CN112708446A - Method for reducing coking of cracking device and application thereof - Google Patents

Method for reducing coking of cracking device and application thereof Download PDF

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Publication number
CN112708446A
CN112708446A CN201911025895.3A CN201911025895A CN112708446A CN 112708446 A CN112708446 A CN 112708446A CN 201911025895 A CN201911025895 A CN 201911025895A CN 112708446 A CN112708446 A CN 112708446A
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cracking
catalytic coating
coking
partial pressure
oxygen partial
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郏景省
王申祥
王红霞
张利军
王国清
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G9/14—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils in pipes or coils with or without auxiliary means, e.g. digesters, soaking drums, expansion means
    • C10G9/18—Apparatus
    • C10G9/20—Tube furnaces
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/32—Manganese, technetium or rhenium
    • B01J23/34—Manganese
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/024—Multiple impregnation or coating
    • B01J37/0244—Coatings comprising several layers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
    • C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
    • C07C4/04—Thermal processes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G9/14—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils in pipes or coils with or without auxiliary means, e.g. digesters, soaking drums, expansion means
    • C10G9/16—Preventing or removing incrustation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G9/14—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils in pipes or coils with or without auxiliary means, e.g. digesters, soaking drums, expansion means
    • C10G9/18—Apparatus
    • C10G9/20—Tube furnaces
    • C10G9/203—Tube furnaces chemical composition of the tubes
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

The invention relates to a method for reducing coking of a cracking device and application thereof. The method comprises the following steps: cracking device under low oxygen partial pressure atmosphere at 800-Is heat treated to form a first catalytic coating on the inner surface of the cracking device; preparing a second catalytic coating on the surface of the first catalytic coating; the first catalytic coating comprises a composition of MnxCr3‑xO4The second catalytic coating comprises the composition AMO3Is (Na) and/or has a composition of2O)yNa2[Al2Si2O8]The triclosane-like substance of (1); wherein A is an alkaline earth metal element, and M is at least one selected from group IIIB elements and group IVB elements; x satisfies: x is more than or equal to 0.5 and less than or equal to 1.5, and y satisfies the following condition: y is more than 0 and less than or equal to 1. The method can obviously reduce coking in the cracking process, particularly in the cracking process of heavy cracking raw materials on the premise of maintaining the yield of the olefin in the cracking product to be basically unchanged.

Description

Method for reducing coking of cracking device and application thereof
Technical Field
The invention relates to the field of cracking device coking, in particular to a method for reducing cracking device coking and application thereof.
Background
Ethylene is one of the most important basic raw materials in the petrochemical industry. At present, the method for producing ethylene mainly adopts a tubular furnace cracking technology, and the technology is widely applied in the world. But the problems of coking and carburization are inevitably generated in the production process of the ethylene, so that the inner diameter of a furnace tube of the cracking furnace is reduced, the pressure drop in the tube is increased, the normal operation of the cracking reaction is hindered, the yield of the ethylene is influenced, and the production efficiency is reduced. In addition, the high temperature of cracking easily causes the inner wall of the furnace tube of the cracking furnace to carburize, i.e., the carbon deposit and the substrate of the furnace tube undergo a chemical reaction, which results in the weakening of the material performance of the furnace tube, influences the service life of the furnace tube and shortens the operation period of the cracking furnace. Therefore, when the temperature of the tube wall of the furnace tube reaches an allowable limit or the pressure drop reaches a certain degree, the furnace must be stopped for decoking in order to ensure the normal operation of the furnace tube of the cracking furnace. Therefore, the development of the method capable of reducing coking of the furnace tube of the hydrocarbon cracking furnace is a key development direction for producing ethylene, and has great practical significance and economic value for the current petrochemical industry.
Generally, the matrix of the cracking device contains iron and nickel, the iron and the nickel can catalyze olefin to generate filamentous coke at high temperature, and the coke is attached to the cracking device, so that the inner diameter of a furnace tube is reduced, the pressure drop in the furnace tube is increased, and the operation period of the cracking furnace is shortened.
Coking in the cracking process is mainly divided into catalytic coking, free radical coking and pitch coking. For light gas cracking raw materials, catalytic coking is mainly performed in coking during cracking, radical coking and asphalt coking are assisted, and for heavy liquid cracking raw materials, catalytic coking is assisted in coking during cracking, radical coking and asphalt coking are mainly performed. In the prior art, a layer of inert coating is prepared on the inner surface of the cracking device mainly by methods such as plasma spraying, hot sputtering, vapor deposition and the like, so that catalytic coking in the cracking process is reduced, but free radical coking and asphalt coking in the cracking process have no obvious effect. Especially for liquid cracking raw materials, the proportion of free radical coking and asphalt coking in coking is larger, and the inert coating on the inner surface of the cracking device can not obviously reduce the coking in the liquid cracking raw materials.
For example, US6537388 discloses that a compound containing Cr and Si is loaded in an ethylene furnace tube, after passivation treatment, elements of Cr and Si are diffused into a base metal of the furnace tube to form a Cr-Si bottom layer, then a compound containing Si and Al is sprayed on the Cr-Si bottom layer by a hot sputtering method, and after heat treatment, an Si-Al outer layer is formed.
CN1399670A discloses a method for treating a metal wall of a cracking reactor, which comprises pretreating the metal surface in contact with organic matter to be cracked with a steam gas stream containing at least one silicon compound and at least one sulfur compound at 300-. The method is characterized in that a layer of inert coating is prepared on the surface of the cracking device, so that catalytic coking in the cracking process can be reduced to a certain extent, and the operation period is prolonged.
CN104619789A discloses a medicineIn the manufacture of catalytic surfaces and coatings for petrochemicals. The patent supports metal powder containing Mn, Ni, Fe, Si, W and other elements on the surface of metal, and controls the oxidation condition to generate Mn on the surface of a coatingxOy、MnCr2O4W-based oxide, etc., and the ability of the coating to gasify coke is adjusted by the content of the W-based oxide.
CN102260519A and CN102295284A disclose the preparation of perovskite material, a triclopyr-like substance, on the inner surface of the cracking apparatus, respectively, to reduce coke deposition during hydrocarbon cracking. However, neither of these methods investigated the effect of materials prepared on the inner surface of the cracker on the cracked product.
The coking reduction method in the prior art has no obvious effect on free radical coking and pitch coking in the cracking process, and only focuses on the coking reduction effect, but does not focus on the influence of the used coking reduction method on the yield of cracking products.
Accordingly, there is a need for a process that effectively reduces coking of the internal surfaces of the cracking unit while not substantially affecting the olefin yield.
Disclosure of Invention
The inventor of the invention finds that the coking reduction method of the prior art generally has the problems of insignificant coking reduction effect, adverse influence on the yield of cracked product olefin and the like, such as singly coating a layer of perovskite type material or a triclopyr-like substance on the inner surface of a cracking device, and generation of a large amount of CO and CO although coking in the cracking process can be reduced2The olefin yield is influenced, and the subsequent separation system is greatly influenced.
In order to solve the above problems, the present inventors have studied and found that a cracking apparatus is sequentially formed to include Mn as a compositionxCr3-xO4The first catalytic coating of the manganese-chromium-oxygen complex comprises the composition AMO3Is (Na) and/or has a composition of2O)yNa2[Al2Si2O8]The second catalytic coating of the triclopyr-like material of (a) can reduce both catalytic coking and cracking during crackingAsphalt coking and free radical coking in the cracking process are solved, and the coking in the cracking process is reduced as much as possible under the condition of keeping the olefin yield in the cracking product basically unchanged; in addition, this process does not adversely increase CO and CO in the product2The yield of (A) was found.
To this end, the present invention provides in a first aspect a method of reducing coking in a cracking unit comprising:
(1) carrying out heat treatment on the inner surface of the cracking device under the atmosphere with low oxygen partial pressure and at the temperature of 800-1200 ℃ so as to form a first catalytic coating on the inner surface of the cracking device;
(2) preparing a second catalytic coating on the surface of the first catalytic coating;
the first catalytic coating comprises a composition of MnxCr3-xO4The second catalytic coating comprises AMO3Is (Na) and/or has a composition of2O)yNa2[Al2Si2O8]The triclosane-like substance of (1); wherein A is an alkaline earth metal element, and M is at least one selected from group IIIB elements and group IVB elements; x satisfies: x is more than or equal to 0.5 and less than or equal to 1.5, and y satisfies the following condition: y is more than 0 and less than or equal to 1.
In a second aspect the invention provides the use of the method of the first aspect of the invention in a hydrocarbon cracking process, preferably a hydrocarbon thermal cracking process.
The method of the invention can obviously reduce coking in the cracking process, particularly in the cracking process of heavy cracking raw materials, on the premise of maintaining the yield of the olefin in the cracking products to be basically unchanged, and in addition, the method can not increase CO and CO in the products disadvantageously2The yield of (A) was found.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In a first aspect, the present invention provides a method for reducing coking in a cracking unit, comprising:
(1) carrying out heat treatment on the inner surface of the cracking device under the atmosphere with low oxygen partial pressure and at the temperature of 800-1200 ℃ so as to form a first catalytic coating on the inner surface of the cracking device;
(2) preparing a second catalytic coating on the surface of the first catalytic coating;
the first catalytic coating comprises a composition of MnxCr3-xO4The second catalytic coating comprises AMO3Is (Na) and/or has a composition of2O)yNa2[Al2Si2O8]The triclosane-like substance of (1); wherein A is an alkaline earth metal element, and M is at least one selected from group IIIB elements and group IVB elements; x satisfies: x is more than or equal to 0.5 and less than or equal to 1.5, and y satisfies the following condition: y is more than 0 and less than or equal to 1.
One embodiment of the present invention provides a cracking furnace tube as a cracking device, wherein the inner surface of the cracking device is the inner wall of the cracking furnace tube.
According to the present invention, preferably, the cracking furnace tubes comprise: 30-40 wt% Cr; 20-50 wt% Ni; 0.2-5 wt% Mn; 0.2-0.6 wt% of C, 0.001-5 wt% of trace elements and 15-40 wt% of Fe. For example, the cracking furnace tube is made of materials including, but not limited to, HK40, HP40, Cr35Ni45, and the like.
As used herein, "trace elements" include C, S, P, Al, Nb, Ti, W, Mo, rare earth elements, and the like.
According to the present invention, preferably, the oxygen partial pressure in the low oxygen partial pressure atmosphere is less than or equal to 10-12atm, preferably, oxygen partial pressure in low oxygen partial pressure atmosphere is less than or equal to 10-18atm, more preferably, the oxygen partial pressure in the low oxygen partial pressure atmosphere is 10-30-10-18atm。
Herein, unless otherwise specified, pressure means absolute pressure; "atm" means atmospheric pressure, for example, "1 atm" means 1 atmosphere.
Preferably, the low oxygen partial pressure atmosphere comprises H2、CO2CO and H2And O. In a specific embodiment, the low oxygen partial pressure atmosphere consists of H2、CO2CO and H2And (C) O.
According to the present invention, in order to obtain the first catalytic coating excellent in both thickness and denseness, it is preferable that in step (1), the heat treatment conditions include: the pressure is 1-4atm, and the time is 5-100 h; preferably, the temperature is 900-.
Preferably, the first catalytic coating comprises 0-15 wt.% Ni, 0-15 wt.% Fe, 0-5 wt.% Si and 70-100 wt.% manganese chromium oxygen complex. The manganese-chromium-oxygen composite comprises at least one of manganese oxide, chromium oxide and manganese-chromium oxide. Oxides of manganese include, but are not limited to, MnO, Mn2O3、Mn3O4、MnO2Manganese chromium oxides include, but are not limited to, MnCr2O4。
In this context, "manganese-chromium-oxygen complex" refers to a mixture of oxides of both elements manganese, chromium.
Herein, "manganese chromium oxide" refers to a compound formed by three elements of manganese, chromium and oxygen.
According to the invention, the thickness of the first catalytic coating is preferably between 0.5 and 20 μm, preferably between 0.5 and 10 μm.
Preferably, the thickness of the second catalytic coating is 0.5-10 μm, preferably 0.5-5 μm.
In the invention, the first catalytic coating not only can inhibit catalytic coking in the cracking process, but also can gasify coke deposited on the surface of the coating.
According to the present invention, preferably, in step (2), the second catalytic coating layer is prepared by impregnating a precursor of the perovskite material and/or a precursor of the triclopyr-like substance on the first catalytic coating layer, followed by calcination; alternatively, the second catalytic coating is prepared by carrying a precursor of the perovskite material and/or a precursor of the triclopyr-like substance into the cracking apparatus using a carrier gas under a low oxygen partial pressure atmosphere at 800-. Preferably, the conditions of the calcination include: the temperature is 900-.
According to the invention, preferably, the carrier gas is selected from nitrogen, helium, hydrogen, CO and CO2At least one of (1).
The precursor of the perovskite material in the present invention is not particularly limited, and the precursor of the perovskite material includes, but is not limited to, various salts, oxides, and the like capable of forming a perovskite material, and may be used in the form of a solution or a sol. Also, the present invention is not particularly limited to the precursor of the triclopyr-like substance, and the precursor of the triclopyr-like substance includes, but is not limited to, various salts, oxides, and the like capable of forming the triclopyr-like substance, and may be used in the form of a solution or a sol. For example, preparation of a catalyst containing BaCeO3During the second catalytic coating of the perovskite material, after the cracking device is subjected to heat treatment under the low oxygen partial pressure atmosphere to form the first catalytic coating, dipping barium oxide sol and cerium oxide sol or dipping barium nitrate solution and cerium nitrate solution on the first catalytic coating, and then roasting at 800-1200 ℃ to obtain the perovskite material; or after the heat treatment is finished under the low oxygen partial pressure atmosphere, carrying the barium oxide sol and the cerium oxide sol by using carrier gas at the temperature of over 800 ℃, or introducing the barium nitrate solution and the cerium nitrate solution into a cracking device to prepare the barium nitrate cerium nitrate barium nitrate cerium nitrate.
In order to reduce cracking coking as much as possible without affecting the yield of cracked olefins according to the present invention, the mass of the second catalytic coating is preferably 0.1 to 50%, preferably 0.1 to 25%, of the mass of the first catalytic coating.
Preferably, in the second catalytic coating, the perovskite material is selected from SrCeO3、SrZr0.3Ce0.7O3、BaMnO3、BaCeO3、BaZr0.3Ce0.7O3、BaZr0.3Ce0.5Y0.2O3、BaZr0.1Ce0.7Y0.2O3、BaZrO3、BaZr0.7Ce0.3O3、BaCe0.5Zr0.5O3、BaCe0.9Y0.1O3、BaCe0.85Y0.15O3And BaCe0.8Y0.2O3At least one of; more preferably selected from BaCeO3、BaCe0.5Zr0.5O3And BaCe0.8Y0.2O3At least one of (1).
Preferably, in the second catalytic coating, the triclopyr-like substance is Na4Al2Si2O9。
Compared with common oxides (such as manganese oxide and chromium oxide), the perovskite material has better high-temperature stability and anti-coking performance, can keep stability for a long time under a cracking atmosphere, has better capability of catalyzing coke gasification, and does not coke on the surface of the perovskite material basically in the cracking process.
According to the invention, the method preferably further comprises treating the inner surface of the cracking unit, for example, cleaning with acid and a cleaning agent, to remove oil stains and other impurities from the inner wall surface of the cracking unit substrate, before the heat treatment to prepare the first catalytic coating. The selection of the cleaning agent in the present invention is not particularly limited as long as the effect of removing oil stains can be achieved, and examples thereof include acids, water, alcohols, and the like; the inner surface of the cracking device can also be polished and the like so as to facilitate the preparation of the subsequent coating.
The coatings (the first catalytic coating and the second catalytic coating) prepared by the method comprise manganese-chromium-oxygen compounds, perovskite oxides and/or triclosan-like substances, and the perovskite oxides and/or the triclosan-like substances have good high-temperature stability and anti-carbonization capability, are inert to catalytic coking, can enable coke and water to generate gasification reaction, and can obviously reduce coking without influencing the yield of olefin.
The first catalytic coating and the second catalytic coating are sequentially formed on the surface of the cracking device, so that the synergistic effect of the manganese-chromium-oxygen compound and the perovskite oxide (and/or the triclosan-like substance) is realized, the asphalt coking and the free radical coking in the heavy cracking raw material can be better reduced on the basis of reducing the catalytic coking, the gasification of the formed coking is facilitated, and the running period of the cracking furnace is prolonged to the maximum extent under the condition of basically not influencing the yield of the cracking product.
In a second aspect, the invention provides the use of the method of the first aspect of the invention in a hydrocarbon cracking process, in particular in a heavy cracking feedstock cracking process.
More particularly, the second aspect of the invention provides the use of the process of the first aspect of the invention in a process for thermal cracking of heavy cracked feedstocks.
For heavy liquid cracking raw material, catalytic coking is used as auxiliary in coking during cracking, free radical coking and asphalt coking are mainly used, and Mn is prepared on the inner surface of a cracking furnace tubexCr3-xO4The first catalytic coating and the composition of AMO3Is (Na) and/or has a composition of2O)yNa2[Al2Si2O8]The ability of catalyzing coke and strengthening coke gasification reaction is reduced, so that free radical coking and pitch coking in the cracking process are reduced to a greater extent.
The method can obviously reduce coking in the cracking process and does not increase H in the cracking product disadvantageously on the premise of maintaining the yield of the olefin in the cracking product to be basically unchanged2、CO、CO2The yield of (A) was found.
The present invention will be described in further detail below by way of examples.
In the following examples and comparative examples, the naphtha used was hydrogenated naphtha produced by a marine refinery, unless otherwise specified.
Reference example 1
In order to examine the catalytic capability of different oxides for catalyzing the gasification reaction of coke (with water vapor), BaCe is added0.8Y0.2O3、MnCr2O4、Al2O3、Mn3O4Respectively and uniformly mixing with carbon powder according to the proportion of 300mg to 30mg, putting the mixture into a hanging basket of a ThermoCahn thermogravimetric analyzer, introducing mixed gas of He gas and 2.3 percent of water vapor, and carrying out temperature programming at 400 ℃ and 950 ℃.
Detecting CO and CO in the outlet gas with SIEMENSULTRAMAT23 infrared analyzer2And measuring the volume (V, L) of the off-gas, the combined gas volume and the CO concentration (C) with a wet flowmeter1，vol％)、CO2Concentration (C)2Vol%) calculated amount of coke reacted (m, g):
m＝V×(C1+C2) X 12X 273.15/(298.15X 22.4), wherein the outlet temperature of the wet flowmeter is 25 ℃ at room temperature, and the atmospheric pressure is 1 atm.
The results of the experiment are shown in table 1. As can be seen, the coke amount of the reaction is BaCe from more to less in turn in the process of temperature rise0.8Y0.2O3>Mn3O4≈MnCr2O4>Al2O3>Carbon powder, from which it can be seen that the ability to catalyze the gasification of coke is ranked from superior to inferior as BaCe0.8Y0.2O3>Mn3O4≈MnCr2O4>Al2O3。
TABLE 1 results of catalytic Coke gasification reactions with different oxide systems
Figure BDA0002248614200000081
Figure BDA0002248614200000091
Comparative example 1
Carrying barium nitrate solution, cerium nitrate solution and iridium nitrate solution into a cracking device by using nitrogen (carrier gas), depositing at 900 ℃ for 0.5h, and preparing BaCe on the inner surface of the cracking device (HK40)0.8Y0.2O3Coating and carrying out naphtha cracking experiments according to the following conditions. While a blank furnace tube was used for naphtha cracking experiments for comparison.
The naphtha feed rate was 100g/h, the water feed rate was 50g/h, the preheating temperature was 600 ℃, the cracking temperature was 850 ℃, and the residence time was about 0.5 s.
After the cracking experiment is finished, the temperature of the furnace tube is controlled at 810 and 840 ℃ by utilizing N2、O2The mixed gas is burnt, and the concentration of CO and CO in the burnt gas2The concentration is measured on line by an ULTRAMAT23 type infrared gas analyzer of Siemens company, Germany, the volume of the scorching gas is measured on line by a TG5/5 type gas wet flowmeter of Ritter company, Germany, the readings of the concentration and the volume are transmitted to a computer through a counter module, and finally the total coking amount in the cracking process is calculated.
According to the coking amount (m) of the blank furnace tube1) And the coking amount (m) of the furnace tube after the coating is formed2) The coking inhibition rate (delta) after the coating layer was formed was calculated according to the following formula (1),
Figure BDA0002248614200000092
the results are shown in Table 2.
As can be seen from Table 2, although the present example has the BaCe-containing tube, it is compared with the blank cracking furnace tube0.8Y0.2O3The coke content of the cracking device of the coating is reduced by 96.1 percent, but H in the product2、CO、CO2The yield is obviously increased, and the yields of ethylene, propylene and butadiene are slightly reduced.
As can be seen, this example has the feature of containing BaCe0.8Y0.2O3The cracking device of the coating can greatly reduce coking in the cracking process, but greatly increases H2、CO、CO2The yield of the olefin is influenced, and great pressure is caused on a subsequent separation system.
Comparative example 2
At an oxygen partial pressure of 10-20Treating cracker (HK40) at 950 deg.C for 10h under atm atmosphere to generate MnCr on the inner surface of the cracker2O4After which a naphtha cracking test was performed under the conditions described in comparative example 1, and scorch and test were performed under the conditions described in comparative example 1, with the results shown in table 2.
As can be seen from Table 2, this example has a bag as compared to a blank lysis deviceContaining MnCr2O4The coke content of the coating was reduced by 64.42%, but the yield of CO in the cracked product was significantly higher, and the yields of ethylene, propylene, and butadiene were significantly lower compared to the blank cracking unit, comparative example 1.
As can be seen, this example has MnCr2O4The cracking device of the coating can reduce the coking amount, but the yield of CO in the cracking product is higher, and the yields of ethylene, propylene and butadiene are obviously lower.
Comparative example 3
Carrying sodium nitrate solution, silica sol and aluminum sol into a cracking device (HK40) by nitrogen (carrier gas), depositing at 850 deg.C for 1h, and generating Na-containing on the inner surface of the cracking device4Al2Si2O9After which a naphtha cracking test was performed under the conditions described in comparative example 1, and scorch and test were performed under the conditions described in comparative example 1, with the results shown in table 2.
As can be seen from Table 2, this example has Na in comparison with the blank cracking apparatus4Al2Si2O9The amount of coking of the coating was reduced by 95.3%, but H2、CO、CO2The yield is obviously increased, and compared with a blank cracking device and a comparative example 1, the yield of ethylene, propylene and butadiene is slightly reduced.
Therefore, this embodiment contains Na4Al2Si2O9The cracking device of the coating can reduce the coking amount, but greatly increases H2、CO、CO2The yield of the olefin is influenced, and great pressure is caused on a subsequent separation system.
Example 1
At an oxygen partial pressure of 10-20Treating cracker (HK40) at 1atm (total pressure) and 950 deg.C for 10h under atm atmosphere, and preparing MnCr on the inner surface of the cracker2O4Then the barium nitrate solution, the cerium nitrate solution and the iridium nitrate solution are carried into a cracking device by nitrogen (carrier gas) and deposited for 0.5h at the temperature of 900 ℃ under the atmosphere of 1atm, and BaCe is prepared on the surface of the first catalytic coating0.8Y0.2O3After the naphtha cracking test was performed under the conditions described in comparative example 1, and the scorch and the test were performed under the conditions described in comparative example 1, the results are shown in table 2.
As can be seen from Table 2, this example has MnCr as compared with the blank cracking apparatus2O4-BaCe0.8Y0.2O3The coking amount of the cracking device of the coating is reduced by 70.19 percent, and H in the cracking product2、CO、CO2The yield is obviously reduced, and the yields of ethylene, propylene and butadiene are slightly reduced.
As can be seen, this example has MnCr2O4-BaCe0.8Y0.2O3The coated cracking unit is capable of maintaining H in the product2、CO、CO2The yield of the catalyst is basically unchanged, and the coking amount is effectively reduced under the condition that the yield of the olefin is basically unchanged.
Example 2
At an oxygen partial pressure of 10-20Treating cracker (HK40) at 1atm (total pressure) and 950 deg.C for 10h under atm atmosphere, and preparing MnCr on the inner surface of the cracker2O4Then carrying the sodium nitrate solution, the silica sol and the aluminum sol into a cracking device by using nitrogen (carrier gas), depositing for 1h at 1atm and 850 ℃, and preparing Na-containing on the surface of the first catalytic coating4Al2Si2O9After the naphtha cracking test was performed under the conditions described in comparative example 1, and the scorch and the test were performed under the conditions described in comparative example 1, the results are shown in table 2.
As can be seen from Table 2, this example has MnCr as compared with the blank cracking apparatus2O4-Na4Al2Si2O9The coke content of the coated cracking unit was reduced by 73.77%, and the product H was compared to comparative examples 1-22、CO、CO2The yield is basically unchanged, and the yields of ethylene, propylene and butadiene are basically unchanged.
As can be seen, this example has MnCr2O4-Na4Al2Si2O9The coated cracking unit is capable of maintaining H in the product2、CO、CO2The yield of the catalyst is basically unchanged, and the coking amount is effectively reduced under the condition that the yield of the olefin is basically unchanged.
TABLE 2 olefin yield and coking amount in naphtha cracking process for cracking unit with different coatings
Figure BDA0002248614200000121
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (10)

1. A method of reducing coking in a cracking unit comprising:
(1) carrying out heat treatment on the inner surface of the cracking device under the atmosphere with low oxygen partial pressure and at the temperature of 800-1200 ℃ so as to form a first catalytic coating on the inner surface of the cracking device;
(2) preparing a second catalytic coating on a surface of the first catalytic coating;
the first catalytic coating comprises a composition of MnxCr3-xO4The second catalytic coating comprises a composition AMO3Is (Na) and/or has a composition of2O)yNa2[Al2Si2O8]The triclosane-like substance of (1); wherein A is an alkaline earth metal element, and M is at least one selected from group IIIB elements and group IVB elements; x satisfies: x is more than or equal to 0.5 and less than or equal to 1.5, and y satisfies the following condition: y is more than 0 and less than or equal to 1.
2. According to claim 1The method of (1), wherein the oxygen partial pressure in the low oxygen partial pressure atmosphere is 10 or less-12atm；
Preferably, the oxygen partial pressure in the low oxygen partial pressure atmosphere is less than or equal to 10-18atm；
More preferably, the oxygen partial pressure in the low oxygen partial pressure atmosphere is 10-30-10-18atm；
Preferably, the low oxygen partial pressure atmosphere comprises H2、CO2CO and H2O。
3. The method according to claim 1 or 2, wherein, in step (1), the conditions of the heat treatment include: the pressure is 1-4atm, and the time is 5-100 h;
preferably, the conditions of the heat treatment include: the temperature is 900-.
4. The method of claim 1, wherein the first catalytic coating comprises 0-15 wt.% Ni, 0-15 wt.% Fe, 0-5 wt.% Si, and 70-100 wt.% of the manganese chromium oxygen complex.
5. A method according to claim 1 or 2, wherein in step (2) the second catalytic coating is prepared by impregnating a precursor of a perovskite material and/or a precursor of a triclopyr-like substance on the first catalytic coating, followed by calcination; or
The second catalytic coating is prepared by carrying a precursor of the perovskite material and/or a precursor of the triclopyr-like substance into a cracking unit using a carrier gas under a low oxygen partial pressure atmosphere at 800 ℃ -.
6. The method of claim 1 or 2, wherein the mass of the second catalytic coating is 0.1-50% of the mass of the second catalytic coating.
7. A method according to claim 1 or 2, wherein the perovskite material is selected from SrCeO3、SrZr0.3Ce0.7O3、BaMnO3、BaCeO3、BaZr0.3Ce0.7O3、BaZr0.3Ce0.5Y0.2O3、BaZr0.1Ce0.7Y0.2O3、BaZrO3、BaZr0.7Ce0.3O3、BaCe0.5Zr0.5O3、BaCe0.9Y0.1O3、BaCe0.85Y0.15O3And BaCe0.8Y0.2O3At least one of (1).
8. The method of claim 1 or 2, wherein the triclopyr-like substance is Na4Al2Si2O9。
9. The method according to claim 1 or 2, wherein the thickness of the first catalytic coating is 0.5-20 μ ι η and the thickness of the second catalytic coating is 0.1-10 μ ι η.
10. Use of the method according to any one of claims 1 to 9 in a hydrocarbon cracking process, preferably in a hydrocarbon cracking process.
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