CN102899065A - Method for producing olefin - Google Patents
Method for producing olefin Download PDFInfo
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- CN102899065A CN102899065A CN2011102170018A CN201110217001A CN102899065A CN 102899065 A CN102899065 A CN 102899065A CN 2011102170018 A CN2011102170018 A CN 2011102170018A CN 201110217001 A CN201110217001 A CN 201110217001A CN 102899065 A CN102899065 A CN 102899065A
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Abstract
he invention provides a method for producing olefin. The method comprises step of placing cracking raw materials in a cracking furnace tube for cracking, so as to obtain the olefin. The cracking furnace tube comprises a cracking furnace tube matrix, and an inert coating attached to an inner wall of the cracking furnace tube matrix. The inert coating can prevent contact between coke and cracking furnace tube matrix, but does not react with the cracking raw materials and / or cracking products; the inert coating has a porous structure with average pore radius of 0.5-15nm, and specific surface area from 1m<2> / g to less than 150m<2>/ g; the inert coating can also catalyze reaction between coke and water vapor; or the inert coating surface is attached by an active catalytic layer capable of catalyzing reaction between coke and water vapor; or the inert coating can catalyze reaction between coke and water vapor, and is also attached by an active catalytic layer capable of catalyzing reaction between coke and water vapor. The method for producing olefin provided by the invention has simple operation and good anti-coking performance.
Description
Technical field
The present invention relates to a kind of production method of alkene.
Background technology
Ethene is one of most important basic material of petroleum chemical industry.At present, produce the method for ethene take the pyrolysis in tubular furnace technology as main, this technology worldwide is widely applied.But can produce inevitably the problem of coking and carburizing in the production process of ethene, thereby the boiler tube internal diameter of pyrolyzer is diminished, tube drop increases, and hinders normally carrying out of scission reaction, has affected the yield of ethene, has reduced production efficiency.In addition, the high temperature of cracking is easy to impel the boiler tube inwall carburizing of pyrolyzer, and namely carbon distribution and boiler tube base material generation chemical reaction cause the reduction of furnace tube material performance, affect the work-ing life of boiler tube, shorten the cycle of operation of pyrolyzer.Therefore, when the boiler tube pipe surface temperature reaches tolerance limit or pressure drop and acquires a certain degree, in order to guarantee the normal operation of cracking furnace tube, must blowing out carry out coke cleaning.This shows, developing the method that can reduce coking of furnace tube of hydrocarbon cracking furnace is the prior development direction of producing ethene, and current petrochemical industry is had very large realistic meaning and economic worth.
At present, the method that suppresses cracking furnace tube coking mainly contains following several: raw material and the production process of (1) production control, for example, adopt the raw material that aromaticity content is low, hydrogen richness is high; Adopt the techniques such as hydrotreatment, Aromatics Extractive Project; (2) material of change cracking furnace tube, i.e. as much as possible minimizing can cause the content of the elements such as Fe, Ni of catalytic coking; (3) change the cracking furnace tube structure, for example, can in cracking furnace pipe, set up enhanced heat transfer member; (4) in cracking stock, add coking inhibitor, still, add coking inhibitor and not only can bring pollution to derived product, also can cause to a certain degree corrodibility to cracking furnace tube; (5) form the coating that one deck has mechanical property and thermostability concurrently by methods such as plasma spraying, hot sputter, vapour depositions at the internal surface of cracking furnace pipe, reducing hydrocarbons contacts with the direct of boiler tube, thereby reduce the catalytic activity of boiler tube surface Fe, Ni, reduce the frictional coefficient on boiler tube surface, effectively prevent sticking of coking particle, can effectively reduce the generation of coking.
For example, US 6537388 discloses to adopt and has contained the compound loaded in the ethene boiler tube of Cr, Si, after Passivation Treatment, Cr, Si Elements Diffusion form the Cr-Si bottom in the boiler tube matrix metal, then adopt the method for hot sputter, the compound that will contain Si, Al sprays on the Cr-Si bottom, forms Si-Al after the thermal treatment outer.Although aforesaid method can suppress the speed of coking to a certain extent, prolong the cycle of operation, the method complex process, equipment cost is high, and the using value of prepared boiler tube coating is not remarkable.
And for example, CN 1399670A discloses a kind for the treatment of process of metallic walls of cracking reactor, the method is included under 300-1100 ℃, to carry out pre-treatment with the water vapour air-flow that contains at least a silicon compound and at least a sulphur compound with treating the metallic surface that the cracking organism contacts, thereby reduce the coking on the metallic walls.
For another example, CN 1928020A discloses after cracker burns with steam and air, with the pretreating agent that the compound of sulfur-bearing and silicon forms, on the boiler tube metal, at first deposit the mixed coating of one deck sulphur and silicon-dioxide, with the bonding force of raising coating and cracking furnace pipe; After the first layer coating is complete, continue to add siliceous compound, add simultaneously the compound that contains magnesium, form layer of silicon dioxide and magnesian composite ceramic coat at silicon-dioxide and sulphur surface, the coke that produces to reduce the hydrocarbon cracking reaction.
But all there is the problem that the coating resistance to elevated temperatures is poor, sulfocompound pollutes the environment in aforesaid method, thereby, limited their applying in actual production.
Summary of the invention
The objective of the invention is in order to overcome the easy coking of cracking furnace pipe in olefin production process, and the high thermal resistance that the method that adopts prior art is processed the coating that obtains to cracking furnace pipe is relatively poor, can be to the defective of environment and complex process, and provide a kind of method that the anti-coking performance is good, high temperature resistant, the cracking furnace pipe of environmental protection carries out olefin production of using.
The invention provides a kind of production method of alkene, the method comprises cracking stock is placed cracking furnace pipe, under cracking condition, carry out cracking, obtain split product alkene, wherein, described cracking furnace pipe comprises the cracking furnace pipe matrix, be attached to the inert coating of cracking furnace pipe matrix inner wall surface, described inert coating is for preventing coke and cracking furnace pipe substrate contact and the coating that does not react with cracking stock and/or split product, described inert coating has vesicular structure, the average pore radius of described vesicular structure is 0.5-15nm, and the specific surface area of described inert coating is 1m
2/ g is extremely less than 150m
2/ g; Described inert coating can also catalytic coke and water vapour react; Perhaps, also adhere to can catalytic coke and the active catalytic layer that reacts of water vapour on described inert coating surface; Perhaps, described inert coating can also catalytic coke and water vapour react, and also adhere to can catalytic coke and the active catalytic layer that reacts of water vapour on described inert coating surface.
Generally, the cracking furnace pipe matrix contains iron and nickel, but described iron and nickel at high temperature catalyzed alkene generate thread coke, this coke is attached on the cracking furnace pipe, makes that the boiler tube internal diameter diminishes, tube drop increases, and has shortened the cycle of operation of pyrolyzer; By the matrix at cracking furnace pipe inert coating is set, can effectively stops contacting of iron and nickel isoreactivity component and hydro carbons, thereby greatly reduce the possibility of coking, improved alkene productive rate, increased cycle of operation of pyrolyzer.In addition, described inert coating can also catalytic coke and water vapour react, and/or set up at described inert coating can catalytic coke and the active catalytic layer that reacts of water vapour, thereby has further reduced the content of the coke on the cracking furnace pipe.The present inventor finds through research, and described inert coating has vesicular structure, and when the average pore radius of described vesicular structure is 0.5-15nm, and the specific surface area of described inert coating is 1 to less than 150m
2During/g, the inert coating of the cracking furnace pipe of gained has good anti-expansion and shrinkage, thereby described inert coating can not crack, and can also stop well contacting of coke and cracking furnace pipe matrix, and anti-coking is effective.In a preferred embodiment of the present invention, before the load inert coating, the cracking furnace pipe matrix is carried out surface treatment, the roughness Ra that makes described cracking furnace pipe surface is 0.2-0.8 μ m, then inert coating can be attached on the cracking furnace pipe matrix well, and the bonding force stronger with cracking furnace pipe formation, namely have excellent resistance to erosion ability.In another preferred embodiment of the present invention, described the first metal oxide is selected from one or more in aluminum oxide, titanium oxide, zirconium white, manganese picotite, magnesium-aluminium spinel and the manganese silicon spinel, the anti-coking excellent performance of the inert coating that is comprised of these first metal oxides can further improve the anti-coking performance of the cracking furnace pipe of gained.
Other features and advantages of the present invention will partly be described in detail in embodiment subsequently.
Embodiment
Below the specific embodiment of the present invention is elaborated.Should be understood that, embodiment described herein only is used for description and interpretation the present invention, is not limited to the present invention.
The production method of alkene provided by the invention comprises cracking stock is placed cracking furnace pipe, under cracking condition, carry out cracking, obtain split product alkene, wherein, described cracking furnace pipe comprises the cracking furnace pipe matrix, be attached to the inert coating of cracking furnace pipe matrix inner wall surface, described inert coating is for preventing coke and cracking furnace pipe substrate contact and the coating that does not react with cracking stock and/or split product, described inert coating has vesicular structure, the average pore radius of described vesicular structure is 0.5-15nm, and the specific surface area of described inert coating is 1m
2/ g is extremely less than 150m
2/ g; Described inert coating can also catalytic coke and water vapour react; Perhaps, also adhere to can catalytic coke and the active catalytic layer that reacts of water vapour on described inert coating surface; Perhaps, described inert coating can also catalytic coke and water vapour react, and also adhere to can catalytic coke and the active catalytic layer that reacts of water vapour on described inert coating surface.
Need to prove, cracking furnace pipe provided by the invention can include only cracking furnace pipe matrix and inert coating, described inert coating not only can prevent coke and cracking furnace pipe substrate contact and not react with cracking stock and/or split product, can also catalytic coke and water vapour react.Perhaps, cracking furnace pipe provided by the invention can comprise cracking furnace pipe matrix, inert coating and active catalytic layer; Described inert coating can prevent coke and cracking furnace pipe substrate contact and not react with cracking stock and/or split product; Described active catalytic layer can catalytic coke and water vapour react.In addition, cracking furnace pipe provided by the invention can also comprise cracking furnace pipe matrix, inert coating and active catalytic layer; Wherein, described inert coating not only can prevent coke and cracking furnace pipe substrate contact and not react with cracking stock and/or split product, can also catalytic coke and water vapour react; Described active catalytic layer can further promote described inert coating catalytic coke and water vapour to react.
According to the present invention, the effect of described inert coating is to prevent coke and cracking furnace pipe substrate contact, and the average pore radius of the vesicular structure by controlling described inert coating is 0.5-15nm, is preferably 0.5-3.7nm; Specific surface area is 1 to less than 150m
2/ g is preferably 10-140m
2/ g not only can guarantee the isolation of described coke and cracking furnace pipe matrix well, can also make the inert coating of described cracking furnace pipe have good anti-expansion and shrinkage, has reduced its possibility that cracks.
According to the present invention, although the selectable range of the thickness of described inert coating is wider,, under the preferable case, in order to improve the anti-coking performance and to guarantee simultaneously work-ing life of cracking furnace pipe, as a rule, when the thickness of described inert coating is 2-100 μ m.The present inventor finds, when the thickness of described inert coating more preferably during 10-50 μ m, the cracking furnace pipe that not only can guarantee gained has good anti-coking performance, can also guarantee that inert coating can stick on the cracking furnace pipe matrix well, smooth, not easy to crack, over-all properties is splendid.
According to the present invention, described inert coating also can variously can prevent coke and cracking furnace pipe substrate contact and the coating that does not react with cracking stock and/or split product for existing, for example, described inert coating contains silicon-dioxide and/or the first metal oxide, perhaps, described inert coating contains silicon-dioxide and/or the first metal oxide and the second metal active constituent; Metal in described the first metal oxide is selected from one or more in aluminium, titanium, zirconium, manganese, chromium, lanthanum and the magnesium; Described active catalytic layer contains the second metal active constituent.
Need to prove, the first metal oxide of the present invention can be for only containing a kind of metal oxide of metal, as being selected from aluminum oxide, titanium oxide, zirconium white, manganese oxide, chromic oxide and the magnesium oxide one or more.Moreover described the first metal oxide can also contain the complex metal oxides of two or more metals, and the metal in the described complex metal oxides can be selected from two or more in aluminium, titanium, zirconium, manganese, chromium, lanthanum and the magnesium.Under the preferable case, described complex metal oxides is spinel type composite metal oxide, for example is in manganese picotite, magnesium-aluminium spinel and the manganese silicon spinel one or more; Perhaps being the perovskite typed complex metal oxides, for example is LaAlO
3, LaMnO
3And MnSiO
3In one or more.The present inventor finds, the existence of lattice oxygen in spinel type composite metal oxide and the perovskite typed complex metal oxides, can promote coke and water vapor generation water-gas reaction, and spinel type composite metal oxide and and the perovskite typed complex metal oxides have good resistance to elevated temperatures and anti-charing ability, therefore, when described the first metal oxide was spinel type composite metal oxide or perovskite typed complex metal oxides, the anti-coking effect of the inert coating of gained was very good.
According to the present invention, the second metal active constituent that contains in the described inert coating can be identical with the second metal active constituent in the active catalytic layer, also can be different, and can be selected from existing various can catalytic coke and the metal active constituent that reacts of water vapour, under the preferable case, described the second metal active constituent all is that the form with metal oxide exists basically, and the metal in described the second metal active constituent can be selected from one or more in lithium, sodium, potassium, rubidium, calcium, strontium, barium, molybdenum, cobalt, nickel, iron, copper, cerium and the praseodymium.
According to the present invention, the charge capacity of described the second metal active constituent can in very large range change, but in order to improve catalytic performance and to reduce production costs, under the preferable case, in metallic element, the charge capacity of described the second metal active constituent is 0.5-40g/m
2, 1-20g/m more preferably
2Described charge capacity refers to the weight of the second metal active constituent of institute's load on the per surface area.
According to the present invention, for the bonding force between the coating that further strengthens described cracking furnace pipe, improve its flushing resistance, preferably, described cracking furnace pipe matrix has coarse inner wall surface, and when the roughness Ra of inner wall surface more than 0.2 μ m, when being preferably 0.2-0.8 μ m, inert coating can load on the described cracking furnace pipe matrix at an easy rate, and the flushing resistance of the cracking furnace pipe of gained is also very good.
According to the present invention, described cracking stock places cracking furnace pipe, carries out cracking and obtain split product alkene under cracking condition; Described cracking condition generally includes cracking temperature and cracking pressure, and described cracking temperature and cracking pressure can carry out choose reasonable according to practical situation, and as a rule, described cracking temperature can be 750-1000 ℃, is preferably 800-900 ℃; Cracking pressure can be 0-0.3MPa, is preferably 0.15-0.25MPa.
In addition, the preparation method of cracking furnace pipe of the present invention is included in cracking furnace pipe matrix inner wall surface and forms inert coating, described inert coating is for preventing coke and cracking furnace pipe substrate contact and the coating that does not react with cracking stock and/or split product, described inert coating has vesicular structure, the average pore radius of described vesicular structure is 0.5-15nm, is preferably 0.5-3.7nm; The specific surface area of described inert coating is 1 to less than 150m
2/ g is preferably 10-140m
2/ g; Described inert coating can also catalytic coke and water vapour react; Perhaps, the method also is included in the active catalytic layer that the enough catalytic cokes of described inert coating surface formation energy and water vapour react; Perhaps, described inert coating can also catalytic coke and water vapour react, and the method also is included in the active catalytic layer that the enough catalytic cokes of described inert coating surface formation energy and water vapour react.
Described inert coating can be by loading on cracking furnace pipe matrix inner wall surface with the first slurry mix and/or the second slurry mix and forming through the first thermal treatment; Described the first slurry mix is for being that 2-5 or pH are under the condition of 9-11 at pH, and at least a, the colloidal sol in silicon-dioxide, the first metal oxide and the first metal oxide hydrate and water are mixed to get; Described the second slurry mix is for being that 2-5 or pH are under the condition of 9-11 at pH, and silicon-dioxide and/or the first metal oxide, the first metal oxide hydrate and water are mixed to get.
For realize described cracking furnace pipe can prevent coke and cracking furnace pipe substrate contact and do not react with cracking stock and/or split product but can catalytic coke and water vapour react; According to a kind of embodiment of the present invention, can also contain bimetallic soluble salt in described the first slurry mix and the second slurry mix; Perhaps, according to another kind of embodiment of the present invention, described cracking furnace pipe also comprises the active catalytic layer that is attached to the inert coating surface, and described active catalytic layer is the coating by bimetallic soluble salt being loaded on described inert coating surface and forming through the second thermal treatment; Perhaps with above-mentioned dual mode combination.
According to the present invention, metal in described the first metal oxide is selected from one or more in aluminium, titanium, zirconium, manganese, chromium, lanthanum and the magnesium, need to prove, the first metal oxide of the present invention can be for only containing a kind of metal oxide of metal, as being selected from aluminum oxide, titanium oxide, zirconium white, manganese oxide, chromic oxide and the magnesium oxide one or more.Moreover described the first metal oxide can also contain the complex metal oxides of two or more metals, and the metal in the described complex metal oxides can be selected from two or more in aluminium, titanium, zirconium, manganese, chromium, lanthanum and the magnesium.The present inventor finds, when described the first metal oxide is complex metal oxides, be preferably spinel type composite metal oxide, for example be in manganese picotite, magnesium-aluminium spinel and the manganese silicon spinel one or more, perhaps being the perovskite typed complex metal oxides, for example is LaAlO
3, LaMnO
3, and MnSiO
3In one or more the time, the anti-coking effect of the inert coating of gained is very good.Metal in described the first metal oxide hydrate is preferably selected from one or more in aluminium, titanium, zirconium, manganese, chromium, lanthanum and the magnesium.Described bimetallic soluble salt can be the soluble salt of existing various metals, as long as guarantee the product that after the first thermal treatment and/or the second thermal treatment, obtains can catalytic coke and water vapour react, for example, described bimetallic soluble salt can be selected from bimetallic nitrate, vitriol, carbonate, phosphoric acid salt, in chlorate and the acetate one or more, metal in the described bimetallic soluble salt can be selected from lithium, sodium, potassium, rubidium, calcium, strontium, barium, molybdenum, cobalt, nickel, iron, copper, in cerium and the praseodymium one or more, preferably, described bimetallic soluble salt is selected from nitrocalcite, nickelous nitrate, SODIUMNITRATE, salt of wormwood, yellow soda ash, vitriolate of tartar, in ferric sulfate and the cerous nitrate one or more.
The present invention is not particularly limited the content of each component in the first slurry mix of forming inert coating and the second slurry mix, can prevent coke and cracking furnace pipe substrate contact and the inert coating that does not react with cracking stock and/or split product as long as can form, and guarantee that the inert coating that obtains has the microvoid structure that average pore radius is 0.5-15nm under the first heat-treat condition, and the specific surface area of described inert coating is 1m
2/ g is extremely less than 150m
2/ g gets final product, for example, the mass ratio of the quality of the quality of the total mass of silicon-dioxide and the first metal oxide and the first metal oxide hydrate, colloidal sol, the second metal soluble salt and water is 0.1-0.8: 0.1-1: 0-0.2 described in described the first slurry mix: 1, be preferably 0.1-0.6: 0.1-1: 0.01-0.2: 1; The mass ratio of the quality of the quality of the total mass of silicon-dioxide and the first metal oxide, the first metal oxide hydrate, the second metal soluble salt and water is 0.1-0.4: 0.01-0.4: 0-0.15 described in described the second slurry mix: 1, be preferably 0.15-0.3: 0.015-0.15: 0.01-0.09: 1.
According to the present invention, need to prove, if when containing simultaneously silicon-dioxide, the first metal oxide and the first metal oxide hydrate in described the first slurry mix, then " total mass " refers to the total mass of silicon-dioxide and the first metal oxide and the first metal oxide hydrate in the aforementioned proportion, and the mass ratio of each material refers to the total mass of silicon-dioxide and the first metal oxide and the first metal oxide hydrate, the quality of colloidal sol, the quality of the second metal soluble salt and the mass ratio of water in the first slurry mix.If when containing any two kinds in silicon-dioxide, the first metal oxide and the first metal oxide hydrate in described the first slurry mix, then " total mass " refers to any two kinds total mass in silicon-dioxide, the first metal oxide and the first metal oxide hydrate, and the mass ratio of each material refers to any two kinds total mass in silicon-dioxide, the first metal oxide and the first metal oxide hydrate, the quality of colloidal sol, the quality of the second metal soluble salt and the mass ratio of water in the first slurry mix; Under the preferable case, described the first slurry mix is silicon-dioxide or the first metal oxide, and the mixture of the first metal oxide hydrate, and the mass ratio of the quality of described silicon-dioxide or the first metal oxide and described the first metal oxide hydrate is 1: 0.05-1.If when only containing a kind of in silicon-dioxide, the first metal oxide or the first metal oxide hydrate in described the first slurry mix, described " total mass " refers to the quality of silicon-dioxide or the first metal oxide or the first metal oxide hydrate, and the mass ratio of each material refers to the quality of silicon-dioxide or the first metal oxide or the first metal oxide hydrate, the quality of colloidal sol, the quality of the second metal soluble salt and the mass ratio of water in the first slurry mix.The mass ratio of each material and above-mentioned equivalent in meaning will repeat no more at this in described the second slurry mix.
According to the present invention, the colloidal sol in described the first slurry mix is selected from one or more in aluminium colloidal sol, silicon sol, titanium colloidal sol and the zirconium colloidal sol.Described colloidal sol can prepare by existing the whole bag of tricks, for example, can be with after sol precursor and the solvent, at a certain temperature, be that the Water Under solution of 9-11 or dissolving, ageing obtain in the pH value for 2-5 or pH; Described sol precursor can be in the soluble inorganic salt of the soluble inorganic salt of the soluble inorganic salt of the oxide compound of the oxide compound of alkoxide, titanyl compound and the hydrate thereof of the alkoxide of the alkoxide of titanium, aluminium, zirconium, aluminium and hydrate thereof, zirconium and hydrate thereof, titanium, aluminium, zirconium and the saturated hydrocarbyl organoalkoxysilane that carbonatoms is 1-20 at least a; Described solvent can be the existing various solvents that are applicable to prepare colloidal sol, but in order to save cost and minimizing to the pollution of environment, generally, described solvent is water; The pH value can be by adding acid or alkali is regulated.
According to the present invention, in order to regulate the first slurry mix of forming inert coating and viscosity and the stability of the second slurry mix, can also contain tensio-active agent and other metal-salts in described the first slurry mix and/or the second slurry mix.Described tensio-active agent can be selected from one or more in polyvinyl alcohol, hydroxy propyl cellulose, methylcellulose gum and the polyoxyethylene glycol usually; Described other metal-salts generally can be one or more of aluminum nitrate, zirconium nitrate and Titanium Nitrate.
According to the present invention, the method of described load inert coating can be existing the whole bag of tricks, for example can be in pickling process, plasma spraying, chemical vapour deposition (CVD), plasma reinforced chemical vapour deposition (PEVCD), physical vapor deposition (PVD) and the sol-gel method one or more; Wherein, physical vapor deposition (PVD) method generally includes again cathode arc, sputter (DC, RF, magnetron) and electron-beam vapor deposition method.The method of described supported active Catalytic Layer also can be existing the whole bag of tricks, for example, the cracking furnace pipe behind the load inert coating can be immersed in the solution that contains active ingredient.
In the process of described cracking furnace pipe preparation, can be by described inert coating of load of above method and active catalytic layer; Also can pass through the repeatedly described inert coating of load and active catalytic layer, until reach desired thickness or charge capacity.The consumption of described the first slurry mix and/or the second slurry mix is preferably 0.5-100 μ m as long as guarantee the thickness of the inert coating of gained, the consumption of described active ingredient is as long as guarantee, in metallic element, the charge capacity of described the second metal active constituent is preferably 0.5-40g/m
2Get final product.
According to the present invention, the described first heat treated condition generally includes treatment temp and treatment time, as long as described treatment temp and treatment time can guarantee the inert coating of the cracking furnace pipe of gained and have vesicular structure, the average pore radius of described vesicular structure is 0.5-15nm, and guarantees that the specific surface area of inert coating is 1m
2/ g is extremely less than 150m
2/ g gets final product, and under the preferable case, the described first heat treated treatment temp is 300-1100 ℃, and more preferably 600-1100 ℃, the treatment time is 0.5-10 hour, more preferably 1-8 hour.
The present invention is to the described second heat treated condition also not restriction, active ingredient can be attached on the inert coating well to be got final product, under the preferable case, the described second heat treated treatment temp is 300-1100 ℃, more preferably 600-1100 ℃, treatment time is 0.5-10 hour, more preferably 1-8 hour.
According to the present invention, the preparation method of described cracking furnace pipe also is included in before the described cracking furnace pipe matrix surface load inert coating, described cracking furnace pipe matrix is carried out surface treatment, as long as described surface-treated condition guarantee makes the roughness Ra of cracking furnace pipe matrix surface of gained more than 0.2 μ m, is preferably 0.2-0.8 μ m and gets final product.Generally, described surface-treated method comprises: in oxidizing atmosphere, under 600-1100 ℃, described cracking furnace pipe matrix was carried out oxide treatment 0.5-24 hour.
Described oxidizing atmosphere refers to generate with the cracking furnace pipe matrix gas of corresponding oxide grain, for example can be in water vapour, carbonic acid gas, air and the oxygen one or more.Keep the method for oxidizing atmosphere can be for passing into above-mentioned any one gas or gaseous mixture in cracking furnace pipe, in order to dilute the concentration of above-mentioned gas, thereby control degree of oxidation and time can also be contained non-oxidizing gas in the described oxidizing atmosphere; Described non-oxidizing gas refers to not any one gas or the gaseous mixture with cracking furnace pipe generation chemical reaction, for example can be in nitrogen and the periodic table of elements zero group gas one or more.
According to the present invention, the surface treatment of matrix also is included in before the oxide treatment, also preferably include cracking furnace pipe matrix inner wall surface is cleaned with clean-out system, with greasy dirt and other impurity of removing described cracking furnace pipe matrix inner wall surface, described clean-out system can for acid, water, alcohol etc. can wipe oil conventional cleaning reagent.
The below will further describe in detail the present invention by embodiment.
In following embodiment and Comparative Examples, obtain the thickness of described inert coating with determination of electron microscopy, and adopt nitrogen absorption BET method to record its specific surface area and average pore radius; Record the charge capacity of active ingredient in the described active catalytic layer with the ICP method.
Preparation Example 1
This Preparation Example illustrates the preparation of colloidal sol provided by the invention.
24g pseudo-boehmite and 200mL deionized water are mixed, obtained mixture in 0.5 hour 85 ℃ of lower stirrings, be the salpeter solution of 1.6mol/L with concentration, the pH value of said mixture is adjusted to 2.5, after 24 hours, obtaining average particulate diameter is stable, the transparent aluminium colloidal sol of 15nm 85 ℃ of lower stirrings in continuation.
Preparation Example 2
This Preparation Example illustrates the preparation of colloidal sol provided by the invention.
40g silica flour, 15mL water glass and 150mL deionized water are mixed, obtained mixture in 1 hour 90 ℃ of lower stirrings, be the sodium hydroxide solution of 1.6mol/L with concentration, the pH value of said mixture is adjusted to 11, after 24 hours, obtaining particle diameter is stable, the transparent silicon sol of 20nm 90 ℃ of lower stirrings in continuation.
Preparation Example 3
This Preparation Example illustrates the preparation of colloidal sol provided by the invention.
The 23g butyl (tetra) titanate is dissolved in the 100mL ethanol, under the room temperature rapid stirring evenly after, with 200mL deionized water mix and blend 0.5h, adding concentration is that the salpeter solution of 1.6mol/L is adjusted to 2 with the pH value, 85 ℃ of lower constant temperature stir 12h, be cooled to constant temperature, obtaining average particulate diameter is stable, the transparent titanium colloidal sol of 100nm.
Embodiment 1
This embodiment explanation the invention provides the preparation of cracking furnace pipe.
(1) pre-treatment:
To be of a size of
HK40 boiler tube matrix ultrasonic cleaning 30min in acetone, then clean 10min in deionized water for ultrasonic, to remove oil, oxide compound and other impurity on the metallic surface.Under 120 ℃, carry out drying with described through the boiler tube matrix after the ultrasonic cleaning, then under 750 ℃ under air atmosphere oxidation 2h, obtain roughness Ra and be 0.3 cracking furnace pipe matrix.
(2) form coating at the cracking furnace pipe matrix:
Behind aluminium colloidal sol, 20g pseudo-boehmite and the 50mL deionized water mixing and ball milling 18h that 30g is made by Preparation Example 1, the salpeter solution that adds concentration and be 1.6mol/L to 3.5, obtains the first slurry mix with the conciliation of pH value.Above-mentioned the first slurry mix is loaded on the cracking furnace pipe matrix that step (1) obtains by pickling process, at 120 ℃ after lower dry 1 hour, place 800 ℃ of lower roastings 2 hours, obtain inert coating.To contain the cracking furnace pipe of inert coating at Ca (NO
3)
2Solution (Ca (NO
3)
2Concentration be 2.5mol/L) in the dipping 5min, after the seasoning, place 800 ℃ of lower roastings 2 hours, obtain the active catalytic layer.Through measuring, the average pore radius of the inert coating of gained cracking furnace pipe is 2nm, and specific surface area is 140m
2/ g, thickness are 20 microns; In calcium constituent, the charge capacity of described active ingredient is 1.3g/m
2
Embodiment 2
This embodiment explanation the invention provides the preparation of cracking furnace pipe.
(1) pre-treatment:
To be of a size of
HP40 boiler tube matrix ultrasonic cleaning 30min in acetone, then soak 10min with 1% aqueous nitric acid, to remove oil, oxide compound and other impurity on the metallic surface.Under 120 ℃, carry out drying with described through the boiler tube matrix after the ultrasonic cleaning, then under 850 ℃ under air atmosphere oxidation 2h, obtain roughness Ra and be 0.5 cracking furnace pipe matrix.
(2) form coating at the cracking furnace pipe matrix:
Behind silicon sol, 20g water glass and the 65mL deionized water mixing and ball milling 18h that 15g is obtained by Preparation Example 2, the ammoniacal liquor that adds concentration and be 1.6mol/L to 10, obtains the first slurry mix with the conciliation of pH value.Above-mentioned the first slurry mix is loaded on the cracking furnace pipe matrix that step (1) obtains by pickling process, at 120 ℃ after lower dry 1 hour, place 900 ℃ of lower roastings 2 hours, obtain inert coating.To contain the cracking furnace pipe of inert coating at Na
2CO
3-K
2CO
3Solution (wherein, Na
2CO
3Concentration be 1.1mol/L; K
2CO
3Concentration be 1.9mol/L) in the dipping 10min, after the seasoning, place 900 ℃ of lower roastings 2 hours, obtain the active catalytic layer.Through measuring, the average pore radius of the inert coating of gained cracking furnace pipe is 2nm, and specific surface area is 120m
2/ g, thickness are 25 microns; In the total amount of sodium and potassium, the charge capacity of described active ingredient is 2.7g/m
2
Embodiment 3
This embodiment explanation the invention provides the preparation of cracking furnace pipe.
(1) pre-treatment:
To be of a size of
3545 boiler tubes ultrasonic cleaning 30min in acetone, then use deionized water ultrasonic cleaning 10min, to remove oil, oxide compound and some impurity on the metallic surface.Under 120 ℃, carry out drying with described through the boiler tube matrix after the ultrasonic cleaning, then (content of nitrogen is 60 volume % under nitrogen and oxygen mix atmosphere under 1000 ℃; The content of oxygen is 40 volume %) oxidation 2h, obtain roughness Ra and be 0.8 cracking furnace pipe matrix.
(2) form coating at the cracking furnace pipe matrix:
Behind the silicon sol that 30g is obtained by Preparation Example 2,20g titanium dioxide, 20g zirconium white, the 130mL deionized water mixing and ball milling 18h, the ammoniacal liquor that adds concentration and be 1.6mol/L to 10, obtains the first slurry mix with the conciliation of pH value.Above-mentioned the first slurry mix is loaded on the cracking furnace pipe matrix that step (1) obtains by pickling process, at 120 ℃ after lower dry 1 hour, place 950 ℃ of lower roastings 2 hours, obtain inert coating.To contain the cracking furnace pipe of inert coating at Ni (NO
3)
2-KNO
3Solution (wherein, Ni (NO
3)
2Concentration be 2.5mol/L; KNO
3Concentration be 2.5mol/L) in the dipping 2min, after the seasoning, place 950 ℃ of lower roastings 2 hours, obtain the active catalytic layer.Through measuring, the average pore radius of the inert coating of gained cracking furnace pipe is 3.5nm, and specific surface area is 80m
2/ g, thickness are 25nm; In the total amount of nickel and potassium, the charge capacity of described active ingredient is 3.3g/m
2
Embodiment 4
This embodiment explanation the invention provides the preparation of cracking furnace pipe.
(1) pre-treatment:
To be of a size of
HK40 boiler tube matrix ultrasonic cleaning 30min in acetone, then clean 10min in deionized water for ultrasonic, to remove oil, oxide compound and other impurity on the metallic surface.Under 120 ℃, carry out drying with described through the boiler tube matrix after the ultrasonic cleaning, then under 750 ℃ under air atmosphere oxidation 2h, obtain roughness Ra and be 0.3 cracking furnace pipe matrix.
(2) form coating at the cracking furnace pipe matrix:
Titanium colloidal sol, 20g pseudo-boehmite, 20g manganese picotite, 5g Ce (NO that 60g is obtained by Preparation Example 3
3)
3, behind the 100mL deionized water mixing and ball milling 18h, the salpeter solution that adds concentration and be 1.6mol/L to 4, obtains the first slurry mix with the conciliation of pH value.Above-mentioned the first slurry mix is loaded to by pickling process on the cracking furnace pipe matrix that is obtained by step (1), after 1 hour, place 1000 ℃ of lower roastings 2 hours 120 ℃ of lower dryings, obtain inert coating.To contain the cracking furnace pipe of inert coating at K
2CO
3Solution (K
2CO
3Concentration be 3.8mol/L) in the dipping 5min, after the seasoning, place 1000 ℃ of lower roastings 2 hours, obtain the active catalytic layer.Through measuring, the average pore radius of the inert coating of gained cracking furnace pipe is 10nm, and specific surface area is 20m
2/ g, thickness are 25 microns; In cerium and potassium element, the charge capacity of described active ingredient is 4.6g/m
2
Embodiment 5
This embodiment explanation the invention provides the preparation of cracking furnace pipe.
(1) pre-treatment:
To be of a size of
HK40 boiler tube matrix ultrasonic cleaning 30min in acetone, then clean 10min in deionized water for ultrasonic, to remove oil, oxide compound and other impurity on the metallic surface.Under 120 ℃, carry out drying with described through the boiler tube matrix after the ultrasonic cleaning, then under 750 ℃ under air atmosphere oxidation 2h, obtain roughness Ra and be 0.3 cracking furnace pipe matrix.
(2) form coating at the cracking furnace pipe matrix:
With 5g pseudo-boehmite, 15g Alpha-alumina, 5g lanthanum nitrate, 5g KNO
3Behind 100mL deionized water mixing and ball milling 18h, adding concentration is that the salpeter solution of 1.6mol/L reconciles the pH value to 4, obtains the first slurry mix.Above-mentioned the first slurry mix is loaded to by pickling process on the cracking furnace pipe matrix that is obtained by step (1), after 1 hour, place 1000 ℃ of lower roastings 2 hours 120 ℃ of lower dryings, obtain the first inert coating.Repeat above-mentioned steps, load the second inert coating on the first inert coating.Through measuring, the average pore radius of the inert coating of gained cracking furnace pipe is 7nm, and specific surface area is 40m
2/ g, thickness are 45nm.
Embodiment 6
This embodiment explanation the invention provides the preparation of cracking furnace pipe.
Method according to embodiment 2 prepares cracking furnace pipe, different is to change the heat-treat condition (namely after 1 hour, placing 700 ℃ of lower roastings 2 hours 120 ℃ of lower dryings) of inert coating, the average pore radius that makes the inert coating that obtains is 1.5nm, and specific surface area is 148m
2/ g.
Embodiment 7
This embodiment explanation the invention provides the preparation of cracking furnace pipe.
Method according to embodiment 2 prepares cracking furnace pipe, different is to change the heat-treat condition (namely after 1 hour, placing 950 ℃ of lower roastings 2 hours 120 ℃ of lower dryings) of inert coating, the average pore radius that makes the inert coating that obtains is 3.8nm, and specific surface area is 102m
2/ g.
Embodiment 8
This embodiment explanation the invention provides the preparation of cracking furnace pipe.
Method according to embodiment 2 prepares cracking furnace pipe, and different is, changes the surface treatment condition of cracking furnace pipe matrix, and the roughness Ra that makes the cracking furnace pipe matrix that obtains is 0.1, that is:
To be of a size of
HP40 boiler tube matrix ultrasonic cleaning 30min in acetone, then soak 10min with 1% aqueous nitric acid, to remove oil, oxide compound and other impurity on the metallic surface.Under 120 ℃, carry out drying with described through the boiler tube matrix after the ultrasonic cleaning, then under 600 ℃ under air atmosphere oxidation 2h, obtain roughness Ra and be 0.1 cracking furnace pipe matrix.
Comparative Examples 1
This Comparative Examples is used for the preparation of explanation reference cracking furnace pipe.
Method according to embodiment 1 prepares cracking furnace pipe, and different is, the cracking furnace pipe matrix is not carried out coating load, that is, concrete steps are:
To be of a size of
HK40 boiler tube matrix ultrasonic cleaning 30min in acetone, then clean 10min in deionized water for ultrasonic, to remove oil, oxide compound and other impurity on the metallic surface.Under 120 ℃, carry out drying with described through the boiler tube matrix after the ultrasonic cleaning, then under 750 ℃ under air atmosphere oxidation 2h, obtain roughness Ra and be 0.3 cracking furnace pipe matrix.
Comparative Examples 2
This Comparative Examples is used for the preparation of explanation reference cracking furnace pipe.
Method according to embodiment 2 prepares cracking furnace pipe, different is to change the heat-treat condition (namely after 1 hour, placing 600 ℃ of lower roastings 3 hours 120 ℃ of lower dryings) of inert coating, the average pore radius that makes the inert coating that obtains is 0.5nm, and specific surface area is 160m
2/ g.
Test case 1-8
This test case is used for the anti-coking performance test of explanation cracking furnace pipe.
The petroleum naphtha that the 200g physical properties is as shown in table 1 passes in the preheater with the speed of 100g/h, simultaneously, the 100g deionized water passes through in the corresponding preheater with the speed of 50g/h, after 600 ℃ of lower preheatings mix, enter in the embodiment 1-8 gained cracking furnace pipe, 850 ℃ of lower cracking 2 hours, obtain splitting gas 160L.After cracking is complete, pass into nitrogen and oxygen to described cracking furnace pipe, the flow of control nitrogen is that the flow of 1L/min, oxygen is 0.2L/min, burns the CO that produces in the burning process and CO under 850 ℃
2Concentration by infrared instrument on-line measurement, the volume of the gas that produces in the roasting is noted down online by wet flow indicator, the carbon content that finally calculates coke gas is the coking amount of cracking process.Detected result is as shown in table 2.
Table 1
Contrast test example 1-2
This test case is used for the anti-coking performance test of explanation cracking furnace pipe.
Detect the anti-coking performance of cracking furnace pipe according to the method for test case 1-8, different is, what detect is the cracking furnace pipe that the method by Comparative Examples 1-2 obtains, and detected result is as shown in table 2.
Table 2
Contrast by test case 1-8 and contrast test example 1-2 can find out, adopts the anti-coking performance of the cracking furnace pipe that method of the present invention obtains good, and do not contain element sulphur in the coating, can not work the mischief to environment; Can find out by test case 2 and the contrast of test case 6-8, adopt the anti-coking performance of the cracking furnace pipe that optimal way of the present invention obtains more excellent.
Claims (15)
1. the production method of an alkene, the method comprises cracking stock is placed cracking furnace pipe, under cracking condition, carry out cracking, obtain split product alkene, it is characterized in that, described cracking furnace pipe comprises the cracking furnace pipe matrix, be attached to the inert coating of cracking furnace pipe matrix inner wall surface, described inert coating is for preventing coke and cracking furnace pipe substrate contact and the coating that does not react with cracking stock and/or split product, described inert coating has vesicular structure, the average pore radius of described vesicular structure is 0.5-15nm, and the specific surface area of described inert coating is 1m
2/ g is extremely less than 150m
2/ g; Described inert coating can also catalytic coke and water vapour react; Perhaps, also adhere to can catalytic coke and the active catalytic layer that reacts of water vapour on described inert coating surface; Perhaps, described inert coating can also catalytic coke and water vapour react, and also adhere to can catalytic coke and the active catalytic layer that reacts of water vapour on described inert coating surface.
2. production method according to claim 1, wherein, the average pore radius of described vesicular structure is 0.5-3.7nm, the specific surface area of described inert coating is 10-140m
2/ g.
3. production method according to claim 1, wherein, the thickness of described inert coating is 2-100 μ m.
4. according to claim 1 or 3 described production methods, wherein, described inert coating contains silicon-dioxide and/or the first metal oxide, perhaps, described inert coating contains silicon-dioxide and/or the first metal oxide and the second metal active constituent, and the metal in described the first metal oxide is selected from one or more in aluminium, titanium, zirconium, manganese, chromium, lanthanum and the magnesium; Described active catalytic layer contains the second metal active constituent; Metal in described the second metal active constituent is selected from one or more in lithium, sodium, potassium, rubidium, calcium, strontium, barium, molybdenum, cobalt, nickel, iron, copper, cerium and the praseodymium.
5. production method according to claim 4, wherein, in metallic element, the charge capacity of described the second metal active constituent is 0.1-40g/m
2, described charge capacity refers to the weight of the second metal active constituent of institute's load on the per surface area.
6. method according to claim 1, wherein, the roughness Ra of described cracking furnace pipe matrix inner wall surface is preferably 0.2-0.8 μ m more than 0.2 μ m.
7. method according to claim 1, wherein, described cracking condition comprises that cracking temperature is 750-1000 ℃; Cracking pressure is 0-0.3MPa.
8. method according to claim 1, wherein, the preparation method of described cracking furnace pipe is included in cracking furnace pipe matrix inner wall surface and forms inert coating, described inert coating is for preventing coke and cracking furnace pipe substrate contact and the coating that does not react with cracking stock and/or split product, described inert coating has vesicular structure, the average pore radius of described vesicular structure is 0.5-15nm, is preferably 0.5-3.7nm; The specific surface area of described inert coating is 1m
2/ g is extremely less than 150m
2/ g is preferably 10-140m
2/ g; Described inert coating can also catalytic coke and water vapour react; Perhaps, the method also is included in the active catalytic layer that the enough catalytic cokes of described inert coating surface formation energy and water vapour react; Perhaps, described inert coating can also catalytic coke and water vapour react, and the method also is included in the active catalytic layer that the enough catalytic cokes of described inert coating surface formation energy and water vapour react.
9. method according to claim 8, wherein, described inert coating is by loading on cracking furnace pipe matrix inner wall surface with the first slurry mix and/or the second slurry mix and forming through the first thermal treatment; Described the first slurry mix is for being that 2-5 or pH are under the condition of 9-11 at pH, and at least a, the colloidal sol in silicon-dioxide, the first metal oxide and the first metal oxide hydrate and water are mixed to get; Described the second slurry mix is for being that 2-5 or pH are under the condition of 9-11 at pH, and silicon-dioxide and/or the first metal oxide, the first metal oxide hydrate and water are mixed to get; Also contain bimetallic soluble salt in described the first slurry mix and the second slurry mix; Perhaps, described active catalytic layer is the coating by bimetallic soluble salt being loaded on described inert coating surface and forming through the second thermal treatment.
10. method according to claim 9, wherein, metal in described the first metal oxide is selected from one or more in aluminium, titanium, zirconium, manganese, chromium, lanthanum and the magnesium, preferably, described the first metal oxide is selected from one or more in aluminum oxide, titanium oxide, zirconium white, manganese picotite, magnesium-aluminium spinel and the manganese silicon spinel; Metal in described the first metal oxide hydrate is selected from one or more in aluminium, titanium, zirconium, manganese, chromium, lanthanum and the magnesium; Described colloidal sol is selected from one or more in silicon sol, aluminium colloidal sol, titanium colloidal sol and the zirconium colloidal sol; Described bimetallic soluble salt is selected from one or more in bimetallic nitrate, vitriol, carbonate, phosphoric acid salt, chlorate and the acetate, metal in the described bimetallic soluble salt is selected from one or more in lithium, sodium, potassium, rubidium, calcium, strontium, barium, molybdenum, cobalt, nickel, iron, copper, cerium and the praseodymium, preferably, described bimetallic soluble salt is selected from one or more in nitrocalcite, nickelous nitrate, SODIUMNITRATE, salt of wormwood, yellow soda ash, vitriolate of tartar, ferric sulfate and the cerous nitrate.
11. method according to claim 9, wherein, the consumption of described the first slurry mix and/or the second slurry mix is so that the thickness of described inert coating is 2-100 μ m; The consumption of bimetallic soluble salt so that, in metallic element, the charge capacity of the second metal active constituent that obtains is 0.1-40g/m
2, described charge capacity refers to the weight of the second metal active constituent of institute's load on the per surface area.
12. method according to claim 9, wherein, the mass ratio of the quality of the quality of the total mass of silicon-dioxide and the first metal oxide and the first metal oxide hydrate, colloidal sol, the second metal soluble salt and water is 0.1-0.8: 0.1-1: 0-0.2 described in described the first slurry mix: 1, be preferably 0.1-0.6: 0.1-1: 0.01-0.2: 1; The mass ratio of the quality of the quality of the total mass of silicon-dioxide and the first metal oxide, the first metal oxide hydrate, the second metal soluble salt and water is 0.1-0.4: 0.01-0.4: 0-0.15 described in described the second slurry mix: 1, be preferably 0.15-0.3: 0.015-0.15: 0.01-0.09: 1.
13. method according to claim 9, wherein, the described first heat treated condition comprises that thermal treatment temp is 300-1100 ℃, and heat treatment time is 0.5-10 hour; The second heat treated condition comprises that thermal treatment temp is 300-1100 ℃, and heat treatment time is 0.5-10 hour.
14. method according to claim 8, wherein, before the method also is included in described cracking furnace pipe matrix surface load inert coating, described cracking furnace pipe matrix is carried out surface treatment, described surface-treated condition makes the roughness Ra of described cracking furnace pipe matrix inner wall surface more than 0.2 μ m, is preferably 0.2-0.8 μ m.
15. method according to claim 14, wherein, described surface-treated method comprises: in oxidizing atmosphere, under 600-1100 ℃, described cracking furnace pipe matrix was carried out oxide treatment 0.5-24 hour.
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