CN102898265A - Method for producing olefin - Google Patents
Method for producing olefin Download PDFInfo
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- CN102898265A CN102898265A CN2011102168037A CN201110216803A CN102898265A CN 102898265 A CN102898265 A CN 102898265A CN 2011102168037 A CN2011102168037 A CN 2011102168037A CN 201110216803 A CN201110216803 A CN 201110216803A CN 102898265 A CN102898265 A CN 102898265A
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Abstract
The invention provides a method for producing olefin. The method comprises step of placing cracking raw materials in a cracking furnace tube for conducting cracking under cracking conditions, so as to obtain the cracking product olefin. The cracking furnace tube comprises a cracking furnace tube matrix, an adhesive layer attached to an inner wall of the cracking furnace tube matrix, and an anti-coking and anti-permeability carbon layer attached to the adhesive layer surface; the adhesive layer is a coating capable of bonding the cracking furnace tube matrix and the anti-coking and anti-permeability carbon layer, and preventing the coke from contacting with the cracking furnace tube matrix; the anti-coking and anti-permeability carbon layer is a coating, which can prevent the coke from contacting with the cracking furnace tube matrix, but does not react with cracking raw materials and / or cracking products; the adhesive layer and the anti-coking and anti-permeability carbon layer have a porous structure; and the average pore radius of the pore structure of the adhesive layer is less than that of the pore structure of the anti-coking and anti-permeability carbon layer. 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 has hindered 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.
Coating is high temperature resistant, the resistance to erosion ability is relatively poor but aforesaid method all exists, and the problem that pollutes the environment of sulfocompound, 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 method that adopts prior art cracking furnace pipe is processed the coating that obtains high temperature resistant, the resistance to erosion ability is relatively poor, can be to the defective of environment and complex process, and provide a kind of and use that the anti-coking performance is good, high temperature resistant, the cracking furnace pipe of resistance to erosion, environmental protection carries out the method for olefin production.
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, is attached to the tack coat of cracking furnace pipe matrix inner wall surface and is attached to the anti-coking of described tie layer surface, impervious carbon-coating; Described tack coat is for can bond described cracking furnace pipe matrix and anti-coking, impervious carbon-coating and can prevent the coating of coke and cracking furnace pipe substrate contact, and described anti-coking, impervious carbon-coating are to prevent coke and cracking furnace pipe substrate contact and the coating that does not react with cracking stock and/or split product; Described tack coat and anti-coking, impervious carbon-coating have microvoid structure, and the average pore radius of the microvoid structure of described tack coat is less than the average pore radius of the microvoid structure of anti-coking, impervious carbon-coating.
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 anti-coking, impervious carbon-coating are set, can effectively stop 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.The present inventor finds, between described cracking furnace pipe matrix and anti-coking, impervious carbon-coating tack coat is set, can make matrix and be coated with interlayer in conjunction with more firm, thereby greatly improved the resistance to erosion ability of gained cracking furnace pipe; And described tack coat and anti-coking, impervious carbon-coating have microvoid structure, and the aperture of the microvoid structure by controlling described tack coat can be so that the anti-coking performance of the cracking furnace pipe of gained be very excellent less than the aperture of the microvoid structure of anti-coking, impervious carbon-coating; Infer that reason may be, described anti-coking, impervious carbon-coating can prevent contacting of coke and cracking furnace pipe matrix, even so, even there is the small part coke to penetrate into anti-coking, impervious carbon-coating, but the aperture of tack coat by the described vesicular structure of control is less than the anti-coking of vesicular structure, the aperture of impervious carbon-coating, this part coke and the cracking furnace pipe substrate contact of anti-coking, impervious carbon-coating be can further prevent from penetrating into, thereby anti-coking, the anti-carburizing energy of cracking furnace pipe effectively reduced.
In a preferred embodiment of the present invention, described formation anti-coking, the average particulate diameter of solid phase is greater than the average particulate diameter of described the first colloidal sol in the first slurry mix of impervious carbon-coating and/or the second slurry mix, as a rule, the roughness of cracking furnace pipe matrix is less, has less particle diameter by control colloidal sol, can guarantee that described colloidal sol can closely be fitted on the cracking furnace pipe matrix, and the larger anti-coking of median size, impervious carbon-coating can fit tightly with described tack coat again, realized the continuous transition between the coating, further strengthened the bonding force between each layer of gained cracking furnace pipe, namely improve its resistance to erosion ability, increased its work-ing life.The anti-coking of the cracking furnace pipe by gained of the present invention, effect and the resistance to erosion ability of impervious carbon are all very good.
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.
According to the present invention, the production method of described alkene 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, is attached to the tack coat of cracking furnace pipe matrix inner wall surface and is attached to the anti-coking of described tie layer surface, impervious carbon-coating; Described tack coat is for can bond described cracking furnace pipe matrix and anti-coking, impervious carbon-coating and can prevent the coating of coke and cracking furnace pipe substrate contact, and described anti-coking, impervious carbon-coating are to prevent coke and cracking furnace pipe substrate contact and the coating that does not react with cracking stock and/or split product; Described tack coat and anti-coking, impervious carbon-coating have microvoid structure, and the average pore radius of the microvoid structure of described tack coat is less than the average pore radius of the microvoid structure of anti-coking, impervious carbon-coating.
According to the present invention, the aperture of the microvoid structure by controlling described tack coat is less than the aperture of the microvoid structure of anti-coking, impervious carbon-coating, can guarantee coke not with or contact with cracking furnace pipe hardly.And the aperture of the microvoid structure of tack coat of the present invention and anti-coking, impervious carbon-coating can in very large range change, as long as the aperture of microvoid structure of satisfying described tack coat is less than the aperture of the microvoid structure of anti-coking, impervious carbon-coating and can play and prevent that coke from contacting with cracking furnace pipe, under the preferable case, the average pore radius of the microvoid structure of described tack coat is 0.2-10nm, and the average pore radius of the microvoid structure of described anti-coking, impervious carbon-coating is 0.5-15nm.
The present invention is not particularly limited the pore volume of the microvoid structure of described tack coat and anti-coking, impervious carbon-coating, but excessive in order to prevent because of pore volume, anti-coking, anti-carburizing can descend, and because pore volume is too small, the anti-expansion of described tack coat and anti-coking, impervious carbon-coating and the not good problem of shrinkage, under the preferable case, the pore volume of described tack coat is 0.01-1.1mL/g, is preferably 0.1-0.8mL/g; The pore volume of described anti-coking, impervious carbon-coating is 0.05-1.2mL/g, is preferably 0.1-1.0mL/g.
According to the present invention, although the selectable range of the thickness of described tack coat and anti-coking, impervious carbon-coating is wider, but, under the preferable case, also guarantee simultaneously the work-ing life of cracking furnace pipe in order to improve the anti-coking performance, as a rule, when the thickness of described tack coat is 0.5-15 μ m, be preferably 2-8 μ m; The thickness of described anti-coking, impervious carbon-coating is 2-100 μ m, and when being preferably 5-50 μ m, the over-all properties of the cracking furnace pipe of gained is splendid.
According to the present invention, described tack coat can and can further prevent the coating of coke and cracking furnace pipe substrate contact for existing various can bond described cracking furnace pipe matrix and anti-cokings, impervious carbon-coating, under the preferable case, described tack coat contains silicon-dioxide and/or metal oxide, metal in the described metal oxide can be selected from one or more in aluminium, titanium and the zirconium, further preferably, described metal oxide is selected from one or more in aluminum oxide, titanium oxide, the zirconium white.
According to the present invention, described anti-coking, impervious carbon-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 anti-coking, impervious carbon-coating can contain silicon-dioxide and/or metal oxide.Need to prove, 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 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 perovskite typed complex metal oxides have good resistance to elevated temperatures and anti-charing ability, therefore, when described metal oxide was spinel type composite metal oxide or perovskite typed complex metal oxides, the anti-coking of gained, the anti-coking of impervious carbon-coating and impervious carbon effect were very good.
According to invention, described cracking furnace pipe also comprises the active catalytic coating that is attached to described anti-coking, impervious carbon-coating surface; Described active catalytic coating can catalytic coke and water vapour react; Described active catalytic coating contains metal active constituent, and the metal in the described 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.
According to the present invention, the charge capacity of described 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 metal active constituent is 0.5-40g/m
2, 1-20g/m more preferably
2Described charge capacity refers to the weight of the 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 work as the roughness Ra of inner wall surface more than 0.2 μ m, when being preferably 0.2-0.8 μ m, the flushing resistance of the cracking furnace pipe of gained is 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 is 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 tack coat, and forms anti-coking, impervious carbon-coating in described tie layer surface; Described tack coat be for boning described cracking furnace pipe matrix and anti-coking, impervious carbon-coating and can prevent coke and the coating of cracking furnace pipe substrate contact, and described anti-coking, impervious carbon-coating are to prevent coke and cracking furnace pipe substrate contact and the coating that does not react with cracking stock and/or split product; Described tack coat and anti-coking, impervious carbon-coating have microvoid structure, and the average pore radius of the microvoid structure of described tack coat is less than the average pore radius of the microvoid structure of anti-coking, impervious carbon-coating.
According to the present invention, described tack coat can be by loading on the first colloidal sol cracking furnace pipe matrix inner wall surface and forming through the first thermal treatment, and described the first colloidal sol is selected from one or more in silicon sol, aluminium colloidal sol, titanium colloidal sol and the zirconium colloidal sol; Described anti-coking, impervious carbon-coating can be by loading on tie layer surface with the first slurry mix and/or the second slurry mix and forming through the second thermal treatment; Described the first slurry mix is for being that 2-5 or pH are under the condition of 9-11 at pH, at least a, the second colloidal sol in silicon-dioxide, metal oxide and the metal oxide hydrate and water are mixed to get, metal in described the first slurry mix in the metal oxide is selected from one or more in aluminium, titanium, zirconium, manganese, chromium, lanthanum and the magnesium, and the second colloidal sol in described the first slurry mix is selected from one or more in silicon sol, aluminium colloidal sol, titanium colloidal sol and the zirconium colloidal sol; Described the second slurry mix is for being that 2-5 or pH are under the condition of 9-11 at pH, silicon-dioxide and/or metal oxide, metal oxide hydrate and water are mixed to get, and the metal in described the second slurry mix in metal oxide and the metal oxide hydrate is selected from one or more in aluminium, titanium, zirconium, manganese, chromium, lanthanum and the magnesium.Metal oxide of the present invention is selected from one or more in aluminum oxide, titanium oxide, zirconium white, manganese picotite, magnesium-aluminium spinel and the manganese silicon spinel.
According to the present invention, under the preferable case, the average particulate diameter of solid phase is greater than the average particulate diameter of described the first colloidal sol in described the first slurry mix and the second slurry mix.Because when the average grain of described the first colloidal sol hour, described the first colloidal sol can fit tightly on the cracking furnace pipe matrix, thereby interpenetrates with described cracking furnace pipe matrix, combination; And in the first slurry mix and the second slurry mix average particulate diameter of solid phase greater than the average particulate diameter of described the first colloidal sol, guaranteed that again the first sol particle and the first slurry mix or the second slurry mix interpenetrate, combination, not only improve anti-coking, the anti-permeability performance of described cracking furnace pipe, also improved its flushing resistance.
The present invention is not particularly limited the average particulate diameter of solid phase in described the first slurry mix and the second slurry mix and the average particulate diameter size of colloidal sol, as long as guarantee that the average particulate diameter of solid phase in described the first slurry mix and the second slurry mix is greater than the average particulate diameter of colloidal sol, under the preferable case, the average particulate diameter of solid phase is 0.5-20 μ m, more preferably 0.5-10 μ m in described the first slurry mix and the second slurry mix; The average particulate diameter of described colloidal sol is 10-500nm, more preferably 20-100nm.
The present invention is to forming anti-coking, the content of each component is not particularly limited in the first slurry mix of impervious carbon-coating and the second slurry mix, can prevent coke and cracking furnace pipe substrate contact and the anti-coking that does not react with cracking stock and/or split product as long as can form, impervious carbon-coating, and guarantee the anti-coking that under the second heat-treat condition, obtains, impervious carbon-coating has the aperture and gets final product less than the vesicular structure in the aperture of tack coat, for example, the total mass of silicon-dioxide and metal oxide and metal oxide hydrate described in described the first slurry mix, the quality of the second colloidal sol and the mass ratio of water are 0.1-0.8: 0.01-1: 1; The mass ratio of total mass, metal oxide hydrate and the water of silicon-dioxide and metal oxide is 0.1-0.4: 0.01-0.4 described in described the second slurry mix: 1.
According to the present invention, need to prove, if when containing simultaneously silicon-dioxide, metal oxide and metal oxide hydrate in described the first slurry mix, then " total mass " refers to the total mass of silicon-dioxide and metal oxide and metal oxide hydrate in the aforementioned proportion, and the mass ratio of each material refers to the total mass of silicon-dioxide and metal oxide and metal oxide hydrate, the quality of the second colloidal sol and the mass ratio of water in the first slurry mix.If when containing any two kinds in silicon-dioxide, metal oxide and the metal oxide hydrate in described the first slurry mix, then " total mass " refers to any two kinds total mass in silicon-dioxide, metal oxide and the metal oxide hydrate, and the mass ratio of each material refers to any two kinds total mass in silicon-dioxide, metal oxide and the metal oxide hydrate, the quality of the second colloidal sol and the mass ratio of water in the first slurry mix; Under the preferable case, described the first slurry mix is silicon-dioxide or metal oxide, and the mixture of metal oxide hydrate, and the mass ratio of the quality of described silicon-dioxide or metal oxide and described metal oxide hydrate is 1: 0.05-1.If when only containing a kind of in silicon-dioxide, metal oxide or the metal oxide hydrate in described the first slurry mix, described " total mass " refers to the quality of silicon-dioxide or metal oxide or metal oxide hydrate, and the mass ratio of each material refers to the quality of silicon-dioxide or metal oxide or metal oxide hydrate, the quality of the second colloidal sol 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, described the first colloidal sol can be identical with the second colloidal sol, also can be different, and be selected from independently of one another in aluminium colloidal sol, silicon sol, titanium colloidal sol and the zirconium colloidal sol one or more.Described the first colloidal sol and the second colloidal sol can prepare by existing the whole bag of tricks, for example, can be with after sol precursor and the solvent, 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; PH can be by adding acid or alkali is regulated.
According to the present invention, to form anti-coking, the first slurry mix of impervious carbon-coating and viscosity and the stability of the second slurry mix in order regulating, can also in described the first slurry mix and/or the second slurry mix, can also to contain tensio-active agent and other metal-salts.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 in aluminum nitrate or aluminum nitrate hydrate, zirconium nitrate or zirconium nitrate hydrate and Titanium Nitrate or the Titanium Nitrate hydrate one or more.
According to the present invention, the method also is included in the active catalytic layer that described anti-coking, the enough catalytic cokes of impervious carbon-coating surface formation energy and water vapour react; Described active catalytic layer is the coating that loads on described anti-coking, impervious carbon-coating surface and form through thermal treatment by the soluble salt with metal.The soluble salt of described metal can be the soluble salt of existing various metals, as long as guarantee the product that after thermal treatment, obtains can catalytic coke and water vapour react, for example, the soluble salt of described metal is selected from the nitrate of metal, vitriol, carbonate, phosphoric acid salt, in chlorate and the acetate one or more, metal in the soluble salt of described metal is selected from lithium, sodium, potassium, rubidium, calcium, strontium, barium, molybdenum, cobalt, nickel, iron, copper, in cerium and the praseodymium one or more, preferably, the soluble salt of described metal 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 charge capacity of the soluble salt of described metal, and preferably, in metallic element, it is 0.5-40g/m that the charge capacity of the soluble salt of metal makes the charge capacity of the metal active constituent in the active catalytic layer that obtains
2Described charge capacity refers to the weight of the metal active constituent of institute's load on the per surface area.
According to the present invention, the method of described formation tack coat and anti-coking, impervious carbon-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), 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 load anti-coking, the impervious carbon-coating can be immersed in the solution that contains active ingredient.
In the process of described cracking furnace pipe preparation, can be by described tack coat of load of above method and anti-coking, impervious carbon-coating; Also can pass through repeatedly the described tack coat of load and anti-coking, impervious carbon-coating, until reach desired thickness.The consumption of described the first colloidal sol is as long as the thickness of the tack coat of assurance gained is for being preferably 0.5-15 μ m, and more preferably 2-8 μ m gets final product; In like manner, the consumption of described the first slurry mix and/or the second slurry mix is preferably 2-100 μ m as long as guarantee the anti-coking of gained, the thickness of impervious carbon-coating, and more preferably 5-50 μ m gets final product.
According to the present invention, described the first thermal treatment and the second heat treated condition generally include treatment temp and treatment time, as long as described treatment temp and treatment time can guarantee tack coat and anti-coking, the impervious carbon-coating of the cracking furnace pipe of gained and have microvoid structure, and the aperture of the microvoid structure of described tack coat gets final product less than the aperture of the microvoid structure of anti-coking, impervious carbon-coating, under the preferable case, the described first heat treated treatment temp is 300-1100 ℃, more preferably 600-1100 ℃, treatment time is 0.5-10 hour, more preferably 1-8 hour; The described second 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.
According to the present invention, the preparation method of described cracking furnace pipe also is included in before described cracking furnace pipe matrix surface load the first colloidal sol, described cracking furnace pipe matrix is carried out surface treatment, as long as described surface-treated method 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 acid and 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 having the tack coat of vesicular structure and have the anti-coking of vesicular structure, the thickness of impervious carbon-coating with determination of electron microscopy; Record average pore radius and pore volume with nitrogen absorption BET method; Average particulate diameter with particle size analyzer (the Rise-2208 type is purchased from the Science and Technology Ltd. of Jinan profit) test colloidal sol, slurry mix; 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 the first colloidal sol provided by the invention and the second colloidal sol.
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, pH regulator to 2.5 with said mixture, 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 the first colloidal sol provided by the invention and the second colloidal sol.
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, pH regulator to 11 with said mixture, 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 the first colloidal sol provided by the invention and the second colloidal sol.
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:
With 3g Al
2O
3H
2O, 2g Al (NO
3)
39H
2O, 20g γ-Al
2O
3Behind 75mL deionized water mixing and ball milling 18h, adding concentration is that the salpeter solution of 1.6mol/L reconciles the pH value to 3.5, obtains the first slurry mix, and the average particulate diameter of solid phase is 1.7 microns in described the first slurry mix.The colloidal sol that will be obtained by Preparation Example 1 loads on the cracking furnace pipe matrix that step (1) obtains by pickling process, at 70 ℃ after lower dry 1 hour, places 600 ℃ of lower roastings 2 hours, obtains tack coat; Above-mentioned the first slurry mix is loaded on the tack coat by pickling process, after 1 hour, place 600 ℃ of lower roastings 2 hours 120 ℃ of lower dryings, obtain anti-coking, impervious carbon-coating.Through measuring, the adhesive layer thickness of gained cracking furnace pipe is that 2 μ m, average pore radius are that 1nm, pore volume are 0.1mL/g; Anti-coking, impervious carbon-coating thickness are that 15 μ m, average pore radius are that 1.5nm, pore volume are 0.3mL/g.
Embodiment 2
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 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 0.6 cracking furnace pipe matrix.
(2) form coating at the cracking furnace pipe matrix:
Behind silicon sol, 40g silicon-dioxide and the 100mL deionized water mixing and ball milling 18h that 60g is obtained by Preparation Example 2, adding concentration is that the ammoniacal liquor of 1.6mol/L reconciles the pH value to 10, obtain the first slurry mix, the average particulate diameter of solid phase is 2.2 microns in described the first slurry mix.The colloidal sol that will be obtained by Preparation Example 2 loads on the cracking furnace pipe matrix that step (1) obtains by pickling process, at 70 ℃ after lower dry 1 hour, places 700 ℃ of lower roastings 2 hours, obtains tack coat; Above-mentioned slurry mix is loaded on the tack coat by pickling process, after 1 hour, place 900 ℃ of lower roastings 2 hours 120 ℃ of lower dryings, obtain anti-coking, impervious carbon-coating.Through measuring, the adhesive layer thickness of gained cracking furnace pipe is that 6 μ m, average pore radius are that 1.5nm, pore volume are 0.4mL/g; Anti-coking, impervious carbon-coating thickness are that 20 μ m, average pore radius are that 2nm, pore volume are 0.5mL/g.
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 silicon sol, 20g manganese silicon spinel, 20g zirconium white and the 130mL deionized water mixing and ball milling 18h that 30g is obtained by Preparation Example 2, adding concentration is that the ammoniacal liquor of 1.6mol/L reconciles the pH value to 10, obtain the first slurry mix, the average particulate diameter of solid phase is 1.5 microns in described the first slurry mix.The colloidal sol that will be obtained by Preparation Example 2 loads on the cracking furnace pipe matrix that step (1) obtains by pickling process, at 30 ℃ after lower dry 2 hours, places 800 ℃ of lower roastings 2 hours, obtains tack coat; Above-mentioned slurry mix is loaded on the tack coat by pickling process, after 1 hour, place 1000 ℃ of lower roastings 2 hours 120 ℃ of lower dryings, obtain anti-coking, impervious carbon-coating.Through measuring, the adhesive layer thickness of gained cracking furnace pipe is that 8 μ m, average pore radius are that 10nm, pore volume are 0.7mL/g; Anti-coking, impervious carbon-coating thickness are that 15 μ m, average pore radius are that 13nm, pore volume are 1.1mL/g.
Embodiment 4
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 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 0.25 cracking furnace pipe matrix.
(2) form coating at the cracking furnace pipe matrix:
Titanium colloidal sol, 20g manganese picotite (MnCr that 50g is obtained by Preparation Example 3
2O
4) and 50mL deionized water mixing and ball milling, adding concentration is that the 1.6mol/L salpeter solution reconciles the pH value to 4, obtains the first slurry mix, the average particulate diameter of solid phase is 1.3nm in described the first slurry mix.The colloidal sol that will be obtained by Preparation Example 3 loads to for twice on the cracking furnace pipe matrix that step (1) obtains repeatedly by pickling process, at 30 ℃ after lower dry 2 hours, places 500 ℃ of lower roastings 2 hours, obtains tack coat; Above-mentioned slurry mix is loaded to for twice on the tack coat repeatedly by pickling process, after 1 hour, place 1000 ℃ of lower roastings 2 hours 120 ℃ of lower dryings, obtain anti-coking, impervious carbon-coating.Through measuring, the adhesive layer thickness of gained cracking furnace pipe is that 9 μ m, average pore radius are that 8nm, pore volume are 0.8mL/g; Anti-coking, impervious carbon-coating thickness are that 30 μ m, average pore radius are that 10nm, pore volume are 1mL/g.
Embodiment 5
This embodiment explanation the invention provides the preparation of cracking furnace pipe.
Method according to embodiment 1 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
HK40 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.
Embodiment 6
Method according to embodiment 1 prepares cracking furnace pipe, and different is that this cracking furnace pipe also comprises the active catalytic coating that loads on anti-coking, the impervious carbon-coating, that is:
The cracking furnace pipe that embodiment 1 is obtained is 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, in calcium constituent, the charge capacity of described active ingredient is 1.3g/m
2
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 1 prepares cracking furnace pipe, and different is that this cracking furnace pipe does not comprise tack coat.
Test case 1-6
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 1-6 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 1-6, 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
Test case 7-12
This test case is used for the test of explanation cracking furnace pipe coating firmness.
In the cracking experiment of test case 1-6, the cracking furnace pipe outlet has a small amount of coke powder after burning, the STRENGTH ON COKE powder carries out ultimate analysis, does not find that the coating element of preparation appears in the outlet coke powder, and this illustrates that prepared coating can stand the impact of cracking atmosphere.In order further to check the coating firmness, adopt respectively the firmness of high temperature thermal shocking experiment and ultrasonic concussion examination coating.The cracking furnace pipe of gained among the embodiment 1-6 at the 500-1100 ℃ of lower 10min that keeps, is then immersed and cools off in the cold water, repeatedly 10 experiments, the coating in the cracking furnace pipe that embodiment 1-4,6 obtains is without obvious obscission; Coating in the cracking furnace pipe that embodiment 5 obtains has a small amount of coming off.Adopting water is ultrasonic medium, the cracking furnace pipe of gained among the embodiment 1-6, processes 20min in ultrasonator, and the coating in the cracking furnace pipe that embodiment 1-4,6 obtains is without obvious obscission; Coating in the cracking furnace pipe that embodiment 5 obtains has a small amount of coming off.This explanation is firm by coating and the combination of boiler tube matrix of the cracking furnace pipe that embodiment 1-4,6 prepares; The coating of the cracking furnace pipe that is prepared by embodiment 5 and boiler tube matrix are in conjunction with comparatively firm.
Contrast test example 3
This test case is used for the test of explanation cracking furnace pipe coating firmness.
Detect the anti-coking performance of cracking furnace pipe according to the method for test case 7-12, different is, what detect is the cracking furnace pipe that the method by Comparative Examples 2 obtains.
In the cracking experiment of contrast test example 2, the cracking furnace pipe outlet has a small amount of coke powder after burning, the STRENGTH ON COKE powder carries out ultimate analysis, does not find that the coating element of preparation appears in the outlet coke powder, and this illustrates that prepared coating can stand the impact of cracking atmosphere.In order further to check the coating firmness, adopt respectively the firmness of high temperature thermal shocking experiment and ultrasonic concussion examination coating.The cracking furnace pipe of gained in the Comparative Examples 2 at the 500-1100 ℃ of lower 10min that keeps, is then immersed and cools off in the cold water, repeatedly 5 experiments, coating begins to occur obscission.Adopting water is ultrasonic medium, the cracking furnace pipe of gained in the Comparative Examples 2, processes 10min in ultrasonator, obscission occurs.This explanation is firm not in conjunction with getting by coating and the boiler tube matrix of the cracking furnace pipe that Comparative Examples 2 prepares.
Claims (18)
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, is attached to the tack coat of cracking furnace pipe matrix inner wall surface and is attached to the anti-coking of described tie layer surface, impervious carbon-coating; Described tack coat is for can bond described cracking furnace pipe matrix and anti-coking, impervious carbon-coating and can prevent the coating of coke and cracking furnace pipe substrate contact, and described anti-coking, impervious carbon-coating are to prevent coke and cracking furnace pipe substrate contact and the coating that does not react with cracking stock and/or split product; Described tack coat and anti-coking, impervious carbon-coating have microvoid structure, and the average pore radius of the microvoid structure of described tack coat is less than the average pore radius of the microvoid structure of described anti-coking, impervious carbon-coating.
2. method according to claim 1, wherein, the average pore radius of the microvoid structure of described tack coat is 0.2-10nm, pore volume is 0.01-1.1mL/g; The average pore radius of the microvoid structure of described anti-coking, impervious carbon-coating is 0.5-15nm, and pore volume is 0.05-1.2mL/g.
3. method according to claim 1 and 2, wherein, the thickness of described tack coat is 0.5-15 μ m, is preferably 2-8 μ m; The thickness of described anti-coking, impervious carbon-coating is 2-100 μ m, is preferably 5-50 μ m.
4. method according to claim 1, wherein, described tack coat contains silicon-dioxide and/or metal oxide, and the metal in the described metal oxide is selected from one or more in aluminium, titanium and the zirconium.
5. method according to claim 1, wherein, described anti-coking, impervious carbon-coating contain silicon-dioxide and/or metal oxide; Metal in the described metal oxide is selected from one or more in aluminium, titanium, zirconium, manganese, chromium, lanthanum and the magnesium.
6. method according to claim 1, wherein, described cracking furnace pipe also comprises the active catalytic coating that is attached to described anti-coking, impervious carbon-coating surface; Described active catalytic coating can catalytic coke and water vapour react; Described active catalytic coating contains metal active constituent, and the metal in the described 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; In metallic element, the charge capacity of described metal active constituent is 0.1-40g/m
2, described charge capacity refers to the weight of the metal active constituent of institute's load on the per surface area.
7. 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.
8. method according to claim 1, wherein, described cracking condition comprises that cracking temperature is 750-1000 ℃; Cracking pressure is 0-0.3MPa.
9. 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 tack coat, and forms anti-coking, impervious carbon coating in described tie layer surface; Described tack coat be for boning described cracking furnace pipe matrix and anti-coking, impervious carbon-coating and can prevent coke and the coating of cracking furnace pipe substrate contact, and described anti-coking, impervious carbon-coating are to prevent coke and cracking furnace pipe substrate contact and the coating that does not react with cracking stock and/or split product; Described tack coat and anti-coking, impervious carbon-coating have microvoid structure, and the average pore radius of the microvoid structure of described tack coat is less than the average pore radius of the microvoid structure of anti-coking, impervious carbon-coating.
10. method according to claim 9, wherein, the average pore radius of the microvoid structure of described tack coat is 0.2-10nm, pore volume is 0.01-1.1mL/g; The average pore radius of the microvoid structure of described anti-coking, impervious carbon-coating is 0.5-15nm, and pore volume is 0.05-1.2mL/g.
11. method according to claim 9, wherein, described tack coat is by loading on the first colloidal sol cracking furnace pipe matrix inner wall surface and forming through the first thermal treatment, and described the first colloidal sol is selected from one or more in silicon sol, aluminium colloidal sol, titanium colloidal sol and the zirconium colloidal sol; Described anti-coking, impervious carbon-coating are by loading on tie layer surface with the first slurry mix and/or the second slurry mix and forming through the second thermal treatment; Described the first slurry mix is for being that 2-5 or pH are under the condition of 9-11 at pH, at least a, the second colloidal sol in silicon-dioxide, metal oxide and the metal oxide hydrate and water are mixed to get, metal in described the first slurry mix in the metal oxide is selected from one or more in aluminium, titanium, zirconium, manganese, chromium, lanthanum and the magnesium, and the second colloidal sol in described the first slurry mix is selected from one or more in silicon sol, aluminium colloidal sol, titanium colloidal sol and the zirconium colloidal sol; Described the second slurry mix is for being that 2-5 or pH are under the condition of 9-11 at pH, silicon-dioxide and/or metal oxide, metal oxide hydrate and water are mixed to get, and the metal in described the second slurry mix in metal oxide and the metal oxide hydrate is selected from one or more in aluminium, titanium, zirconium, manganese, chromium, lanthanum and the magnesium.
12. method according to claim 11, wherein, the consumption of described the first colloidal sol is preferably 2-8 μ m so that the thickness of tack coat is 0.5-15 μ m; The consumption of described the first slurry mix and/or the second slurry mix is preferably 5-50 μ m so that the thickness of described anti-coking, impervious carbon-coating is 2-100 μ m.
13. according to claim 11 or 12 described methods, wherein, the average particulate diameter of solid phase is greater than the average particulate diameter of described the first colloidal sol in described the first slurry mix and the second slurry mix, and the average particulate diameter of solid phase is 0.5-20 μ m in described the first slurry mix and the second slurry mix, and the average particulate diameter of described the first colloidal sol is 10-500nm.
14. according to claim 11 or 12 described methods, wherein, the mass ratio of the quality of the total mass of silicon-dioxide and metal oxide and metal oxide hydrate, the second colloidal sol and water is 0.1-0.8: 0.01-1 described in described the first slurry mix: 1; The mass ratio of total mass, metal oxide hydrate and the water of silicon-dioxide and metal oxide is 0.1-0.4: 0.01-0.4 described in described the second slurry mix: 1.
15. method according to claim 11, 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.
16. method according to claim 11, wherein, the method also is included in before described cracking furnace pipe matrix surface load the first colloidal sol, 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.
17. method according to claim 16, 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.
18. method according to claim 9, the method also are included in the active catalytic layer that described anti-coking, the enough catalytic cokes of impervious carbon-coating surface formation energy and water vapour react; Described active catalytic layer is the coating that loads on described anti-coking, impervious carbon-coating surface and form through thermal treatment by the soluble salt with metal; The soluble salt of described metal is selected from one or more in nitrate, vitriol, carbonate, phosphoric acid salt, chlorate and the acetate of metal, metal in the soluble salt of described metal is selected from one or more in lithium, sodium, potassium, rubidium, calcium, strontium, barium, molybdenum, cobalt, nickel, iron, copper, cerium and the praseodymium, preferably, the soluble salt of described metal 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; The consumption of the soluble salt of described metal so that, in metallic element, the charge capacity of the metal active constituent that obtains is 0.1-40g/m
2, described charge capacity refers to the weight of the metal active constituent of institute's load on the per surface area.
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| CN105087044A (en) * | 2014-05-05 | 2015-11-25 | 中国石油化工股份有限公司 | On-line treating method for inner surface of hydrocarbon cracking furnace pipe |
| CN112204279A (en) * | 2018-05-30 | 2021-01-08 | Ksb股份有限公司 | Shaft sealing device |
| CN113004724A (en) * | 2021-03-08 | 2021-06-22 | 华东理工大学 | Coating for inhibiting furnace tube coking and preparation method thereof |
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