CN113337306A - Method for increasing yield of low-carbon olefin by thermally cracking petroleum hydrocarbon - Google Patents

Method for increasing yield of low-carbon olefin by thermally cracking petroleum hydrocarbon Download PDF

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CN113337306A
CN113337306A CN202010099964.1A CN202010099964A CN113337306A CN 113337306 A CN113337306 A CN 113337306A CN 202010099964 A CN202010099964 A CN 202010099964A CN 113337306 A CN113337306 A CN 113337306A
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mass
polymerization inhibitor
alkali metal
thermal cracking
contact agent
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CN113337306B (en
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王志宏
龚剑洪
魏晓丽
宋宝梅
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
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
    • C10G9/34—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert preheated fluids, e.g. with molten metals or salts
    • C10G9/36—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert preheated fluids, e.g. with molten metals or salts with heated gases or vapours
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/20—C2-C4 olefins
    • 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)
  • Oil, Petroleum & Natural Gas (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

The invention provides a method for increasing the yield of low-carbon olefin by thermally cracking petroleum hydrocarbon, which comprises the following steps: in a thermal cracking reactor, under the thermal cracking condition, raw petroleum hydrocarbon oil and steam are contacted with a polymerization inhibitor and a contact agent to carry out thermal cracking reaction, and a thermal cracking oil gas product rich in low-carbon olefin, a spent polymerization inhibitor with accumulated carbon and a spent contact agent with accumulated carbon are generated; wherein the polymerization inhibitor contains a silica substrate and an alkali metal element bonded to the silica substrate; taking the total mass of the polymerization inhibitor as a reference, the content of the alkali metal element is 0.1-10 mass%, and the content of the silicon oxide matrix is 90-99.9 mass%; the contact agent is a thermal cracking contact agent containing a solid acid center. The invention can obviously change the product distribution of the thermal cracking petroleum hydrocarbon, thereby obviously improving the yield of the low-carbon olefin.

Description

Method for increasing yield of low-carbon olefin by thermally cracking petroleum hydrocarbon
Technical Field
The invention belongs to the field of petrochemical industry, and particularly relates to a method for increasing the yield of low-carbon olefin by thermally cracking petroleum hydrocarbon.
Background
The low-carbon olefin comprises ethylene, propylene and butylene, and is a very important basic chemical raw material, and the steam thermal cracking is to carry out thermal cracking on petroleum hydrocarbon at the temperature of more than 800 ℃ in the presence of steam, and is one of important ways for producing the low-carbon olefin.
Steam thermal cracking includes tubular furnace steam cracking, catalytic thermal cracking, and contact thermal cracking. The tubular furnace steam cracking is difficult to process heavy raw materials, and the catalytic thermal cracking process of heavy raw materials has high coke yield and low olefin yield.
Catalytic thermal cracking refers to a hydrocarbon cracking reaction carried out in the presence of a catalyst, and can reduce the temperature of the thermal cracking reaction and improve the selectivity and the product yield. For example, CN1083092A is a CPP process developed by the institute of petrochemical science and technology, which uses an acidic molecular sieve catalyst containing a layered column clay molecular sieve and/or a rare earth-containing pentasil zeolite in the presence of high temperature steam. For another example, CN101228104A and CN101282784A are ACO processes of SK energy corporation in korea, which use a ZSM-5 highly acidic molecular sieve catalyst.
Contact thermal cracking refers to the rapid contact of a preheated hydrocarbon feedstock directly with a contact agent, which generally contains no molecular sieve or a small amount of molecular sieve, and which may or may not have catalytic activity. For example, CN110129091A discloses a contact agent made of petroleum coke.
The existing steam thermal cracking technology still has the defects of poor raw material adaptability and lower total olefin yield.
Disclosure of Invention
The invention aims to overcome the defects of poor raw material adaptability and lower total olefin yield of the existing steam thermal cracking technology, and provides a method for thermally cracking petroleum hydrocarbon, which can use inferior raw materials and improve the total olefin yield.
The inventors of the present invention have surprisingly found that, after an alkali metal element is bonded to a silicon oxide substrate, a polymerization inhibitor which inhibits the polymerization of low carbon olefins during the thermal cracking process can be obtained, so that the total olefin yield of the low carbon olefins produced by the thermal cracking of petroleum hydrocarbons can be significantly improved, the polymerization inhibitor is used in combination with a contact agent having a certain catalytic activity, and the yield ratio of propylene to ethylene can be adjusted by adjusting the relative proportions of the polymerization inhibitor and the contact agent, thereby obtaining the present invention.
Thus, the present invention provides a method for thermally cracking petroleum hydrocarbons to increase the yield of lower olefins, the method comprising: in a thermal cracking reactor, under the thermal cracking condition, raw petroleum hydrocarbon oil and steam are contacted with a polymerization inhibitor and a contact agent to carry out thermal cracking reaction, and a thermal cracking oil gas product rich in low-carbon olefin, a spent polymerization inhibitor with accumulated carbon and a spent contact agent with accumulated carbon are generated; wherein the polymerization inhibitor comprises a silica substrate and an alkali metal oxide bonded to the silica substrate; based on the total mass of the polymerization inhibitor, the content of the alkali metal oxide is 0.1-10 mass%, and the content of the silica matrix is 90-99.9 mass%; the contact agent is a thermal cracking contact agent containing a solid acid center.
By the technical scheme, based on the polymerization inhibitor formed by combining the alkali metal element on the silicon oxide substrate, the product distribution of thermally cracked petroleum hydrocarbon can be obviously changed when heavy oil raw materials are used, so that the total yield of olefin can be obviously improved, and the yield ratio of propylene to ethylene can be adjusted by adjusting the relative proportion of the polymerization inhibitor and the contact agent.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
In one aspect, the present invention provides a method for thermally cracking petroleum hydrocarbons to increase propylene yield, the method comprising: in a thermal cracking reactor, under the thermal cracking condition, raw petroleum hydrocarbon oil and steam are contacted with a polymerization inhibitor and a contact agent to carry out thermal cracking reaction, and a thermal cracking oil gas product rich in low-carbon olefin, a spent polymerization inhibitor with accumulated carbon and a spent contact agent with accumulated carbon are generated; wherein the polymerization inhibitor comprises a silica substrate and an alkali metal oxide bonded to the silica substrate; based on the total mass of the polymerization inhibitor, the content of the alkali metal oxide is 0.1-10 mass%, and the content of the silica matrix is 90-99.9 mass%; the contact agent is a thermal cracking contact agent containing a solid acid center.
Optionally, wherein the mass ratio of the polymerization inhibitor to the contact agent is 0.5-20:1, preferably 1-10:1, more preferably 2-5: 1.
Optionally, wherein the lower limit of the content of the alkali metal oxide in the polymerization inhibitor is 0.2 mass%, 0.3 mass%, 0.4 mass%, 0.5 mass%, 0.6 mass%, 0.7 mass%, 0.8 mass%, 0.9 mass%, 1.0 mass%, 1.1 mass%, 1.2 mass%, 1.3 mass%, 1.4 mass%, 1.5 mass%, 1.6 mass%, 1.7 mass%, 1.8 mass%, 1.9 mass%, or 2.0 mass%.
Optionally, wherein the upper limit value of the content of the alkali metal oxide in the polymerization inhibitor is 9.5 mass%, 9.0 mass%, 8.5 mass%, 8.0 mass%, 7.5 mass%, 7.0 mass%, 6.5 mass%, 6.0 mass%, 5.5 mass%, 5.0 mass%, 4.5 mass%, 4.0 mass%, 3.5 mass%, 3.0 mass%, 2.5 mass%, 2.4 mass%, 2.3 mass%, 2.2 mass%, or 2.1 mass%.
The content of the polymerization inhibitor may be optionally determined by a combination of the above upper limit value and the above lower limit value, and for example, the content of the alkali metal oxide in the polymerization inhibitor may be in the range of 0.2 to 3.0% by mass, or may be in the range of 0.3 to 2.1% by mass. For example, in the polymerization inhibitor, the content of the alkali metal oxide may be in the range of 0.2 to 9.5 mass%, 0.2 to 2.1 mass%, 0.3 to 9.5 mass%, 0.3 to 2.1 mass%, 0.4 to 9.5 mass%, 0.4 to 2.1 mass%, 0.5 to 9.5 mass%, or 0.5 to 2.1 mass%.
Optionally, wherein the alkali metal oxide is sodium oxide and/or potassium oxide; the silicon oxide substrate comprises at least one of quartz sand, quartz powder and white carbon black; the particle size of the quartz sand is 50-10 mm, the particle size of the quartz powder is less than 50-5 μm, and the particle size of the white carbon black is 1-5 μm; preferably, the silica matrix is quartz sand; more preferably, the quartz sand is at least one of chemically pure quartz sand, analytically pure quartz sand, high-grade pure quartz sand, industrial acid-washed quartz sand meeting the SJ _ T10380 + 1993 standard and high-purity quartz sand for photovoltaic meeting the GB/T32649 + 2016 standard.
Alternatively, the particle size of the polymerization inhibitor may vary widely according to the characteristics and requirements of the thermal cracking reactor, and may be 2nm to 10mm, preferably 40nm to 3mm, more preferably 10 μm to 200 μm, and still more preferably 50 μm to 150 μm.
Optionally, wherein the polymerization inhibitor does not contain a solid acid center, i.e., subjecting the polymerization inhibitor to NH3When the acid amount is measured by the TPD method, the acid amount cannot be detected.
Alternatively, the inhibitor has substantially no cracking activity, i.e., no micro-reactivity is detectable when the inhibitor is tested by a micro-reactivity test using an industrial equilibrium catalyst for RIPP 92-90 catalytic cracking.
Optionally, wherein the polymerization inhibitor is prepared by a method comprising the following steps: an alkali metal compound is mixed with the silica matrix and then heat-treated at 500-1000 deg.C, preferably 600-900 deg.C.
Wherein the material subjected to the heat treatment can be used as the polymerization inhibitor, and can also be optionally subjected to appropriate crushing and screening to be used as the polymerization inhibitor.
Optionally, wherein the alkali metal compound is at least one of hydroxide, carbonate, nitrate, nitrite, sulfite, silicate and organic acid salt of an alkali metal. The compound containing an alkali metal element may be decomposed in the heat treatment to generate an alkali metal oxide, thereby becoming a component of the polymerization inhibitor.
Optionally, wherein the heat treatment is performed in a carrier gas containing at least one of water vapor, nitrogen, carbon dioxide, hydrogen, carbon monoxide, and a hydrocarbon, or the carrier gas contains at least one of water vapor, nitrogen, carbon dioxide, oxygen, and air. The carrier gas may assist the alkali metal element-containing compound in being converted into an alkali metal oxide and becoming a component of the polymerization inhibitor.
Optionally, wherein the heat treatment is performed in a flowing carrier gas containing water vapor, and the alkali metal compound is a halide of an alkali metal, preferably a chloride of an alkali metal. Wherein the halogen in the alkali metal halide can generate hydrogen halide under the action of water vapor and flow out, and the alkali metal element in the alkali metal halide can be converted into alkali metal oxide and become a component of the polymerization inhibitor.
Optionally, wherein the time of the heat treatment is 10 seconds to 2 hours, preferably 1 to 30 minutes.
Alternatively, wherein the operation of mixing the silicon oxide substrate with the compound containing an alkali metal element comprises mixing an aqueous solution containing an alkali metal element with the silicon oxide substrate, followed by drying or not, and then the heat treatment.
Optionally, wherein the contact agent is NH3The amount of acid, measured by the TPD method, is between 0.5 and 15. mu. mol/g, preferably between 1 and 10. mu. mol/g.
Optionally, the contact agent has a microreflection activity of 1% to 20%, preferably 2% to 15%, as determined by the microreflection activity test method for RIPP 92-90 catalytic cracking industrial equilibrium catalysts and expressed in percent. The higher the microresistivity, the higher the cleavage activity, and the lower the cleavage activity when the microresistivity is lower.
Optionally, the contact agent comprises at least one of montmorillonite, kaolin, halloysite, and bentonite.
Optionally, the contact agent further comprises a binder. The binder may be a silica sol.
Optionally, wherein the thermal cracking reactor is one or more of a fixed bed reactor, a moving bed reactor, a dense phase bed reactor, and a riser reactor.
Optionally, wherein the thermal cracking conditions comprise: the cracking temperature is 600-900 ℃, the cracking reaction time is 0.5-360 seconds, the weight ratio of water vapor to the raw petroleum hydrocarbon oil is 0.05-2: 1, and the weight ratio of the total weight of the polymerization inhibitor and the contact agent to the raw petroleum hydrocarbon oil is 5-100: 1; the cracking temperature is preferably 650-735 ℃, and the cracking reaction time is preferably 1-120 seconds.
Optionally, wherein the petroleum hydrocarbon feedstock oil comprises at least one of lower alkanes, naphtha, vacuum residuum, atmospheric residuum, hydrogenated residuum, coker gas oil, deasphalted oil, high carbon residue crude oil, heavy oil, ultra heavy oil, coal liquefaction oil, oil sand oil, and shale oil.
Optionally, wherein the method further comprises: and carrying out scorching regeneration on the spent polymerization inhibitor with the accumulated carbon and the spent contact agent with the accumulated carbon to obtain a regenerated polymerization inhibitor and a regenerated contact agent, and returning the regenerated polymerization inhibitor and the regenerated contact agent to the thermal cracking reactor to participate in the thermal cracking reaction.
Optionally, wherein the char regeneration is in-situ char regeneration or char regeneration performed in a regenerator; the temperature for coke burning regeneration is 640-900 ℃; the gas used for coke burning regeneration is oxygen and/or air.
Optionally, wherein the method further comprises: and separating the thermal cracking oil gas product to obtain low-carbon olefin and low-carbon alkane, and returning part or all of the low-carbon alkane to the thermal cracking reactor for recycling.
The following examples further illustrate the invention but are not intended to limit the invention thereto.
Preparation of example 1
Analytically pure quartz sand (from Tianjin quartz)The grain diameter of the chemical branch works of the Tanshou city in the Bell plant is 100-200 meshes and SiO2Content of more than 99.7% by mass, the same applies hereinafter) as a silica matrix was mixed with an aqueous sodium chloride solution (concentration of 10% by mass), and the amount of silica sand and the amount of aqueous sodium chloride solution were used so that the mass ratio of the silica matrix to sodium element (amount converted to sodium oxide) was 99.4: 0.6. drying the mixed materials to be solid, then heating to 700 ℃, introducing flowing steam, maintaining the temperature at 700 ℃ for 30 minutes, and cooling to obtain the polymerization inhibitor 1. The results of the elemental analysis, the measurement of the solid acid center content and the measurement of the slight reaction activity of the polymerization inhibitor 1 are shown in Table 1, and the elemental analysis of the polymerization inhibitor 1 revealed that the polymerization inhibitor 1 contained no chlorine element.
Preparation of example 2
The contact agent is prepared by spray drying a mixture formed by a binder (silica sol) and montmorillonite according to the weight ratio of 5:95 and then roasting at 700 ℃.
Test example 1
Inhibitor 1 was tested with analytically pure quartz sand and the contact agent of preparation example 2 as follows:
the thermal cracking tests were carried out on a small riser apparatus for continuous reaction-regeneration operation using the atmospheric residue shown in Table 2 as the petroleum hydrocarbon feedstock. The test adopts a one-pass operation mode, the petroleum hydrocarbon raw oil is heated to about 200 ℃ by a preheating furnace and then enters the inlet of a riser reactor, the weight ratio of water vapor to the petroleum hydrocarbon raw oil is 0.5:1, the petroleum hydrocarbon raw oil is contacted with high-temperature water vapor and a hot polymerization inhibitor in the riser to carry out cracking reaction, the reaction temperature is 700 ℃, and the ratio of the total weight of the polymerization inhibitor and the contact agent to the weight of the petroleum hydrocarbon raw oil is 15: 1, the cleavage reaction time was 2.5 seconds. The thermal cracking oil gas product enters a settler from a spent polymerization inhibitor with carbon deposit and a spent contact agent with carbon deposit from the outlet of the reactor, the thermal cracking oil gas product is rapidly separated from the spent polymerization inhibitor with carbon deposit and the spent contact agent with carbon deposit in the settler, the flow of the thermal cracking oil gas product is rapidly quenched and separated into a gas product and a liquid product, and the spent polymerization inhibitor with carbon deposit and the spent contact agent with carbon deposit are separated into the gas product and the liquid product by gravityThe reaction is carried out in a stripper, and the spent polymerization inhibitor and the hydrocarbon substances adsorbed on the spent contact agent are stripped by steam. The stripped spent polymerization inhibitor with the carbon deposit and the spent contact agent with the carbon deposit enter a regenerator and contact with heated oxygen for burning, and the burning temperature is controlled to be about 800 ℃. The inhibitor and contact agent after charring regeneration are stripped with steam in the transfer line to remove non-hydrocarbon gas impurities (such as CO, CO) adsorbed on the regenerated inhibitor and contact agent2Etc.). The stripped regenerated polymerization inhibitor and regenerated contact agent are returned to the riser reactor for recycling. The operating conditions and results of the tests are shown in Table 3.
Test example 2
Inhibitor 1 was tested with analytically pure quartz sand and the contact agent of preparation example 2 according to the method of test example 1, except that: as the petroleum hydrocarbon feedstock oil, wax oils shown in Table 2 were used. The operating conditions and results of the tests are shown in Table 4.
As can be seen from the results of tables 3 and 4, the polymerization inhibitor combined with the silica matrix of alkali metal elements according to the present invention can significantly change the product distribution of thermally cracked petroleum hydrocarbons, compared to the use of quartz sand containing no alkali metal elements and the use of only existing contact agents, thereby significantly improving the olefin yield of lower olefins from thermally cracked petroleum hydrocarbons. Also, the alkali metal element can be stably present in the polymerization inhibitor at the time of the regeneration cycle, and the polymerization inhibitor can also function as a heat carrier. Further, the polymerization inhibitor is used in combination with a contact agent having a certain catalytic activity, and the ratio of the production of propylene to the production of ethylene can also be adjusted by adjusting the relative proportions of the polymerization inhibitor and the contact agent, wherein the propylene/ethylene value is higher when the relative proportions of the polymerization inhibitor and the contact agent are higher, and correspondingly, the propylene/ethylene value is lower when the relative proportions of the polymerization inhibitor and the contact agent are lower.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
TABLE 1
Figure BDA0002386619200000091
TABLE 2
Raw oil Atmospheric residuum Wax oil
Density (20 ℃ C.)/g-cm-3 0.8951 0.8597
Composition of hydrocarbons/m%
Alkane hydrocarbons 41.6 52.0
Cycloalkanes 20.4 34.6
Aromatic hydrocarbons 21.9 13.4
TABLE 3 Petroleum Hydrocarbon base oils as atmospheric residuum
Figure BDA0002386619200000092
TABLE 4 Petroleum Hydrocarbon raw oil is wax oil
Figure BDA0002386619200000093

Claims (20)

1. A method for increasing the yield of low-carbon olefins by thermally cracking petroleum hydrocarbons, the method comprising:
in a thermal cracking reactor, under the thermal cracking condition, raw petroleum hydrocarbon oil and steam are contacted with a polymerization inhibitor and a contact agent to carry out thermal cracking reaction, and a thermal cracking oil gas product rich in low-carbon olefin, a spent polymerization inhibitor with accumulated carbon and a spent contact agent with accumulated carbon are generated;
wherein the polymerization inhibitor comprises a silica substrate and an alkali metal oxide bonded to the silica substrate; based on the total mass of the polymerization inhibitor, the content of the alkali metal oxide is 0.1-10 mass%, and the content of the silica matrix is 90-99.9 mass%;
the contact agent is a thermal cracking contact agent containing a solid acid center.
2. The process according to claim 1, wherein the mass ratio of the polymerization inhibitor to the contact agent is 0.5 to 20:1, preferably 1 to 10:1, more preferably 2 to 5: 1.
3. The method according to claim 1, wherein the lower limit of the content of the alkali metal oxide in the polymerization inhibitor is 0.2 mass%, 0.3 mass%, 0.4 mass%, 0.5 mass%, 0.6 mass%, 0.7 mass%, 0.8 mass%, 0.9 mass%, 1.0 mass%, 1.1 mass%, 1.2 mass%, 1.3 mass%, 1.4 mass%, 1.5 mass%, 1.6 mass%, 1.7 mass%, 1.8 mass%, 1.9 mass%, or 2.0 mass%.
4. The method according to claim 3, wherein the upper limit of the content of the alkali metal oxide in the polymerization inhibitor is 9.5 mass%, 9.0 mass%, 8.5 mass%, 8.0 mass%, 7.5 mass%, 7.0 mass%, 6.5 mass%, 6.0 mass%, 5.5 mass%, 5.0 mass%, 4.5 mass%, 4.0 mass%, 3.5 mass%, 3.0 mass%, 2.5 mass%, 2.4 mass%, 2.3 mass%, 2.2 mass%, or 2.1 mass%.
5. The process according to any one of claims 1 to 4, wherein the alkali metal oxide is sodium oxide and/or potassium oxide; the silicon oxide substrate comprises at least one of quartz sand, quartz powder and white carbon black; the particle size of the quartz sand is 50-10 mm, the particle size of the quartz powder is less than 50-5 μm, and the particle size of the white carbon black is 1-5 μm; preferably, the silica matrix is quartz sand; more preferably, the quartz sand is at least one of chemically pure quartz sand, analytically pure quartz sand, high-grade pure quartz sand, industrial acid-washed quartz sand meeting the SJ _ T10380 + 1993 standard and high-purity quartz sand for photovoltaic meeting the GB/T32649 + 2016 standard.
6. The process according to any one of claims 1 to 4, wherein the polymerization inhibitor has a particle size of 2nm to 10mm, preferably 40nm to 3mm, more preferably 10 μm to 200 μm, and still more preferably 50 μm to 150 μm.
7. The method of any one of claims 1-4,
the polymerization inhibitor does not contain a solid acid center;
and/or the presence of a gas in the gas,
the polymerization inhibitor has no microreactivity.
8. The method of any one of claims 1-4,
the polymerization inhibitor is prepared by a method comprising the following steps:
an alkali metal compound is mixed with the silica matrix and then heat-treated at 500-1000 deg.C, preferably 600-900 deg.C.
9. The method according to claim 8, wherein the alkali metal compound is at least one of hydroxide, carbonate, nitrate, nitrite, sulfite, silicate and organic acid salt of an alkali metal.
10. The method of claim 8, wherein the heat treatment is performed in a carrier gas containing at least one of water vapor, nitrogen, carbon dioxide, hydrogen, carbon monoxide, and a hydrocarbon, or the carrier gas containing at least one of water vapor, nitrogen, carbon dioxide, oxygen, and air.
11. A process according to claim 8, wherein the heat treatment is carried out in a flowing carrier gas containing water vapour, the alkali metal compound being a halide of an alkali metal, preferably a chloride of an alkali metal.
12. The method according to claim 8, wherein the heat treatment is carried out for a period of time of 10 seconds to 2 hours, preferably 1 to 30 minutes.
13. The method according to claim 8, wherein the mixing of the silicon oxide substrate with the compound containing the alkali metal element comprises mixing an aqueous solution containing the alkali metal element with the silicon oxide substrate, followed by drying or not, and then the heat treatment.
14. The method of any one of claims 1-4, wherein the contact agent is NH3The amount of acid, measured by the TPD method, is between 0.5 and 15. mu. mol/g, preferably between 1 and 10. mu. mol/g;
and/or the presence of a gas in the gas,
the micro-inverse activity of the contact agent is 1% -20%, preferably 2% -15%; and/or the presence of a gas in the gas,
the contact agent contains at least one of montmorillonite, kaolin, halloysite and bentonite;
and/or the presence of a gas in the gas,
the contact agent also contains a binder.
15. The process of any one of claims 1-4, wherein the thermal cracking reactor is one or more of a fixed bed reactor, a moving bed reactor, a dense bed reactor, and a riser reactor.
16. The method of any of claims 1-4, wherein the thermal cracking conditions comprise: the cracking temperature is 600-900 ℃, the cracking reaction time is 0.5-360 seconds, and the weight ratio of the water vapor to the petroleum hydrocarbon raw oil is 0.05-2: 1, the weight ratio of the total weight of the polymerization inhibitor and the contact agent to the petroleum hydrocarbon raw oil is 5-100: 1; the cracking temperature is preferably 650-735 ℃, and the cracking reaction time is preferably 1-120 seconds.
17. The method of any one of claims 1-4, wherein the petroleum hydrocarbon feedstock oil comprises at least one of lower alkanes, naphtha, vacuum residuum, atmospheric residuum, hydrogenated residuum, coker gas oil, deasphalted oil, high carbon residue crude oil, heavy oil, super heavy oil, coal liquefied oil, oil sand oil, and shale oil.
18. The method of any of claims 1-4, wherein the method further comprises: and carrying out scorching regeneration on the spent polymerization inhibitor with the accumulated carbon and the spent contact agent with the accumulated carbon to obtain a regenerated polymerization inhibitor and a regenerated contact agent, and returning the regenerated polymerization inhibitor and the regenerated contact agent to the thermal cracking reactor to participate in the thermal cracking reaction.
19. The method of claim 18, wherein the char regeneration is an in-situ char regeneration or a char regeneration performed in a regenerator; the temperature for coke burning regeneration is 640-900 ℃; the gas used for coke burning regeneration is oxygen and/or air.
20. The method of any of claims 1-4, wherein the method further comprises: and separating the thermal cracking oil gas product to obtain low-carbon olefin and low-carbon alkane, and returning part or all of the low-carbon alkane to the thermal cracking reactor for recycling.
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CN102453502A (en) * 2010-10-26 2012-05-16 中国石油化工股份有限公司 Conversion method for hydrocarbon oil

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CN1031834A (en) * 1987-08-08 1989-03-22 中国石油化工总公司石油化工科学研究院 Produce the hydrocarbons catalytic conversion method of low-carbon alkene
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