CN102899065B - Method for producing olefin - Google Patents
Method for producing olefin Download PDFInfo
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- CN102899065B CN102899065B CN201110217001.8A CN201110217001A CN102899065B CN 102899065 B CN102899065 B CN 102899065B CN 201110217001 A CN201110217001 A CN 201110217001A CN 102899065 B CN102899065 B CN 102899065B
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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 based on pyrolysis in tubular furnace technology, this technology is worldwide widely applied.But inevitably produce the problem of coking and carburizing in the production process of ethene, thus make the boiler tube internal diameter of pyrolyzer diminish, tube drop increases, and hinders normally carrying out of scission reaction, have impact on the yield of ethene, reduce production efficiency.In addition, the high temperature of cracking is easy to the boiler tube inwall carburizing impelling pyrolyzer, and namely carbon distribution and boiler tube base material generation chemical reaction, cause furnace tube material performance to weaken, affect the work-ing life of boiler tube, shortens the cycle of operation of pyrolyzer.Therefore, when boiler tube pipe surface temperature reaches tolerance limit or pressure drop acquires a certain degree, in order to ensure the normal operation of cracking furnace tube, blowing out coke cleaning must be carried out.As can be seen here, developing the method that can reduce coking of furnace tube of hydrocarbon cracking furnace is produce the prior development direction of ethene, has very large realistic meaning and economic worth to current petrochemical industry.
At present, suppress the method for cracking furnace tube coking to mainly contain following several: the raw material of (1) production control and production process, such as, adopt the raw material that aromaticity content is low, hydrogen richness is high; Adopt the technique such as hydrotreatment, Aromatics Extractive Project; (2) change the material of cracking furnace tube, namely reduce the content that can cause the elements such as Fe, Ni of catalytic coking as much as possible; (3) change cracking furnace tube structure, such as, enhanced heat transfer member can be set up in cracking furnace pipe; (4) in cracking stock, coking inhibitor is added, but, add coking inhibitor and not only can bring pollution to derived product, also can cause corrodibility to a certain degree to cracking furnace tube; (5) form at the internal surface of cracking furnace pipe the coating that one deck has mechanical property and thermostability concurrently by methods such as plasma spraying, heat sputtering, vapour depositions, reduce hydrocarbons to contact with the direct of boiler tube, thus reduce the catalytic activity of tube skin Fe, Ni, reduce the frictional coefficient of tube skin, sticking of effective slagging prevention particle, effectively can reduce the generation of coking.
Such as, US 6537388 discloses to adopt and contains the compound loaded in ethene boiler tube of Cr, Si, after Passivation Treatment, Cr-Si bottom is formed in Cr, Si Elements Diffusion to boiler tube matrix metal, then the method for heat sputtering is adopted, by the compound application containing Si, Al on Cr-Si bottom, after thermal treatment, form Si-Al skin.Although aforesaid method can suppress the speed of coking to a certain extent, extend 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, at the method is included in 300-1100 DEG C, by with treat that metallic surface that cracking organism the contacts water vapour air-flow containing at least one silicon compound and at least one sulphur compound carries out pre-treatment, thus reduce the coking in metallic walls.
For another example, CN 1928020A discloses after cracker steam and air burn, with the pretreating agent of the compound composition of sulfur-bearing and silicon, first boiler tube metal deposits the mixed coating of one deck sulphur and silicon-dioxide, to improve the bonding force of coating and cracking furnace pipe; After the first layer coating, continue to add siliceous compound, add the compound containing magnesium simultaneously, form layer of silicon dioxide and magnesian composite ceramic coat at silicon-dioxide and sulphur surface, to reduce the coke that hydrocarbon cracking reaction produces.
But coating resistance to elevated temperatures is poor, sulfocompound pollutes the environment problem that aforesaid method all exists, thus, limits their applying in actual production.
Summary of the invention
The object of the invention is to overcome the easy coking of cracking furnace pipe in olefin production process, and adopt the method for prior art cracking furnace pipe is processed the high thermal resistance of the coating obtained poor, can to the defect of environment and complex process, and provide a kind of and apply the method that anticoking capability is good, high temperature resistant, the cracking furnace pipe of environmental protection carries out olefin production.
The invention provides a kind of production method of alkene, the method comprises cracking stock is placed in cracking furnace pipe, cracking is carried out under cracking condition, obtain split product alkene, wherein, described cracking furnace pipe comprises cracking furnace pipe matrix, be attached to the inert coating of cracking furnace pipe matrix inner wall surface, described inert coating is can prevent coke and cracking furnace pipe substrate contact and the coating do not reacted 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, the specific surface area of described inert coating is 1m
2/ g is to being less than 150m
2/ g, described inert coating can also catalytic coke and water vapour react, or described inert coating surface also attachment can the active catalytic layer that reacts of catalytic coke and water vapour, or described inert coating can also catalytic coke and water vapour react, and also attachment can the active catalytic layer that reacts of catalytic coke and water vapour on described inert coating surface.
Under normal circumstances, cracking furnace pipe matrix contains iron and nickel, and described iron and nickel at high temperature can generate thread coke by catalyzed alkene, and this coke is attached on cracking furnace pipe, makes that boiler tube internal diameter diminishes, tube drop increases, shorten the cycle of operation of pyrolyzer; By arranging inert coating on the matrix of cracking furnace pipe, effectively can stop contacting of iron and nickel isoreactivity component and hydro carbons, thus greatly reducing the possibility of coking, improve the productive rate of alkene, increase the cycle of operation of pyrolyzer.In addition, described inert coating can also catalytic coke and water vapour react, and/or set up on described inert coating can the active catalytic layer that reacts of catalytic coke and water vapour, thus reduce further the content of the coke on 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 being less than 150m
2during/g, the inert coating of the cracking furnace pipe of gained has good resistance to expansion and shrinkage, thus described inert coating can not crack, and can also stop the contact of coke and cracking furnace pipe matrix well, and anti-coking is effective.In a preferred embodiment of the present invention, before loaded inert coating, surface treatment is carried out to cracking furnace pipe matrix, the roughness Ra on described cracking furnace pipe surface is made to be 0.2-0.8 μm, then inert coating can be attached on cracking furnace pipe matrix well, and form stronger bonding force with cracking furnace pipe, namely there is excellent resistance to erosion ability.In another preferred embodiment of the present invention, described first metal oxide be selected from aluminum oxide, titanium oxide, zirconium white, manganese picotite, magnesium-aluminium spinel and manganese silicon spinel one or more, the anticoking capability of the inert coating be made up of these first metal oxides is excellent, can further improve the anticoking capability of the cracking furnace pipe of gained.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The production method of alkene provided by the invention comprises cracking stock is placed in cracking furnace pipe, cracking is carried out under cracking condition, obtain split product alkene, wherein, described cracking furnace pipe comprises cracking furnace pipe matrix, be attached to the inert coating of cracking furnace pipe matrix inner wall surface, described inert coating is can prevent coke and cracking furnace pipe substrate contact and the coating do not reacted 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 to being less than 150m
2/ g; Described inert coating can also catalytic coke and water vapour react; Or described inert coating surface also attachment can the active catalytic layer that reacts of catalytic coke and water vapour; Or described inert coating can also catalytic coke and water vapour react, and also attachment can the active catalytic layer that reacts of catalytic coke and water vapour on described inert coating surface.
It should be noted that, cracking furnace pipe provided by the invention can only include cracking furnace pipe matrix and inert coating, described inert coating can not only 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.Or 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 can not only 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 promote that described inert coating catalytic coke and water vapour react further.
According to the present invention, the effect of described inert coating prevents coke and cracking furnace pipe substrate contact, is 0.5-15nm by controlling the average pore radius of the vesicular structure of described inert coating, is preferably 0.5-3.7nm; Specific surface area is 1 to being less than 150m
2/ g, is preferably 10-140m
2/ g, can not only ensure that described coke and cracking furnace pipe matrix are isolated well, the inert coating of described cracking furnace pipe can also be made to have good resistance to expansion and shrinkage, reduce the possibility that it cracks.
According to the present invention, although the selectable range of the thickness of described inert coating is wider, under preferable case, also ensure the work-ing life of cracking furnace pipe to improve anticoking capability, as a rule, when the thickness of described inert coating is 2-100 μm simultaneously.The present inventor finds, when described inert coating thickness more preferably 10-50 μm time, can not only ensure that the cracking furnace pipe of gained has good anticoking capability, can also ensure that inert coating can stick on cracking furnace pipe matrix well, smooth, not easy to crack, over-all properties is splendid.
According to the present invention, described inert coating also variously can prevent coke and cracking furnace pipe substrate contact and the coating do not reacted with cracking stock and/or split product for existing, such as, described inert coating contains silicon-dioxide and/or the first metal oxide, or described inert coating contains silicon-dioxide and/or the first metal oxide and the second metal active constituent; Metal in described first metal oxide be selected from aluminium, titanium, zirconium, manganese, chromium, lanthanum and magnesium one or more; Described active catalytic layer contains the second metal active constituent.
It should be noted that, the first metal oxide of the present invention can be the metal oxide only containing a kind of metal, one or more as being selected from aluminum oxide, titanium oxide, zirconium white, manganese oxide, chromic oxide and magnesium oxide.Moreover described first metal oxide can also complex metal oxides containing two or more metal, the metal in described complex metal oxides can be selected from aluminium, titanium, zirconium, manganese, chromium, lanthanum and magnesium two or more.Under preferable case, described complex metal oxides is spinel type composite metal oxide, such as, be one or more in manganese picotite, magnesium-aluminium spinel and manganese silicon spinel; Such as, or being perovskite typed complex metal oxides, 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 perovskite typed complex metal oxides, coke and water vapor generation water-gas reaction can be promoted, and spinel type composite metal oxide and and perovskite typed complex metal oxides there is good resistance to elevated temperatures and anti-charing ability, therefore, when described first metal oxide be spinel type composite metal oxide or perovskite typed complex metal oxides time, the anti-coking effect of the inert coating of gained is very good.
According to the present invention, the second metal active constituent contained in described inert coating can be identical with the second metal active constituent in active catalytic layer, also can be different, and can be selected from existing various can the metal active constituent that reacts of catalytic coke and water vapour, under preferable case, described second metal active constituent is all exist with the form of metal oxide substantially, the metal in described second metal active constituent can be selected from lithium, sodium, potassium, rubidium, calcium, strontium, barium, molybdenum, cobalt, nickel, iron, copper, cerium and praseodymium one or more.
According to the present invention, the charge capacity of described second metal active constituent can in very large range change, but in order to improve catalytic performance and reduce production cost, under preferable case, with elemental metal, the charge capacity of described second metal active constituent is 0.5-40g/m
2, more preferably 1-20g/m
2; Described charge capacity refers to the weight of the second metal active constituent of institute's load in per surface area.
According to the present invention, in order to strengthen described cracking furnace pipe further coating between bonding force, improve its flushing resistance, preferably, described cracking furnace pipe matrix has coarse inner wall surface, and when the roughness Ra of inner wall surface is more than 0.2 μm, when being preferably 0.2-0.8 μm, inert coating can load on described cracking furnace pipe matrix easily, and the flushing resistance of the cracking furnace pipe of gained is also very good.
According to the present invention, described cracking stock is placed in 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 DEG C, is preferably 800-900 DEG C; 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 can prevent coke and cracking furnace pipe substrate contact and the coating do not reacted 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 being less than 150m
2/ g, is preferably 10-140m
2/ g; Described inert coating can also catalytic coke and water vapour react; Or the method is also included in the active catalytic layer that the enough catalytic cokes of described inert coating surface formation energy and water vapour react; Or described inert coating can also catalytic coke and water vapour react, and the method is also 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 by being formed the first slurry mix and/or the second slurry mix load through the first thermal treatment in cracking furnace pipe matrix inner wall surface; Described first slurry mix is be 2-5 or pH be the condition of 9-11 at pH under, at least one, colloidal sol and the water in silicon-dioxide, the first metal oxide and the first metal oxide hydrate is mixed to get; Described second slurry mix is be 2-5 or pH be the condition of 9-11 at pH under, silicon-dioxide and/or the first metal oxide, the first metal oxide hydrate and water are mixed to get.
Coke and cracking furnace pipe substrate contact can be prevented in order to realize described cracking furnace pipe and do not react with cracking stock and/or split product and can catalytic coke and water vapour react; According to a kind of embodiment of the present invention, in described first slurry mix and the second slurry mix, bimetallic soluble salt can also be contained; Or, according to another kind of embodiment of the present invention, described cracking furnace pipe also comprises the active catalytic layer being attached to inert coating surface, and described active catalytic layer is the coating by bimetallic soluble salt load being formed on described inert coating surface and through the second thermal treatment; Or above-mentioned two kinds of modes are combined.
According to the present invention, metal in described first metal oxide be selected from aluminium, titanium, zirconium, manganese, chromium, lanthanum and magnesium one or more, it should be noted that, first metal oxide of the present invention can be the metal oxide only containing a kind of metal, one or more as being selected from aluminum oxide, titanium oxide, zirconium white, manganese oxide, chromic oxide and magnesium oxide.Moreover described first metal oxide can also complex metal oxides containing two or more metal, the metal in described complex metal oxides can be selected from aluminium, titanium, zirconium, manganese, chromium, lanthanum and magnesium two or more.The present inventor finds, when described first metal oxide is complex metal oxides, be preferably spinel type composite metal oxide, be such as one or more in manganese picotite, magnesium-aluminium spinel and manganese silicon spinel, such as, or being perovskite typed complex metal oxides, is LaAlO
3, LaMnO
3, and MnSiO
3in one or more time, the anti-coking effect of the inert coating of gained is very good.Metal in described first metal oxide hydrate be preferably selected from aluminium, titanium, zirconium, manganese, chromium, lanthanum and magnesium one or more.Described bimetallic soluble salt can be the soluble salt of existing various metal, as long as ensure that the product that obtains after the first thermal treatment and/or the second thermal treatment can catalytic coke and water vapour react, such as, described bimetallic soluble salt can be selected from bimetallic nitrate, vitriol, carbonate, phosphoric acid salt, one or more in chlorate and acetate, metal in described bimetallic soluble salt can be selected from lithium, sodium, potassium, rubidium, calcium, strontium, barium, molybdenum, cobalt, nickel, iron, copper, one or more in cerium and praseodymium, preferably, described bimetallic soluble salt is selected from nitrocalcite, nickelous nitrate, SODIUMNITRATE, salt of wormwood, sodium carbonate, potassium sulfate, one or more in ferric sulfate and cerous nitrate.
The present invention is not particularly limited the content of each component in the first slurry mix of formation inert coating and the second slurry mix, coke and cracking furnace pipe substrate contact can be prevented and the inert coating do not reacted with cracking stock and/or split product as long as can be formed, and ensure that the inert coating obtained under the first heat-treat condition has the microvoid structure that average pore radius is 0.5-15nm, and the specific surface area of described inert coating is 1m
2/ g is to being less than 150m
2/ g, such as, the total mass of silicon-dioxide and the first metal oxide and the first metal oxide hydrate described in described first slurry mix, the quality of colloidal sol, the quality of the second metal soluble salt and the mass ratio of water are 0.1-0.8: 0.1-1: 0-0.2: 1, are preferably 0.1-0.6: 0.1-1: 0.01-0.2: 1; The total mass of silicon-dioxide and the first metal oxide described in described second slurry mix, the quality of the first metal oxide hydrate, the quality of the second metal soluble salt and the mass ratio of water are 0.1-0.4: 0.01-0.4: 0-0.15: 1, are preferably 0.15-0.3: 0.015-0.15: 0.01-0.09: 1.
According to the present invention, it should be noted that, if time in described first slurry mix simultaneously containing silicon-dioxide, the first metal oxide and the first metal oxide hydrate, then in aforementioned proportion, " total mass " refers to the total mass of silicon-dioxide and the first metal oxide and the first metal oxide hydrate, and in the first slurry mix, 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.If when containing any two kinds in silicon-dioxide, the first metal oxide and the first metal oxide hydrate in described first slurry mix, then " total mass " refers to the total mass of any two kinds in silicon-dioxide, the first metal oxide and the first metal oxide hydrate, in the first slurry mix the mass ratio of each material refer in silicon-dioxide, the first metal oxide and the first metal oxide hydrate any two kinds total mass, the quality of colloidal sol, the quality of the second metal soluble salt and the mass ratio of water; Under preferable case, described first slurry mix is silicon-dioxide or the first metal oxide, and first mixture of metal oxide hydrate, and the mass ratio of the quality of described silicon-dioxide or the first metal oxide and described first metal oxide hydrate is 1: 0.05-1.If time in described first slurry mix only containing a kind of in silicon-dioxide, the first metal oxide or the first metal oxide hydrate, described " total mass " refers to the quality of silicon-dioxide or the first metal oxide or the first metal oxide hydrate, and in the first slurry mix, 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.The mass ratio of each material and above-mentioned equivalent in meaning in described second slurry mix, will repeat no more at this.
According to the present invention, the colloidal sol in described first slurry mix be selected from Alumina gel, silicon sol, titanium colloidal sol and zirconium colloidal sol one or more.Described colloidal sol can be prepared by existing various method, such as, can by after sol precursor and solvent, at a certain temperature, obtain in the Water Under solution of pH value to be 2-5 or pH be 9-11 or dissolving, ageing; Described sol precursor can be at least one in the saturated hydrocarbyl organoalkoxysilane of 1-20 for the soluble inorganic salt of the oxide compound of the oxide compound of the alkoxide of the alkoxide of the alkoxide of titanium, aluminium, zirconium, titanyl compound and hydrate thereof, aluminium and hydrate thereof, zirconium and hydrate thereof, titanium, the soluble inorganic salt of aluminium, the soluble inorganic salt of zirconium and carbonatoms; Described solvent can be the existing various solvent preparing colloidal sol that is applicable to, but in order to pollution that is cost-saving and that reduce environment, under normal circumstances, described solvent is water; PH value can by adding acid or alkali regulates.
According to the present invention, form the first slurry mix of inert coating and the viscosity of the second slurry mix and stability to regulate, can also containing tensio-active agent and other metal-salts in described first slurry mix and/or the second slurry mix.Described tensio-active agent usually can be selected from polyvinyl alcohol, hydroxy propyl cellulose, methylcellulose gum and polyoxyethylene glycol one or more; Other metal-salts described can be generally one or more of aluminum nitrate, zirconium nitrate and Titanium Nitrate.
According to the present invention, the method of described loaded inert coating can be existing various method, such as, can be one or more in pickling process, plasma spraying, chemical vapour deposition (CVD), plasma reinforced chemical vapour deposition (PEVCD), physical vapor deposition (PVD) and sol-gel method; Wherein, physical vapor deposition (PVD) method generally includes again cathode arc, sputtering (DC, RF, magnetron) and electron-beam vapor deposition method.The method of described supported active Catalytic Layer also can be existing various method, such as, the cracking furnace pipe after loaded inert coating can be immersed in the solution containing active ingredient.
In process prepared by described cracking furnace pipe, can by inert coating and active catalytic layer described in the load of above method; Also by repeatedly inert coating described in load and active catalytic layer, until reach desired thickness or charge capacity.As long as the consumption of described first slurry mix and/or the second slurry mix ensures that the thickness of the inert coating of gained is preferably 0.5-100 μm, as long as the consumption of described active ingredient ensures, with elemental metal, the charge capacity of described second metal active constituent is preferably 0.5-40g/m
2.
According to the present invention, described first heat treated condition generally includes treatment temp and treatment time, as long as described treatment temp and treatment time can ensure that the inert coating of the cracking furnace pipe of gained has vesicular structure, the average pore radius of described vesicular structure is 0.5-15nm, and the specific surface area ensureing inert coating is 1m
2/ g is to being less than 150m
2/ g, under preferable case, described first heat treated treatment temp is 300-1100 DEG C, more preferably 600-1100 DEG C, and the treatment time is 0.5-10 hour, more preferably 1-8 hour.
The present invention does not also limit described second heat treated condition, active ingredient can only be enable to be attached to well on inert coating, under preferable case, described second heat treated treatment temp is 300-1100 DEG C, more preferably 600-1100 DEG C, treatment time is 0.5-10 hour, more preferably 1-8 hour.
According to the present invention, before the preparation method of described cracking furnace pipe is also included in described cracking furnace pipe matrix surface loaded inert coating, described cracking furnace pipe matrix is carried out surface treatment, as long as described surface-treated condition ensures to make the roughness Ra of the cracking furnace pipe matrix surface of gained more than 0.2 μm, be preferably 0.2-0.8 μm.Under normal circumstances, described surface-treated method comprises: in oxidizing atmosphere, at 600-1100 DEG C, described cracking furnace pipe matrix is carried out oxide treatment 0.5-24 hour.
Described oxidizing atmosphere refers to generate the gas of corresponding oxide grain to cracking furnace pipe matrix, such as, can be one or more in water vapour, carbonic acid gas, air and oxygen.Keep the method for oxidizing atmosphere can for pass into any one gas above-mentioned or gaseous mixture in cracking furnace pipe, in order to dilute the concentration of above-mentioned gas, thus controlled oxidization degree and time, can also non-oxidizing gas be contained in described oxidizing atmosphere; Described non-oxidizing gas refer to not with any one gas or the gaseous mixture of cracking furnace pipe generation chemical reaction, can be such as one or more in nitrogen and periodic table of elements zero group gas.
According to the present invention, before also oxide treatment is included in the surface treatment of matrix, also preferably include and cracking furnace pipe matrix inner wall surface clean-out system is cleaned, to remove greasy dirt and other impurity of described cracking furnace pipe matrix inner wall surface, described clean-out system can be that acid, water, alcohol etc. can the conventional cleaning reagents of wipe oil.
To be described in further detail the present invention by embodiment below.
In following embodiment and comparative example, obtain the thickness of described inert coating with determination of electron microscopy, and adopt N2 adsorption BET method to record its specific surface area and average pore radius; The charge capacity of active ingredient in described active catalytic layer is recorded by ICP method.
Preparation embodiment 1
This prepares the preparation that embodiment illustrates colloidal sol provided by the invention.
By 24g pseudo-boehmite and the mixing of 200mL deionized water, stir at 85 DEG C and obtain mixture in 0.5 hour, be the salpeter solution of 1.6mol/L by concentration, the pH value of said mixture is adjusted to 2.5, continue to stir after 24 hours at 85 DEG C, obtain stable, the transparent Alumina gel that average particulate diameter is 15nm.
Preparation embodiment 2
This prepares the preparation that embodiment illustrates colloidal sol provided by the invention.
40g silica flour, 15mL water glass and 150mL deionized water are mixed, stir at 90 DEG C and obtain mixture in 1 hour, be the sodium hydroxide solution of 1.6mol/L by concentration, the pH value of said mixture is adjusted to 11, continue to stir after 24 hours at 90 DEG C, obtain stable, the transparent silicon sol that particle diameter is 20nm.
Preparation embodiment 3
This prepares the preparation that embodiment illustrates colloidal sol provided by the invention.
23g butyl (tetra) titanate is dissolved in 100mL ethanol, under room temperature rapid stirring evenly after, with 200mL deionized water mix and blend 0.5h, adding concentration is that pH value is adjusted to 2 by the salpeter solution of 1.6mol/L, at 85 DEG C, constant temperature stirs 12h, be cooled to constant temperature, obtain stable, the transparent titanium colloidal sol that average particulate diameter is 100nm.
Embodiment 1
This embodiment illustrates the preparation that the invention provides cracking furnace pipe.
(1) pre-treatment:
To be of a size of
hK40 boiler tube matrix ultrasonic cleaning 30min in acetone, then ultrasonic cleaning 10min in deionized water, to remove oil, oxide compound and other impurity on metallic surface.Described boiler tube matrix after ultrasonic cleaning is carried out drying at 120 DEG C, then at 750 DEG C, is oxidized 2h in air atmosphere, obtain the cracking furnace pipe matrix that roughness Ra is 0.3.
(2) on cracking furnace pipe matrix, coating is formed:
By 30g by after preparing embodiment 1 obtained Alumina gel, 20g pseudo-boehmite and 50mL deionized water mixing and ball milling 18h, adding concentration is that pH value is reconciled to 3.5 by the salpeter solution of 1.6mol/L, obtains the first slurry mix.Load on the cracking furnace pipe matrix that step (1) obtains by above-mentioned first slurry mix by pickling process, at 120 DEG C after dry 1 hour, at being placed in 800 DEG C, roasting 2 hours, obtains inert coating.By the cracking furnace pipe containing inert coating at Ca (NO
3)
2solution (Ca (NO
3)
2concentration be 2.5mol/L) in dipping 5min, after seasoning, at being placed in 800 DEG C, roasting 2 hours, obtains 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 is 20 microns; In calcium constituent, the charge capacity of described active ingredient is 1.3g/m
2.
Embodiment 2
This embodiment illustrates the preparation that the invention provides cracking furnace pipe.
(1) pre-treatment:
To be of a size of
hP40 boiler tube matrix ultrasonic cleaning 30min in acetone, then with 1% aqueous nitric acid soak 10min, to remove oil, oxide compound and other impurity on metallic surface.Described boiler tube matrix after ultrasonic cleaning is carried out drying at 120 DEG C, then at 850 DEG C, is oxidized 2h in air atmosphere, obtain the cracking furnace pipe matrix that roughness Ra is 0.5.
(2) on cracking furnace pipe matrix, coating is formed:
By 15g by after preparing silicon sol, 20g water glass and 65mL deionized water mixing and ball milling 18h that embodiment 2 obtains, adding concentration is that pH value is reconciled to 10 by the ammoniacal liquor of 1.6mol/L, obtains the first slurry mix.Load on the cracking furnace pipe matrix that step (1) obtains by above-mentioned first slurry mix by pickling process, at 120 DEG C after dry 1 hour, at being placed in 900 DEG C, roasting 2 hours, obtains inert coating.By the cracking furnace pipe containing 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 dipping 10min, after seasoning, at being placed in 900 DEG C, roasting 2 hours, obtains 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 is 25 microns; With the total amount of sodium and potassium, the charge capacity of described active ingredient is 2.7g/m
2.
Embodiment 3
This embodiment illustrates the preparation that the invention provides 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 metallic surface.Described boiler tube matrix after ultrasonic cleaning is carried out drying at 120 DEG C, and then at 1000 DEG C, under nitrogen and oxygen mix atmosphere, (content of nitrogen is 60 volume %; The content of oxygen is 40 volume %) be oxidized 2h, obtain the cracking furnace pipe matrix that roughness Ra is 0.8.
(2) on cracking furnace pipe matrix, coating is formed:
By 30g by after preparing silicon sol that embodiment 2 obtains, 20g titanium dioxide, 20g zirconium white, 130mL deionized water mixing and ball milling 18h, adding concentration is that pH value is reconciled to 10 by the ammoniacal liquor of 1.6mol/L, obtains the first slurry mix.Load on the cracking furnace pipe matrix that step (1) obtains by above-mentioned first slurry mix by pickling process, at 120 DEG C after dry 1 hour, at being placed in 950 DEG C, roasting 2 hours, obtains inert coating.By the cracking furnace pipe containing 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 dipping 2min, after seasoning, at being placed in 950 DEG C, roasting 2 hours, obtains 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 is 25nm; With the total amount of nickel and potassium, the charge capacity of described active ingredient is 3.3g/m
2.
Embodiment 4
This embodiment illustrates the preparation that the invention provides cracking furnace pipe.
(1) pre-treatment:
To be of a size of
hK40 boiler tube matrix ultrasonic cleaning 30min in acetone, then ultrasonic cleaning 10min in deionized water, to remove oil, oxide compound and other impurity on metallic surface.Described boiler tube matrix after ultrasonic cleaning is carried out drying at 120 DEG C, then at 750 DEG C, is oxidized 2h in air atmosphere, obtain the cracking furnace pipe matrix that roughness Ra is 0.3.
(2) on cracking furnace pipe matrix, coating is formed:
By 60g by the titanium colloidal sol, 20g pseudo-boehmite, 20g manganese picotite, the 5g Ce (NO that prepare embodiment 3 and obtain
3)
3, after 100mL deionized water mixing and ball milling 18h, adding concentration is that pH value is reconciled to 4 by the salpeter solution of 1.6mol/L, obtains the first slurry mix.Loaded to by pickling process by above-mentioned first slurry mix on the cracking furnace pipe matrix obtained by step (1), at 120 DEG C after dry 1 hour, at being placed in 1000 DEG C, roasting 2 hours, obtains inert coating.By the cracking furnace pipe containing inert coating at K
2cO
3solution (K
2cO
3concentration be 3.8mol/L) in dipping 5min, after seasoning, at being placed in 1000 DEG C, roasting 2 hours, obtains 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 is 25 microns; In cerium and potassium element, the charge capacity of described active ingredient is 4.6g/m
2.
Embodiment 5
This embodiment illustrates the preparation that the invention provides cracking furnace pipe.
(1) pre-treatment:
To be of a size of
hK40 boiler tube matrix ultrasonic cleaning 30min in acetone, then ultrasonic cleaning 10min in deionized water, to remove oil, oxide compound and other impurity on metallic surface.Described boiler tube matrix after ultrasonic cleaning is carried out drying at 120 DEG C, then at 750 DEG C, is oxidized 2h in air atmosphere, obtain the cracking furnace pipe matrix that roughness Ra is 0.3.
(2) on cracking furnace pipe matrix, coating is formed:
By 5g pseudo-boehmite, 15g Alpha-alumina, 5g lanthanum nitrate, 5g KNO
3after 100mL deionized water mixing and ball milling 18h, add concentration be 1.6mol/L salpeter solution by pH value reconcile to 4, obtain the first slurry mix.Loaded to by pickling process by above-mentioned first slurry mix on the cracking furnace pipe matrix obtained by step (1), at 120 DEG C after dry 1 hour, at being placed in 1000 DEG C, roasting 2 hours, obtains the first inert coating.Repeat above-mentioned steps, load 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 is 45nm.
Embodiment 6
This embodiment illustrates the preparation that the invention provides cracking furnace pipe.
Method according to embodiment 2 prepares cracking furnace pipe, unlike, change the heat-treat condition (namely at 120 DEG C after dry 1 hour, roasting 2 hours at being placed in 700 DEG C) of inert coating, make the average pore radius of the inert coating obtained be 1.5nm, specific surface area is 148m
2/ g.
Embodiment 7
This embodiment illustrates the preparation that the invention provides cracking furnace pipe.
Method according to embodiment 2 prepares cracking furnace pipe, unlike, change the heat-treat condition (namely at 120 DEG C after dry 1 hour, roasting 2 hours at being placed in 950 DEG C) of inert coating, make the average pore radius of the inert coating obtained be 3.8nm, specific surface area is 102m
2/ g.
Embodiment 8
This embodiment illustrates the preparation that the invention provides cracking furnace pipe.
Method according to embodiment 2 prepares cracking furnace pipe, unlike, change the surface treatment condition of cracking furnace pipe matrix, make the roughness Ra of the cracking furnace pipe matrix obtained be 0.1, that is:
To be of a size of
hP40 boiler tube matrix ultrasonic cleaning 30min in acetone, then with 1% aqueous nitric acid soak 10min, to remove oil, oxide compound and other impurity on metallic surface.Described boiler tube matrix after ultrasonic cleaning is carried out drying at 120 DEG C, then at 600 DEG C, is oxidized 2h in air atmosphere, obtain the cracking furnace pipe matrix that roughness Ra is 0.1.
Comparative example 1
This comparative example is for illustration of the preparation of reference lysis boiler tube.
Method according to embodiment 1 prepares cracking furnace pipe, unlike, do not carry out coating load to cracking furnace pipe matrix, that is, concrete steps are:
To be of a size of
hK40 boiler tube matrix ultrasonic cleaning 30min in acetone, then ultrasonic cleaning 10min in deionized water, to remove oil, oxide compound and other impurity on metallic surface.Described boiler tube matrix after ultrasonic cleaning is carried out drying at 120 DEG C, then at 750 DEG C, is oxidized 2h in air atmosphere, obtain the cracking furnace pipe matrix that roughness Ra is 0.3.
Comparative example 2
This comparative example is for illustration of the preparation of reference lysis boiler tube.
Method according to embodiment 2 prepares cracking furnace pipe, unlike, change the heat-treat condition (namely at 120 DEG C after dry 1 hour, roasting 3 hours at being placed in 600 DEG C) of inert coating, make the average pore radius of the inert coating obtained be 0.5nm, specific surface area is 160m
2/ g.
Test case 1-8
This test case is tested for illustration of the anticoking capability of cracking furnace pipe.
Petroleum naphtha as shown in table 1 for 200g physical properties is passed in preheater with the speed of 100g/h, simultaneously, 100g deionized water passes through in corresponding preheater with the speed of 50g/h, at 600 DEG C after preheating mixing, enter in embodiment 1-8 gained cracking furnace pipe, at 850 DEG C, cracking 2 hours, obtains splitting gas 160L.After cracking is complete, pass into nitrogen and oxygen to described cracking furnace pipe, control that the flow of nitrogen is 1L/min, the flow of oxygen is 0.2L/min, burn at 850 DEG C, CO and CO produced in burning process
2concentration by radar stealthy materials on-line measurement, the volume of the gas produced in roasting is noted down online by wet flow indicator, and the carbon content finally calculating 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 tested for illustration of the anticoking capability of cracking furnace pipe.
The anticoking capability of cracking furnace pipe is detected according to the method for test case 1-8, unlike, what detect is the cracking furnace pipe obtained by the method for comparative example 1-2, and detected result is as shown in table 2.
Table 2
By test case 1-8 and contrast test example 1-2 contrast can find out, the anticoking capability of the cracking furnace pipe adopting method of the present invention to obtain is good, and in coating containing element sulphur, can not work the mischief to environment; Can be found out by the contrast of test case 2 with test case 6-8, the anticoking capability of the cracking furnace pipe adopting optimal way of the present invention to obtain is more excellent.
Claims (18)
1. the production method of an alkene, the method comprises cracking stock is placed in cracking furnace pipe, cracking is carried out under cracking condition, obtain split product alkene, it is characterized in that, described cracking furnace pipe comprises cracking furnace pipe matrix, be attached to the inert coating of cracking furnace pipe matrix inner wall surface, described inert coating is can prevent coke and cracking furnace pipe substrate contact and the coating do not reacted 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, the specific surface area of described inert coating is for being more than or equal to 1m
2/ g is to being less than 150m
2/ g, described inert coating can also catalytic coke and water vapour react, or described inert coating surface also attachment can the active catalytic layer that reacts of catalytic coke and water vapour, or described inert coating can also catalytic coke and water vapour react, and also attachment can the active catalytic layer that reacts of catalytic coke and water vapour on described inert coating surface, described inert coating contains silicon-dioxide and/or the first metal oxide, or, described inert coating contains silicon-dioxide and/or the first metal oxide and the second metal active constituent, the metal in described first metal oxide be selected from aluminium, titanium, zirconium, manganese, chromium, lanthanum and magnesium one or more, described active catalytic layer contains the second metal active constituent, metal in the second metal active constituent in described inert coating and active catalytic layer be selected from lithium, sodium, potassium, rubidium, calcium, strontium, barium, molybdenum, cobalt, nickel, iron, copper, cerium and praseodymium independently of one another one or more.
2. method according to claim 1, wherein, the average pore radius of described vesicular structure is 0.5-3.7nm, and the specific surface area of described inert coating is 10-140m
2/ g.
3. method according to claim 1, wherein, the thickness of described inert coating is 2-100 μm.
4. method according to claim 1, wherein, with elemental metal, the charge capacity of described 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 in per surface area.
5. method according to claim 1, wherein, the roughness Ra of described cracking furnace pipe matrix inner wall surface is more than 0.2 μm.
6. method according to claim 5, wherein, the roughness Ra of described cracking furnace pipe matrix inner wall surface is 0.2-0.8 μm.
7. method according to claim 1, wherein, it is 750-1000 DEG C that described cracking condition comprises cracking temperature; Cracking pressure is 0-0.3MPa.
8. method according to claim 1, wherein, described cracking furnace pipe prepares in accordance with the following methods: form inert coating in cracking furnace pipe matrix inner wall surface, described inert coating is can prevent coke and cracking furnace pipe substrate contact and the coating do not reacted with cracking stock and/or split product, described inert coating has vesicular structure, and the average pore radius of described vesicular structure is 0.5-15nm; The specific surface area of described inert coating is for being more than or equal to 1m
2/ g is to being less than 150m
2/ g; Described inert coating can also catalytic coke and water vapour react; Or the method is also included in the active catalytic layer that the enough catalytic cokes of described inert coating surface formation energy and water vapour react; Or described inert coating can also catalytic coke and water vapour react, and the method is also 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 is by being formed the first slurry mix and/or the second slurry mix load through the first thermal treatment in cracking furnace pipe matrix inner wall surface; Described first slurry mix is be 2-5 or pH be the condition of 9-11 at pH under, at least one, colloidal sol and the water in silicon-dioxide, the first metal oxide and the first metal oxide hydrate is mixed to get; Described second slurry mix is be 2-5 or pH be the condition of 9-11 at pH under, silicon-dioxide and/or the first metal oxide, the first metal oxide hydrate and water are mixed to get;
Metal in described first metal oxide be selected from aluminium, titanium, zirconium, manganese, chromium, lanthanum and magnesium one or more; Metal in described first metal oxide hydrate be selected from aluminium, titanium, zirconium, manganese, chromium, lanthanum and magnesium one or more; Described colloidal sol be selected from silicon sol, Alumina gel, titanium colloidal sol and zirconium colloidal sol one or more;
Described in described first slurry mix, the mass ratio of silicon-dioxide and the total mass of the first metal oxide and the first metal oxide hydrate, the quality of colloidal sol and water is 0.1-0.8:0.1-1:1; The mass ratio of the total mass of silicon-dioxide and the first metal oxide described in described second slurry mix, the quality of the first metal oxide hydrate and water is 0.1-0.4:0.01-0.4:1;
When described inert coating can also catalytic coke and water vapour react time, also containing bimetallic soluble salt in described first slurry mix and the second slurry mix;
Described active catalytic layer is the coating by bimetallic soluble salt load being formed on described inert coating surface and through the second thermal treatment;
The bimetallic soluble salt contained in described first slurry mix and the second slurry mix and the bimetallic soluble salt forming described active catalytic layer are selected from bimetallic nitrate independently of one another, vitriol, carbonate, phosphoric acid salt, one or more in chlorate and acetate, metal in the bimetallic soluble salt contained in described first slurry mix and the second slurry mix and the bimetallic soluble salt forming described active catalytic layer is selected from lithium independently of one another, sodium, potassium, rubidium, calcium, strontium, barium, molybdenum, cobalt, nickel, iron, copper, one or more in cerium and praseodymium.
9. method according to claim 8, wherein, the average pore radius of described vesicular structure is 0.5-3.7nm.
10. method according to claim 8, wherein, the specific surface area of described inert coating is 10-140m
2/ g.
11. methods according to Claim 8 in-10 described in any one, wherein, described first metal oxide be selected from aluminum oxide, titanium oxide, zirconium white, manganese picotite, magnesium-aluminium spinel and manganese silicon spinel one or more.
12. methods according to claim 11, wherein, described bimetallic soluble salt be selected from nitrocalcite, nickelous nitrate, SODIUMNITRATE, salt of wormwood, sodium carbonate, potassium sulfate, ferric sulfate and cerous nitrate one or more.
13. methods according to claim 8, wherein, the consumption of described first slurry mix and/or the second slurry mix makes the thickness of described inert coating be 2-100 μm; The consumption of bimetallic soluble salt makes, and with elemental metal, the charge capacity of the second metal active constituent obtained is 0.1-40g/m
2, described charge capacity refers to the weight of the second metal active constituent of institute's load in per surface area.
14. methods according to claim 8, wherein, the quality of the total mass of silicon-dioxide and the first metal oxide and the first metal oxide hydrate described in described first slurry mix, colloidal sol, the quality of bimetallic soluble salt and the mass ratio of water are 0.1-0.6:0.1-1:0.01-0.2:1; The total mass of silicon-dioxide and the first metal oxide described in described second slurry mix, the quality of the first metal oxide hydrate, the quality of bimetallic soluble salt and the mass ratio of water are 0.15-0.3:0.015-0.15:0.01-0.09:1.
15. methods according to claim 8, wherein, it is 300-1100 DEG C that described first heat treated condition comprises thermal treatment temp, and heat treatment time is 0.5-10 hour; It is 300-1100 DEG C that second heat treated condition comprises thermal treatment temp, and heat treatment time is 0.5-10 hour.
16. methods according to Claim 8 in-10 described in any one, wherein, before the method is also included in described cracking furnace pipe matrix surface loaded inert coating, described cracking furnace pipe matrix is carried out surface treatment, and described surface-treated condition makes the roughness Ra of described cracking furnace pipe matrix inner wall surface more than 0.2 μm.
17. methods according to claim 16, wherein, described surface-treated condition makes the roughness Ra of described cracking furnace pipe matrix inner wall surface be 0.2-0.8 μm.
18. methods according to claim 16, wherein, described surface-treated method comprises: in oxidizing atmosphere, at 600-1100 DEG C, described cracking furnace pipe matrix is carried out oxide treatment 0.5-24 hour.
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| EP0739696A1 (en) * | 1995-04-24 | 1996-10-30 | AVE Umwelttechnik GmbH | Gang saw with plural gang saw frames |
| US6228253B1 (en) * | 1997-06-05 | 2001-05-08 | Zalman Gandman | Method for removing and suppressing coke formation during pyrolysis |
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