high-temperature heat treatment are carried out to the described cracking furnace pipe containing manganese element or manganese, aluminium element pervious course, form manganese picotite or manganese-aluminium spinelle coating at described cracking furnace pipe internal surface; Described low oxygen partial pressure gas is containing H
2with the mixed gas of water vapour; First stage H
2be 1792 ~ 107: 1, subordinate phase H with the mol ratio of water vapour
2be 1 ~ 1791: 1 with the mol ratio of water vapour.
In the specific implementation, in described manganese element pervious course, the molar fraction of manganese element is 0.1-30%, and all the other are boiler tube matrix; In described manganese element and aluminium element pervious course, the molar fraction of manganese element is 0.1-20%, and the molar fraction of aluminium element is 0.1-40%, and all the other are boiler tube matrix.The thickness of described pervious course is 0.1-2.0mm.One or more in nitrogen, argon gas, helium, hydrocarbon cracking gas are also comprised in described low oxygen partial pressure gas.The treatment temp that described cracking furnace pipe carries out each stage high-temperature heat treatment is respectively 800 DEG C ~ 1100 DEG C.The treatment time that described cracking furnace pipe carries out each stage high-temperature heat treatment is respectively 5 ~ 50 hours.When described cracking furnace pipe internal skin forms manganese element pervious course, adopt described subordinate phase low oxygen partial pressure high-temperature heat treatment, preferably adopt described first stage and subordinate phase low oxygen partial pressure high-temperature heat treatment; When described cracking furnace pipe internal skin forms manganese, aluminium element pervious course, adopt described first stage low oxygen partial pressure high-temperature heat treatment.
When forming manganese picotite, formed pervious course mainly comprise element of Fe, Ni, Cr, Mn and about 1.5% Si element, in these 5 kinds of elements, be Si > Mn > Cr > Fe > Ni to the order of oxygen affinity.As H in low oxygen partial pressure gas
2with the molar ratio range of water vapour 1792 ~ 10
7between time, the oxygen partial pressure formed is very low, and under this oxygen partial pressure, these 5 kinds of elements only have Si, Mn oxidized, and Cr, Fe, Ni are not oxidized, finally form SiO
2and MnO, wherein SiO
2there is the effect of diffusion barrier, Cr, Fe, Ni element in alloy can be stoped to a certain extent to the oxygen element in top layer diffusion and atmosphere to internal diffusion.As H in low oxygen partial pressure gas
2and when the molar ratio range of water vapour is between 1 ~ 1791, under this oxygen partial pressure, Cr element is through SiO
2diffusion barrier diffuses to superficial oxidation and forms Cr
2o
3.Final result is that boiler tube internal surface grows containing with manganese picotite, MnO, SiO
2be main coating, and Fe and Ni element is capped.
When forming manganese picotite, formed pervious course mainly comprise element of Fe, Cr, Ni, Mn, Al and about 1.5% Si element, in these 6 kinds of elements, be Al > Si > Mn > Cr > Fe > Ni to the order of oxygen affinity.As H in low oxygen partial pressure gas
2and when the molar ratio range of water vapour is between 1792 ~ 107, the oxygen partial pressure formed is very low, under this oxygen partial pressure, these 6 kinds of elements only have Al, Si, Mn oxidized, and Cr, Fe, Ni are not oxidized, define Al
2o
3, SiO
2and MnO, wherein SiO
2content less, consequently boiler tube internal surface grows with manganese-aluminium spinelle is the coating of main component, and Cr, Fe, Ni element is capped.
Spinel coating of the present invention covers Fe, Ni element with catalytic activity, coating is very fine and close, can prevent carbon from penetrating into boiler tube matrix, and the thermal expansivity of coating and matrix closely, and the thermal stresses produced between matrix is little, the requirement of hydrocarbon cracking boiler tube life-time service can be met.
Relative to Nova patent, a kind of hydrocarbon cracking boiler tube suppressing coking of the present invention and preparation method thereof, has the following advantages:
(1) can be suitable for new and old boiler tube, Mn element source in Nova patent is in boiler tube matrix, and Mn element of the present invention is entered by the principle infiltration of glow discharge, therefore the method that the present invention forms spinel coating stands good in old cracking furnace pipe, old cracking furnace pipe surface is containing oxide compound and carbide, be difficult to allow Mn element move to surface through zone of oxidation and carburization zone by the mode of the low oxygen partial pressure slow oxidation of Nova, and just there is not this problem in the present invention;
(2) the spinel MnCr after the process of Nova patent
2o
4in easily form Cr
2o
3phase, this can cause MnCr
2o
4the decline of protective layer anti-coking, anti-carbon potential, and Mn of the present invention is excessive, can form MnO phase, allows manganese picotite more easily keep the structure of its spinel, therefore the life-span is longer;
(3) in use two step low oxygen partial pressure oxidation style of the present invention, the SiO that the first step is formed
2diffusion barrier can allow the rate of oxidation of Cr in second step slower, the manganese picotite particle of final formation is more tiny, fine and close, stronger with boiler tube bonding force, and relative to Nova patent, diffuse to the Cr element minimizing that top layer participates in oxidizing reaction, the Cr in manganese picotite coating
2o
3reduce mutually, be conducive to the structure that manganese picotite more easily keeps its spinel;
(4) in use two step low oxygen partial pressure oxidation style of the present invention, the first step oxidation can make the SiO of matrix surface
2content raises, SiO
2the resistance of oxidation of manganese picotite can be improved, and improve the bonding force with matrix;
(5) hydrocarbon cracking process can produce H
2if suitably control the percentage composition of dilution steam generation, ensure the H in splitting gas
2with the mol ratio of water vapour 1 ~ 1791, form SiO containing manganese element pervious course boiler tube of the present invention through the oxidation of the first step low oxygen partial pressure
2after MnO, in-service also can Nature creating manganese picotite coating.
(6) manganese-aluminium spinelle MnAl of the present invention
2o
4than manganese picotite MnCr
2o
4have stronger resisting carbonization, therefore spinel coating stability of the present invention is better, the life-span is longer.
Embodiment
Be described in further detail technical scheme of the present invention below in conjunction with embodiment, protection scope of the present invention is not limited to following embodiment.
Comparative example 1
Employing is of a size of
material is the new boiler tube of 3545 nichrome, is numbered A, B, C, and boiler tube A, B, C be not containing any coating.Machined rear boiler tube internal surface light, non-scale, with X-ray energy dispersion spectroscopy instrument (Energy Dispersive Spectrometer is called for short EDS) analytical furnace tube-surface composition, the results are shown in Table 2.Boiler tube A, B, C, on the laboratory installation of 200g/h inlet amount, are cracking stock with petroleum naphtha, carry out cracking coking evaluation test.Utilize air to burn after cracking completes, burn CO and CO in gas
2concentration is by radar stealthy materials on-line measurement, and the volume burning gas, by wet flow indicator online record, finally calculates the coking amount that the carbon amounts of burning in gas is cracking process.Breaking test condition is as follows:
Raw material: industrial naphthas (physical property is in table 1) pyrolysis time: 2 hours
Preheater temperature: 600 DEG C of pyrolyzer temperature: 850 DEG C
Water-oil ratio: 0.5 residence time: 0.35 second
Table 1
According to the round-robin test that above-mentioned condition is carried out 5 cracking to blank boiler tube A, B, C and burnt, the coking amount of different cracking number of times is in table 3.
Comparative example 2
Employing size, the new boiler tube that material is identical with comparative example 1, this boiler tube prepares spinel coating according to the method for US6436202 at internal surface, allows boiler tube be the H of 0.15% at water vapour volumn concentration
2-H
2the lower 650 DEG C of insulations of O low oxygen partial pressure atmosphere 10 hours, then rise to 900 DEG C, are incubated 30 hours.After cooling, with X-ray energy dispersion spectroscopy instrument (Energy Dispersive Spectrometer is called for short EDS) analytical furnace pipe internal surface composition, the results are shown in Table 2.
Adopt the round-robin test that the cracking condition of comparative example 2 carries out 5 cracking to this boiler tube and burns, the coking amount of different cracking number of times is in table 3.
Embodiment 1
Adopt the new boiler tube that size is identical with comparative example 1 with material, this boiler tube prepares coating according to method of the present invention.Using new boiler tube as barrel-shaped negative electrode, be placed in by manganese material in this boiler tube, glow discharge 5 hours at 800 DEG C and in the rough vacuum argon shield atmosphere of 0.5Pa, the manganese element pervious course XL-30 Flied emission environmental scanning electronic microscope of formation observes about 0.3mm.Boiler tube containing manganese pervious course is first at 99.97%H on the device described in comparative example 1
2-0.03%H
2o (H
2with H
2the mol ratio of O is 3332: 1) atmosphere in 1000 DEG C of insulations 20 hours, then at 50%Ar-49.7%H
2-0.3%H
2o (H
2with H
2the mol ratio of O is 166: 1) 1000 DEG C of insulations 10 hours in atmosphere, after cooling, form with X-ray energy dispersion spectroscopy instrument (Energy Dispersive Spectrometer is called for short EDS) analytical furnace pipe internal surface, the results are shown in Table 2.
Adopt the round-robin test that the cracking condition of comparative example 1 carries out 5 cracking to this boiler tube and burns, the coking amount of different cracking number of times is in table 3.
Embodiment 2
Adopt the new boiler tube that size is identical with comparative example 1 with material, this boiler tube prepares coating according to method provided by the invention.Using new boiler tube as barrel-shaped negative electrode; manganese material, aluminium are placed in this boiler tube; glow discharge 5 hours at 800 DEG C and in the rough vacuum argon shield atmosphere of 0.5Pa, manganese element, the aluminium element pervious course XL-30 Flied emission environmental scanning electronic microscope of formation observe about 0.4mm.Boiler tube containing pervious course on the device described in comparative example 1 at 99.97%H
2-0.03%H
2in O (mol ratio of H2 and H2O is 3332: 1) atmosphere, 1000 DEG C are incubated 20 hours, after cooling, with X-ray energy dispersion spectroscopy instrument (EnergyDispersive Spectrometer is called for short EDS) analytical furnace pipe internal surface composition, the results are shown in Table 2.
Adopt the round-robin test that the cracking condition of comparative example 1 carries out 5 cracking to this boiler tube and burns, the coking amount of different cracking number of times is in table 3.
Comparative example 3
The boiler tube adopted is old boiler tube, and be the boiler tube A having carried out 5 cracking in comparative example 1 and burnt, be numbered A ', this boiler tube prepares spinel coating according to the method for US6436202 at internal surface, allows boiler tube be the H of 0.15% at water vapour volumn concentration
2-H
2the lower 650 DEG C of insulations of O low oxygen partial pressure atmosphere 10 hours, then rise to 900 DEG C, are incubated 30 hours.After cooling, with X-ray energy dispersion spectroscopy instrument (EnergyDispersive Spectrometer is called for short EDS) analytical furnace pipe internal surface composition, the results are shown in Table 2.
Adopt the round-robin test that the cracking condition of comparative example 1 carries out 5 cracking to this boiler tube and burns, the coking amount of different cracking number of times is in table 3.
Embodiment 3
The boiler tube adopted is old boiler tube, and be the boiler tube B having carried out 5 cracking in comparative example 1 and burnt, be numbered B ', this boiler tube prepares coating according to method provided by the invention.Using boiler tube B ' as barrel-shaped negative electrode, be placed in by manganese material in boiler tube B ', glow discharge 5 hours at 800 DEG C and in the rough vacuum argon shield atmosphere of 0.5Pa, the manganese element pervious course XL-30 Flied emission environmental scanning electronic microscope of formation observes about 0.4mm.Boiler tube containing pervious course is first at 99.95%H on the device described in comparative example 1 at the boiler tube containing manganese pervious course on the device described in comparative example 1
2-0.05%H
2o (H
2with H
2the mol ratio of O is 1999: 1) atmosphere in 1000 DEG C of insulations 20 hours, then at 50%Ar-49.4%H
2-0.6%H
2o (H
2with H
2the mol ratio of O is 82: 1) 1000 DEG C of insulations 10 hours in atmosphere, after cooling, form with X-ray energy dispersion spectroscopy instrument (Energy Dispersive Spectrometer is called for short EDS) analytical furnace pipe internal surface, the results are shown in Table 2.
Adopt the round-robin test that the cracking condition of comparative example 1 carries out 5 cracking to this boiler tube and burns, the coking amount of different cracking number of times is in table 3.
Embodiment 4
The boiler tube adopted is old boiler tube, and be the boiler tube C having carried out 5 cracking in comparative example 1 and burnt, be numbered C ', this boiler tube prepares coating according to method provided by the invention.Using boiler tube C ' as barrel-shaped negative electrode, be placed in this boiler tube C ' by manganese material, aluminium, glow discharge 5 hours at 800 DEG C and in the rough vacuum argon shield atmosphere of 0.5Pa, the manganese element pervious course XL-30 Flied emission environmental scanning electronic microscope of formation observes about 0.4mm.Boiler tube containing pervious course on the device described in comparative example 1 at 50%Ar-49.98%H
2-0.02%H
2o (H
2with H
2the mol ratio of O is 2499: 1) 900 DEG C of insulations 20 hours in atmosphere, after cooling, form with X-ray energy dispersion spectroscopy instrument (Energy Dispersive Spectrometer is called for short EDS) analytical furnace pipe internal surface, the results are shown in Table 2.
Adopt the round-robin test that the cracking condition of comparative example 1 carries out 5 cracking to this boiler tube and burns, the coking amount of different cracking number of times is in table 3.
Table 2
Table 3
From the ultimate analysis of table 2, the boiler tube of embodiment 1, embodiment 3, surface defines the oxide compound of Cr, Mn, Si, and Fe, Ni constituent content with catalytic activity is very low, relative to comparative example 2 (US6436202), the content of Mn, Si is high, and this more easily allows manganese picotite keep the structure of its spinel, and stability is better; The boiler tube of embodiment 2, embodiment 4, the oxide compound of Mn, Al that surface is formed, almost covers Fe, Ni element.
As shown in Table 3, relatively, 5 times coking amount is about 1.2 grams to the coking amount of the blank boiler tube in comparative example 1; In comparative example 2, first time coking amount very low, reduce more than 90%, but along with cracking with burn increasing of number of times, coking amount increases gradually; In embodiment 1, embodiment 2, coking amount decreased average 90%, and also along with cracking with burn increasing of number of times, coking amount does not have the trend of showed increased; In comparative example 3, coking amount is almost the twice of blank value; In embodiment 3, embodiment 4, coking amount decreased average more than 80%, and also along with cracking with burn increasing of number of times, coking amount does not have the trend of showed increased.
Comparative example 4
Change the furnace tube material in comparative example 1 into HP40, be numbered D, E, F, other condition is constant, and tube skin composition is in table 4, and coking amount is in table 5.
Comparative example 5
Change the furnace tube material in comparative example 2 into HP40, other condition is constant, and after process, tube skin composition is in table 4, and coking amount is in table 5.
Embodiment 5
Change the furnace tube material in embodiment 1 into HP40, other condition is constant, and after process, tube skin composition is in table 4, and coking amount is in table 5.
Embodiment 6
Change the furnace tube material in embodiment 2 into HP40, other condition is constant, and after process, tube skin composition is in table 4, and coking amount is in table 5.
Comparative example 6
The boiler tube adopted is the old boiler tube in comparative example 4, and be numbered D ', other condition is identical with comparative example 3, and after process, tube skin composition is in table 4, and coking amount is in table 5.
Embodiment 7
The boiler tube adopted is the old boiler tube in comparative example 4, and be numbered F ', other condition is identical with embodiment 3, and after process, tube skin composition is in table 4, and coking amount is in table 5.
Embodiment 8
The boiler tube adopted is the old boiler tube in comparative example 4, and be numbered F ', other condition is identical with embodiment 4, and after process, tube skin composition is in table 4, and coking amount is in table 5.
Table 4
Table 5
From the ultimate analysis of table 4, the boiler tube of embodiment 5, embodiment 7, surface defines the oxide compound of Cr, Mn, Si, and Fe, Ni constituent content with catalytic activity is very low, relative to comparative example 5 (US6436202), the content of Mn, Si is high, and this more easily allows manganese picotite keep the structure of its spinel, and stability is better; The boiler tube of embodiment 6, embodiment 8, surface defines the oxide compound of Mn, Al, is almost covered by Fe, Ni element.
As shown in Table 5, relatively, 5 times coking amount is about 1.5 grams to the coking amount of the blank boiler tube in comparative example 4; In comparative example 5, first time coking amount very low, reduce more than 90%, but along with cracking with burn increasing of number of times, coking amount increases gradually; In embodiment 5, embodiment 6, coking amount decreased average 90%, and also along with cracking with burn increasing of number of times, coking amount does not have the trend of showed increased; In comparative example 6, coking amount is almost the twice of blank value; In embodiment 7, embodiment 8, coking amount on average reduces 75%, 85% respectively, and along with cracking with burn increasing of number of times, coking amount does not have the trend of showed increased.
Claims (10)
1. a hydrocarbon cracking boiler tube for anti-coking, is characterized in that:
The internal surface of described cracking furnace pipe has manganese picotite or manganese-aluminium spinelle coating; Described manganese picotite coating contains Mn
xcr
3-xo
4, MnO, SiO
2, Fe and Ni; Described manganese-aluminium spinelle coating contains Mn
xal
3-xo
4, Al
2o
3, SiO
2, Fe and Ni;
Described spinel coating, it is the mixture by simple substance manganese or simple substance manganese and pure aluminum, utilize glow discharge principle, generate high-octane mn ion and aluminum ion, be splashed to stove cracking furnace pipe internal surface fast, and at 800 DEG C-1000 DEG C, the internal skin of described cracking furnace pipe is infiltrated fast along lattice defect, form the pervious course of manganese element or manganese, the change of aluminium element concentration in gradient; Then containing H
2with under the low oxygen partial pressure gas of water vapour, one or two stage high-temperature heat treatment are carried out to the cracking furnace pipe containing manganese element or manganese, aluminium element pervious course, is formed at the internal surface of described cracking furnace pipe.
2. cracking furnace pipe according to claim 1, is characterized in that:
By weight percentage, the composition of described cracking furnace pipe matrix is: chromium 12 ~ 50%, nickel 20 ~ 50%, manganese 0.2 ~ 3%, silicon 0 ~ 3%, carbon <0.75%, the trace element of 0 ~ 5% and trace elements, and surplus is iron; Described trace element is selected from one or more in niobium, titanium, tungsten, aluminium, rare earth element, and described trace elements is that sulphur is or/and phosphorus.
3. cracking furnace pipe according to claim 1, is characterized in that:
In described manganese picotite coating, described Mn
xcr
3-xo
4molar fraction be 30-99.6%, the molar fraction of described MnO is 0.1-30%, described SiO
2molar fraction be 0.1-20%, the molar fraction of described Fe is 0.1-10%, and the molar fraction of described Ni is 0.1-10%;
In described manganese-aluminium spinelle coating, described Mn
xal
3-xo
4molar fraction be 30-99.6%, described Al
2o
3molar fraction be 0.1-30%, described SiO
2molar fraction be 0.1-20%, the molar fraction of described Fe is 0.1-10%, and the molar fraction of described Ni is 0.1-10%.
4. cracking furnace pipe according to claim 1, is characterized in that:
The structural formula of described manganese picotite is Mn
xcr
3-xo
4, in formula, the numerical value of x is 0.5 ~ 1.5;
The structural formula of described manganese-aluminium spinelle is Mn
xal
3-xo
4, in formula, the numerical value of x is 0.5 ~ 1.5.
5. a preparation method for anti-coking hydrocarbon cracking boiler tube, the preparation method of the described cracking furnace pipe of one of Claims 1 to 4 comprises the following steps successively:
(1) using cracking furnace pipe as barrel-shaped negative electrode, simple substance manganese or manganese aluminium mixture are placed in described barrel-shaped negative electrode, by glow discharge principle in the rough vacuum argon shield atmosphere of 0.1 ~ 30Pa, produce high-octane mn ion or mn ion, aluminum ions mixture, be splashed to boiler tube internal surface fast, high-energy metals ion infiltrates the internal skin of described cracking furnace pipe fast at 800 DEG C-1000 DEG C along lattice defect, form the pervious course of manganese element or manganese, the change of aluminium element concentration in gradient;
(2) in certain low oxygen partial pressure atmosphere, one or two stage high-temperature heat treatment are carried out to the described cracking furnace pipe containing manganese element or manganese, aluminium element pervious course, form manganese picotite or manganese-aluminium spinelle coating at described cracking furnace pipe internal surface; Described low oxygen partial pressure gas is containing H
2with the mixed gas of water vapour; First stage H
2be 1792 ~ 10 with the mol ratio of water vapour
7: 1, subordinate phase H
2be 1 ~ 1791:1 with the mol ratio of water vapour.
6. preparation method according to claim 5, is characterized in that:
In described manganese element pervious course, the molar fraction of manganese element is 0.1-30%, and all the other are boiler tube matrix;
In described manganese element and aluminium element pervious course, the molar fraction of manganese element is 0.1-20%, and the molar fraction of aluminium element is 0.1-40%, and all the other are boiler tube matrix.
7. preparation method according to claim 5, is characterized in that:
The thickness of described pervious course is 0.1-2.0mm.
8. preparation method according to claim 5, is characterized in that:
Also containing one or more in following material in described low oxygen partial pressure gas: nitrogen, argon gas, helium and hydrocarbon cracking gas.
9. preparation method according to claim 5, is characterized in that:
The treatment temp that described cracking furnace pipe carries out each stage high-temperature heat treatment is respectively 800 DEG C ~ 1100 DEG C, and the treatment time is respectively 5 ~ 50 hours.
10. preparation method according to claim 5, is characterized in that:
When described cracking furnace pipe internal skin forms manganese element pervious course, adopt described first stage and subordinate phase low oxygen partial pressure high-temperature heat treatment; When described cracking furnace pipe internal skin forms manganese, aluminium element pervious course, adopt described first stage low oxygen partial pressure high-temperature heat treatment.
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| CA2883863A1 (en) * | 2015-03-04 | 2016-09-04 | Nova Chemicals Corporation | Improved ducting for manufacture of iron |
| CN106590724B (en) * | 2015-10-15 | 2018-07-20 | 中国石油化工股份有限公司 | A kind of online method for repairing cracking furnace pipe manganese picotite film |
| CN106756775B (en) * | 2015-11-25 | 2019-04-12 | 华东理工大学 | A kind of alloy surface forms the preparation method of spinelle coating |
| CN107177815B (en) * | 2017-04-27 | 2019-08-09 | 华东理工大学 | A kind of high-temperature alloy surface composite ceramic coat and preparation method thereof |
| CA3037315A1 (en) * | 2019-03-20 | 2020-09-20 | Nova Chemicals Corporation | Stable manganochromite spinel on stainless steel surface |
| CN112725578B (en) * | 2019-10-28 | 2022-12-13 | 中国石油化工股份有限公司 | Method for treating inner surface of quenching boiler tube |
| CN111690961B (en) * | 2020-07-14 | 2021-09-07 | 四川轻化工大学 | Preparation of nitrogen-doped MnCr on FeCrNi alloy surface2O4Method for coating |
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