CN102399574B - Method for preparing lower carbon number olefins by petroleum hydrocarbon catalytic pyrolysis - Google Patents
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Abstract
The invention provides method for preparing lower carbon number olefins by petroleum hydrocarbon catalytic pyrolysis. The method comprises the following steps that petroleum hydrocarbon is introduced into an olefin cracking furnace and then undergoes a cracking reaction when passing through a radiant section furnace tube of the olefin cracking furnace, wherein an inner surface of the radiant section furnace tube is provided with a metal oxide film containing at least one of Cr, Ni, Fe, Mn, Ti, Ca, Ba, Zr and Mg; and the thickness of the metal oxide film is in a range of 0.1 to 30 micrometers. The method has the advantages that through the method, reconstruction processes on the existing olefin production device are avoided and when a cracking furnace tube needs to be replaced, only the radiant section furnace tube with the metal oxide film on the inner surface is replaced; and effects are obvious, wherein a desired product ethylene yield and a desired product propylene yield are above 5%.
Description
Technical field
The present invention relates to petroleum hydrocarbon catalytic pyrolysis method, more specifically, relate to a kind of method of preparing lower carbon number olefins by petroleum hydrocarbon catalytic pyrolysis.
Background technology
Ethene is the basic material of petrochemical industry.Output, industrial scale and the technology of ethene indicates the developmental level of a national petrochemical complex.The method of producing ethene is at present take tube furnace cracking petroleum hydrocarbon vapor technology as main, and according to statistics, propylene more than about 99% ethene and 50% is produced by the method in the world.Because steam cracking method operates at present in very harsh conditions, the temperature in latter stage of for example crack furnance radiation section furnace tube reaches or exceedes 1125 ℃, the residence time of material in radiant coil shorten to 0.2 second even shorter, therefore under current state of the art, the possibility that makes the yield of the light alkenes such as ethene, propylene and divinyl further improve by steam cracking method is very little.For this reason, investigator has carried out the research of alternate manner production light alkene technology, for example catalytic pyrolysis technology, methane oxidation coupling technology both at home and abroad, natural gas via methanol-to-olefins technology etc., it is technology of greatest concern that its Petroleum Hydrocarbon is produced olefine in low carbon number technology through catalytic pyrolysis.
Catalytic pyrolysis is the technology that petroleum hydrocarbon is converted into olefine in low carbon number under catalyzer exists.Catalytic pyrolysis has can reduce cracking temperature, improve ethene, propene yield, the advantage such as cut down the consumption of raw materials, and can reduce the quantity discharged of greenhouse gases, and its superiority and importance are self-evident.From the raw material of current production light alkene, petroleum naphtha accounts for 56%, and the catalytic pyrolysis technology that therefore exploitation is applicable to petroleum naphtha can significantly reduce energy consumption and the material consumption of producing light alkene, and competitive power develops skill.The catalytic pyrolysis technology that is applicable to petroleum naphtha of developing is at present mainly fixed-bed catalytic cracking technique, as CN 1218783C, SU91O728, SU 910729, SU 968055, the disclosed technology of CN 1OO338184C, its technical characteristics is to have the component potassium aluminate of catalytic activity, vanadic acid calcium, alkaline-earth metal, transition metal oxide, unformed metallic compound, Si-Al zeolite etc., load on the carrier that zeolite or other material form or moulding separately, form the granules of catalyst of specified shape, granules of catalyst is placed on and in reactor, forms a fixed bed that has katalysis, petroleum hydrocarbon enters fixed-bed reactor after preheating, when reactor is heated to certain temperature, in reactor, there is catalytic pyrolysis effect and generate ethene in petroleum hydrocarbon, the object products such as propylene.There is engineering scale-up problem in fixed-bed catalytic cracking technique, as builds a pyrolyzer that is equivalent to steam cracking output, and cost of investment can be more much higher than the cost of conventional steam cracking furnace.
Pyrolyzer is generally nichrome pipe with boiler tube, is made up of the material such as HK-40, HP-40, is conventionally formed by the manufacture of metal mold centrifugal casting method, and this cracking furnace pipe is mainly made up of metallic elements such as Ni, Cr, Fe.At high temperature, in petroleum hydrocarbon and boiler tube metal, iron, nickel interact and dehydrogenation deposit carbon, and iron, nickel element have remarkable katalysis to petroleum hydrocarbon in the coking of cracking furnace pipe internal surface.Meanwhile, the metallic element on coke and boiler tube surface forms a large amount of carbide, causes boiler tube carburizing and then inefficacy.
Adopt the method that applies anti-scorch coating at cracking furnace pipe internal surface, a kind of tube coking means that effectively suppress, object is to form one deck mechanical property and all good barrier coats of thermal stability at boiler tube internal surface, isolation petroleum hydrocarbon material contacts with boiler tube internal surface nickel, ferrous metal, thereby reduce the catalytic coking activity of boiler tube Surface Fe, nickel metal, slow down whole coking and the cementation process of crack furnance radiation section furnace tube.
There is the cracking furnace pipe of anti-scorch coating; there are two kinds of different preparation methods; one is by means such as plasma spraying, hot sputter, high temperature sintering, chemical vapour depositions; being formed on internal surface has as the cracking furnace pipe of the metals such as chromic oxide, silicon oxide, aluminum oxide and titanium oxide or nonmetal oxide protective layer; shortcoming is that the combination of protective layer and boiler tube matrix is firm not; coating is easily peeled off and preparation process complexity, as U.S. Pat 6585864, US 6579628, US 6537388 etc.Another kind is that the internal surface generating in position has the cracking furnace pipe of protective oxide film by specific atmosphere processing under certain temperature, and advantage is that the bonding force of protective layer and boiler tube matrix is strong, and coating is incrust and preparation process is relatively simple.
The gas that ZL 200310110224.X produces after adopting liquefied ammonia to decompose carries out atmosphere processing to ethene boiler tube, then the alloy powder preparing and binding agent furnishing slurries are coated onto to atmosphere boiler tube after treatment surface and carry out Alloying Treatment, finally form the alloy layer that can suppress with slow down coking at boiler tube internal surface, in testing laboratory's coking evaluation test of carrying out with 2500g petroleum naphtha, coking amount reduces 50～90%.The shortcoming of this method is that preparation technology of coating complexity, cost are high.
US 6423415 is by the K of certain mol proportion composition
2o, SiO
2, Al
2o
3, ZnO, MgO, Co
3o
4, Na
2o, ZrO
2spray on ethene boiler tube Deng inorganics, at high temperature H
2, N
2, water vapour atmosphere in sintering, form glass coating.The shortcoming of the method is that the coefficient of expansion of inorganic coating and boiler tube matrix differs larger, and after the temperature of production, coke cleaning changes repeatedly, the life-span of coating can be affected.
US 5648178 discloses a kind of method of preparing HP-50 Metal Cr coating with chemical Vapor deposition process, by CrCl
2powder is made the coating of certain viscosity, is coated to behind metallic surface at pure H
2thermal treatment under atmosphere, forms firmly chromiumcoating, then uses the hydrogen that contains propane to the charing of Cr coating dry type, forms rich charcoal key coat and is attached to matrix surface, then uses N
2process, form CrN and fill crack, finally use steam treatment, form thin Cr
2o
3layer, covers chromium layer surface.The shortcoming of this method is coating preparation process complexity, step is many, cost is high.
NOVA chemical company of Canada discloses a collection of patent that obtains internal surface and have the cracking furnace pipe of metal oxide protective layer of processing under low oxygen partial pressure atmosphere with hydrogen and water vapor mixture body; comprise US5630887, US 6824883, US 7156979, US 6436202 etc.; metal oxide protective layer is wherein mainly chromium galaxite; in atmosphere processing, vapour content is lower, and preparation time is longer.
US 6585864 adopts the methods such as physical vapor deposition, thermospray, magnetic sputter to prepare compound coating at boiler tube internal surface, comprise take Al, Ti and Si as main diffusion layer, structure are as the interlayer of NiCrAlY and aluminum oxide skin, after 1030 ℃～1160 ℃ high temperature hot dippings are processed, finally form the compound coating being formed by diffusion-barrier coating and enriched layer again.The shortcoming of this method is coating preparation process complexity, step is many, cost is high.
Also do not process formation metal oxide membrane technique by atmosphere at present and be applied to the report in catalytic cracking reaction boiler tube.
Summary of the invention
In order to improve the yield and quality of olefine in low carbon number in petroleum hydrocarbon catalytic pyrolysis, the invention provides a kind of method of preparing lower carbon number olefins by petroleum hydrocarbon catalytic pyrolysis.
The method of preparing lower carbon number olefins by petroleum hydrocarbon catalytic pyrolysis of the present invention is achieved in that
Method of the present invention comprises to be introduced petroleum hydrocarbon in ethane cracking furnace, makes its radiant coil by ethane cracking furnace carry out scission reaction; The internal surface of described radiant coil has the oxide film that one deck at least comprises following middle a kind of element: Cr, Ni, Fe, Mn, Ti, Ca, Ba, Zr, Mg;
The thickness of described metal oxide film is 0.1～30 μ m; Preferably 0.1～15 μ m.
In concrete enforcement,
The chemical constitution of described oxide film by weight percentage, comprising:
Cr 25～45；
Ni 1～4；
Fe 1～10；
Mn 5～20；
C 0～0.5；
O 20～40；
Be selected from least one element 10～30 in Ca, Ba, Zr, Mg or Ti.
The preferred chemical constitution of described oxide film by weight percentage, comprising:
Cr 30～40；
Ni 2～3.5；
Fe 2～9；
Mn 7～15；
C 0～0.5；
O 25～35；
Be selected from least one element 12～25 in Ca, Ba, Zr, Mg or Ti.
Described radiant coil directly adds at least one element being selected from Ca, Ba, Zr, Mg or Ti to make tubing by the nichrome that includes Cr, Ni, Fe, Mn, C element in the conventional manufacturing processed of radiant coil, again described tubing is heat-treated under low oxygen partial pressure atmosphere, therein the sull of Surface Creation layer of metal.
The described nichrome for the manufacture of catalytic pyrolysis boiler tube is selected from one of following alloy: HK-40, HP-40, HP-45,35Cr45Ni steel, 28Cr35Ni steel.Wherein, HK-40 alloying element consists of: 23～27%Cr, 17～22%Ni, 0.35～0.45%C, < 1.5%Mn, surplus are Fe and micro impurity element; HP-40 alloying element consists of: 23～27%Cr, 33～37%Ni, 0.37～0.50%C, 0.8～2.0%Mn, surplus are Fe and other trace metals or non-metallic element; HP-45 alloying element consists of: 24～27%Cr, 33～37%Ni, 0.40～0.45%C, 1.0～1.5%Mn, surplus are Fe and other trace metals or non-metallic element; 35Cr45Ni Steel Alloy is elementary composition is: 33～37%Cr, 43～47%Ni, 0.40～0.60%C, 0.8～1.2%Mn, surplus are Fe and other trace metals or non-metallic element; 28Cr35Ni Steel Alloy is elementary composition is: 26～30%Cr, 33～37%Ni, 0.40～0.60%C, 0.8～1.2%Mn, 3.0～7.0%W, 13～17%Co, surplus are Fe and other trace metals or non-metallic element.
Described at least one element being selected from Ca, Ba, Zr, Mg or Ti is to add in the smelting process of nichrome with simple substance or oxide form; It is 0.1～10wt% that its addition accounts for nichrome total weight percent.Comparative optimization, its addition is to account for the Ca that nichrome total weight percent is 0.1～4.0wt%, and/or accounts for the Ba that nichrome total weight percent is 0.1～4.0wt%, and/or accounts for the Ti that nichrome total weight percent is 0.1～2.0wt%; More preferred, its addition is that to account for nichrome total weight percent be the metallic element Ca of 0.1～4.0wt% and accounts for the metallic element Ba that nichrome total weight percent is 0.1～4.0wt%.
Described low oxygen partial pressure atmosphere gas is selected from CO
2, CO, CH
4, NH
3, H
2o, H
2, N
2, Ar, He, airborne at least one, its oxygen partial pressure is less than or equal to 10
-16pa.Wherein, one of preferred following mixture: CO
2gaseous mixture, H with CO
2the gaseous mixture of O and CO, H
2and H
2the gaseous mixture of O; More preferably H
2and H
2the gaseous mixture of O, at described H
2and H
2in the gaseous mixture low oxygen partial pressure atmosphere gas of O, H
2the percent by volume that O accounts for low oxygen partial pressure atmosphere gas is 0.0006%～10.0%.
Described thermal treatment temp is 500 ℃～1100 ℃; Preferably 700 ℃～1100 ℃.The described heat treated time is 5～200 hours; Preferably 10～100 hours.
In sum, the sull on catalytic cracker pipe internal surface of the present invention is metal oxide film, and its chemical composition can be metallic element oxide compound separately, can be also the complex oxide of multiple element.This sull and boiler tube matrix mortise, can improve the yield of object product ethene, propylene significantly.
The present invention adopts centrifugal casting process to manufacture nichrome pipe, can be to make common smooth nichrome pipe, can be also abnormally-structured nichrome pipe.After the boiler tube made is machined, its internal surface light, non-scale, oxygen level < 5%.Then, this boiler tube of manufacturing is processed under above-mentioned temperature and low oxygen partial pressure atmosphere, under such condition, Ca, Ti, Ba, Cr, Mn, Zr, what the metallic elements such as Mg easily generated one deck densification to boiler tube rich surface base and by slow oxidation is combined firmly metal oxide film with boiler tube matrix, and Fe in boiler tube, the metallic element of the catalytic cokings such as Ni is substantially not oxidized and move mutually to body, result just generates in nichrome boiler tube internal surface original position the metal oxide film that one deck contains catalytic pyrolysis active ingredient, comprise: calcium oxide, titanium oxide, ba oxide, Mn oxide, chromated oxide, Zirconium oxide, magnesium oxide etc.This kind of method technique is simple, and effect is remarkable.In the time carrying out scission reaction in the nichrome boiler tube that petroleum hydrocarbon is containing this metal oxide film, can obviously improve the yield of object product ethene, propylene.
At present, the catalytic pyrolysis technology of what catalytic pyrolysis field was being developed be applicable to petroleum naphtha is mainly fixed-bed catalytic cracking technique, its technical characteristics is to have the component potassium aluminate of catalytic activity, vanadic acid calcium, alkaline-earth metal, transition metal oxide, unformed metallic compound, Si-Al zeolite etc., load on the carrier that zeolite or other material form or moulding separately, form the granules of catalyst of specified shape, granules of catalyst is placed on and in reactor, forms a fixed bed that has katalysis, petroleum hydrocarbon enters fixed-bed reactor after preheating, when reactor is heated to certain temperature, in reactor, there is catalytic pyrolysis effect and generate ethene in petroleum hydrocarbon, the object products such as propylene.Fixed-bed catalytic cracking technique not only needs newly-built fixed-bed reactor, and need to prepare the catalyzer of specified shape, therefore cannot on existing industrial ethylene pyrolyzer, implement.
Adopt method of the present invention, use a kind of special cracking furnace pipe, on the internal surface of this boiler tube, there is the metal oxide film of one deck densification, wherein contain catalytic pyrolysis active ingredient, carry out the catalytic pyrolysis of petroleum hydrocarbon.Because the metal oxides such as the calcium oxide in boiler tube internal surface metal oxide film, titanium oxide, chromic oxide, barium oxide have good catalytic cracking reaction activity, therefore make the yield of object product ethene, propylene obviously improve.Method of the present invention can be for laboratory scale simulation cracker, also can be in the pyrolyzer of industrial production ethene, and effect is good.Specifically, the beneficial effect that method of the present invention has is as follows:
1, use method of the present invention not need existing ethylene unit to carry out any transformation, the boiler tube that contains catalytic pyrolysis active ingredient in only need changing internal surface metal oxide film of the present invention in the time changing crack furnance radiation section furnace tube or the boiler tube in pyrolyzer is carried out to described processing.
2, use method of the present invention, can improve the yield of object product ethene and propylene more than 5%.
3, use method of the present invention, due to needn't filling solid catalyst, some problems of current research fixed-bed catalytic cracking technique be therefore avoided, as fixed-bed catalytic catalyst for cracking cannot bear comparatively high temps, or the shortcomings such as coking is serious under cracking temperature, and catalyst life is short.
Embodiment
Embodiment 1
In HK-40 nichrome smelting process, add and account for the alkaline earth metals calcium that alloy total weight percent is 2.0wt% (adding with oxide form), adopt centrifugal casting process to make
boiler tube, machined rear boiler tube internal surface light, non-scale, oxygen level is 2.97%, forms with X-ray energy dispersion spectrometer (EnergyDispersive Spectrometer is called for short EDS) analytical furnace tube-surface, the results are shown in Table 1.
Use this
boiler tube on the laboratory installation of homemade 200g/h inlet amount, carry out the processing of low oxygen partial pressure atmosphere, adopt H
2and H
2the gaseous mixture of O is processed gas, wherein H as low oxygen partial pressure atmosphere
2o accounts for H
2and H
2the percent by volume of O gaseous mixture is 2.0%, and concrete treatment condition are as follows:
Boiler tube size:
Oxidizing temperature: 900 ℃
Oxidization time: 20 hours
H
2flow velocity: 200ml/min
Flow rates: 4.08ml/min
Oxygen partial pressure: 10
-20pa
After cooling, with scanning electron microscope and its surface composition of energy spectrometer analysis, to analyze and show to generate at boiler tube internal surface the metal oxide film that a layer thickness is 1.8 μ m left and right, its main component is calcium, chromium, manganese, oxygen etc., the content of iron and nickel significantly reduces, and concrete outcome is in table 1.
Boiler tube internal surface component distribution (wt%) before and after processing in table 1 embodiment 1
| Cr | Ni | Fe | Ca | Mn | C | O | Other | (μ m) for thickness | |
| Before processing | 24.83 | 20.27 | 47.61 | 1.98 | 1.05 | 0.42 | 2.97 | 0.87 | / |
| After processing | 34.81 | 2.22 | 8.09 | 13.63 | 12.11 | 0.39 | 27.86 | 0.89 | 1.8 |
Take petroleum naphtha as cracking stock, to carrying out respectively cracking evaluation test through low oxygen partial pressure atmosphere boiler tube of the present invention after treatment and prior art HK-40 boiler tube described in embodiment 1, breaking test condition is as follows:
Raw material: industrial naphthas (physical property is in table 2)
Table 2 industrial naphthas physical property
Preheating temperature: 600 ℃
Cracking temperature: 825 ℃
Water-oil ratio: 0.5
Breaking test result is as shown in table 3, and it is high by 5.04% that boiler tube of the present invention adds propene yield than the ethene of prior art HK-40 boiler tube.
Comparative test result is evaluated in the cracking of table 3 embodiment 1
| Object product yield wt% | Hydrogen | Methane | Ethene | Propylene | Divinyl |
| HK-40 boiler tube | 0.88 | 12.79 | 24.56 | 12.18 | 3.13 |
| Boiler tube of the present invention | 0.91 | 11.48 | 26.91 | 14.87 | 4.42 |
Embodiment 2
In HP-40 nichrome smelting process, add that to account for alloy total weight percent be 2.0% alkaline earth metals calcium and 2.0% alkaline-earth metal barium (all adding with oxide form), adopt centrifugal casting process to make
boiler tube, machined rear boiler tube internal surface light, non-scale, oxygen level is 0.17%, forms with X-ray energy dispersion spectrometer (Energy Dispersive Spectrometer is called for short EDS) analytical furnace tube-surface, the results are shown in Table 4.
Use this
boiler tube on the laboratory installation of homemade 200g/h inlet amount, carry out the processing of low oxygen partial pressure atmosphere, adopt CO and H
2the gaseous mixture of O is processed gas, wherein H as low oxygen partial pressure atmosphere
2o accounts for CO and H
2the percent by volume of O gaseous mixture is 8.0%, and concrete treatment condition are as follows:
Boiler tube size:
Oxidizing temperature: 950 ℃
Oxidization time: 12 hours
CO flow velocity: 200ml/min
Flow rates: 17.4ml/min
Oxygen partial pressure: 10
-19pa
After cooling, with scanning electron microscope and its surface composition of energy spectrometer analysis, to analyze and show to generate at boiler tube internal surface the metal oxide film that a layer thickness is 2.5 μ m left and right, its main component is chromium, calcium, barium, manganese, oxygen etc., the content of iron and nickel significantly reduces, and concrete outcome is in table 4.
Boiler tube surface composition element distribution (wt%) before and after processing in table 4 embodiment 2
| Cr | Ni | Fe | Ca | Ba | Mn | C | O | Other | (μ m) for thickness | |
| Before processing | 25.13 | 34.78 | 33.56 | 1.94 | 1.97 | 1.12 | 0.45 | 0.17 | 0.88 | / |
| After processing | 30.49 | 3.12 | 3.23 | 12.31 | 11.75 | 7.57 | 0.42 | 30.26 | 0.85 | 2.5 |
Adopt cracking stock and the breaking test condition identical with embodiment 1, to carrying out respectively cracking evaluation test through low oxygen partial pressure atmosphere boiler tube of the present invention after treatment and prior art HP-40 boiler tube described in embodiment 2, test-results is as shown in table 5, and it is high by 7.11% that boiler tube of the present invention adds propene yield than the ethene of prior art HP-40 boiler tube.
Comparative test result is evaluated in the cracking of table 5 embodiment 2
| Object product yield wt% | Hydrogen | Methane | Ethene | Propylene | Divinyl |
| HP-40 boiler tube | 0.87 | 12.81 | 24.41 | 12.09 | 3.16 |
| Boiler tube of the present invention | 0.91 | 11.50 | 27.82 | 15.79 | 4.32 |
Embodiment 3
In 35Cr45Ni nichrome (be called for short 3545 nickel-chrome alloy steels) smelting process, add that to account for alloy total weight percent be 0.8% transition metals Ti and to account for Tube alloys total weight percent be 3.0% alkaline earth metals calcium (all adding with oxide form), adopt centrifugal casting process to make
boiler tube, machined rear boiler tube internal surface light, non-scale, oxygen level is zero, forms with X-ray energy dispersion spectrometer (EnergyDispersive Spectrometer is called for short EDS) analytical furnace tube-surface, the results are shown in Table 6.
Use this
boiler tube on the laboratory installation of homemade 200g/h inlet amount, carry out the processing of low oxygen partial pressure atmosphere, adopt CO
2process gas with the gaseous mixture of CO as low oxygen partial pressure atmosphere, concrete treatment condition are as follows:
Boiler tube size:
Oxidizing temperature: 1000 ℃
Oxidization time: 24 hours
CO flow velocity: 150ml/min
CO
2flow velocity: 50ml/min
Oxygen partial pressure: 10
-18pa
After cooling, with scanning electron microscope and its surface composition of energy spectrometer analysis, to analyze and show to generate at boiler tube internal surface the metal oxide film that a layer thickness is 3.2 μ m left and right, its main component is chromium, titanium, calcium, manganese, oxygen etc., the content of iron and nickel significantly reduces, and concrete outcome is in table 6.
Boiler tube surface composition element distribution (wt%) before and after processing in table 6 embodiment 3
| Cr | Ni | Fe | Ti | Ca | Mn | C | O | Other | (μ m) for thickness | |
| Before processing | 34.77 | 45.03 | 14.90 | 0.77 | 2.89 | 0.82 | / | / | 0.82 | / |
| After processing | 38.08 | 3.07 | 2.86 | 5.45 | 13.41 | 7.11 | / | 29.23 | 0.79 | 3.2 |
Adopt cracking stock and the breaking test condition identical with embodiment 1, to carrying out respectively cracking evaluation test through low oxygen partial pressure atmosphere boiler tube of the present invention after treatment and prior art 3545 boiler tubes described in embodiment 3, test-results is as shown in table 7, and it is high by 6.48% that boiler tube of the present invention adds propene yield than the ethene of prior art 3545 boiler tubes.
Comparative test result is evaluated in the cracking of table 7 embodiment 3
| Object product yield wt% | Hydrogen | Methane | Ethene | Propylene | Divinyl |
| 3545 boiler tubes | 0.88 | 12.80 | 24.38 | 12.05 | 3.13 |
| Boiler tube of the present invention | 0.91 | 11.49 | 27.29 | 15.62 | 4.17 |
Claims (5)
1. a method for preparing lower carbon number olefins by petroleum hydrocarbon catalytic pyrolysis, is characterized in that:
Described method comprises to be introduced petroleum hydrocarbon in ethane cracking furnace, makes its radiant coil by ethane cracking furnace carry out scission reaction;
The internal surface of described radiant coil has the oxide film that one deck at least comprises following middle a kind of element: Cr, Ni, Fe, Mn, Ti, Ca, Ba, Zr, Mg;
The thickness of described metal oxide film is 0.1～3.2 μ m;
Described radiant coil directly adds at least one element being selected from Ca, Ba, Zr, Mg or Ti to make tubing by the nichrome that includes Cr, Ni, Fe, Mn, C element in the conventional manufacturing processed of radiant coil, again described tubing is heat-treated under low oxygen partial pressure atmosphere, therein the sull of Surface Creation layer of metal;
By weight percentage, the chemical constitution of described oxide film comprises:
Be selected from least one element 10～30 in Ca, Ba, Zr, Mg or Ti;
Described low oxygen partial pressure atmosphere gas is selected from one of following mixture:
CO
2gaseous mixture, H with CO
2the gaseous mixture of O and CO, H
2and H
2the gaseous mixture of O, the oxygen partial pressure of described low oxygen partial pressure atmosphere gas is less than or equal to 10
-16pa;
CO
2in the gaseous mixture of CO, CO
2flow velocity: 50ml/min, the flow velocity of CO: 150ml/min;
H
2in the gaseous mixture of O and CO, the flow velocity of water vapour: 17.4ml/min, the flow velocity of CO: 200ml/min;
H
2and H
2the gaseous mixture of O, H
2flow velocity: 200ml/min, the flow velocity of water vapour: 4.08ml/min;
Described thermal treatment temp is 500 ℃～1100 ℃; The described heat treated time is 5～200 hours.
2. the method for catalytic pyrolysis preparing olefine in low carbon number as claimed in claim 1, is characterized in that by weight percentage, and the chemical constitution of described oxide film comprises:
Be selected from least one element 12～25 in Ca, Ba, Zr, Mg or Ti.
3. the method for catalytic pyrolysis preparing olefine in low carbon number as claimed in claim 1, is characterized in that:
The described nichrome for the manufacture of catalytic pyrolysis boiler tube is selected from one of following alloy:
HK-40, HP-40, HP-45,35Cr45Ni steel, 28Cr35Ni steel.
4. the method for catalytic pyrolysis preparing olefine in low carbon number as claimed in claim 1, is characterized in that:
Described at least one element being selected from Ca, Ba, Zr, Mg or Ti is to add in the smelting process of nichrome with simple substance or oxide form.
5. the method for catalytic pyrolysis preparing olefine in low carbon number as claimed in claim 1, is characterized in that:
Described thermal treatment temp is 700 ℃～1100 ℃; The described heat treated time is 10～100 hours.
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