CN114410346B - Method for preparing low-carbon olefin and aromatic hydrocarbon from crude oil - Google Patents

Method for preparing low-carbon olefin and aromatic hydrocarbon from crude oil Download PDF

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CN114410346B
CN114410346B CN202111606347.7A CN202111606347A CN114410346B CN 114410346 B CN114410346 B CN 114410346B CN 202111606347 A CN202111606347 A CN 202111606347A CN 114410346 B CN114410346 B CN 114410346B
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oxide
oil
catalyst
content
molecular sieve
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CN114410346A (en
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吴青
辛利
臧甲忠
靳凤英
范景新
郭春垒
赵闯
刘航
马明超
董子超
刘晗
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China National Offshore Oil Corp CNOOC
CNOOC Tianjin Chemical Research and Design Institute Co Ltd
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China National Offshore Oil Corp CNOOC
CNOOC Tianjin Chemical Research and Design Institute Co Ltd
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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
    • C10G55/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process
    • C10G55/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process plural serial stages only
    • C10G55/06—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process plural serial stages only including at least one catalytic cracking step
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
    • B01J27/198—Vanadium
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/005—Mixtures of molecular sieves comprising at least one molecular sieve which is not an aluminosilicate zeolite, e.g. from groups B01J29/03 - B01J29/049 or B01J29/82 - B01J29/89
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/084—Y-type faujasite
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/82—Phosphates
    • B01J29/83—Aluminophosphates (APO compounds)
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
    • 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
    • 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
    • Y02P20/584—Recycling of catalysts

Abstract

The invention relates to a method for preparing low-carbon olefin and aromatic hydrocarbon from crude oil, which comprises the steps of spraying the crude oil into a riser reactor to perform a first catalytic reaction with a first catalyst to obtain a first oil-gas product, introducing the first oil-gas product into a downstream bed reactor in a gas phase state, performing a reaction under the action of a second catalyst to generate a second oil-gas product, and separating the second oil-gas product to obtain the low-carbon olefin, light aromatic hydrocarbon and heavy aromatic hydrocarbon products. The method can be used for preparing low-carbon olefin and aromatic hydrocarbon from the intermediate base crude oil, and has the characteristic of high yield of the low-carbon olefin and the aromatic hydrocarbon.

Description

Method for preparing low-carbon olefin and aromatic hydrocarbon from crude oil
Technical Field
The invention relates to a method for preparing low-carbon olefin and aromatic hydrocarbon from crude oil.
Background
In recent years, the oil refining industry in China has been greatly developed, and the oil refining capacity is remarkably improved. By 2019, the national oil refining capacity reaches 8.6 hundred million tons, the capacity utilization rate is only 76%, and the phenomenon of excess capacity is serious. In 2025, the oil refining capacity of 2.1 million tons per year is expected to be increased in China, and the excess of the capacity is more serious. On the other hand, as China gradually enters the new economic normal state, the economy is high in acceleration, the fuel oil requirements such as gasoline and diesel oil enter the bottleneck period, and in addition, the development of new energy industry in China, the popularization of electric vehicles is continuously increased, the market space of finished oil in the future is limited, and the conversion of oil products to the production of chemical products such as low-carbon olefin and aromatic hydrocarbon in refineries is greatly facilitated. The catalytic cracking technology is an effective method for producing low-carbon olefin and aromatic hydrocarbon from petroleum raw materials.
Chinese patent CN110724551A proposes a method and a system for catalytic cracking by adopting a dilute phase transport bed and a turbulent fluidized bed, the method comprises the steps of carrying out a primary reaction on preheated heavy oil and a catalyst in a transport way to generate a first oil-gas product and a semi-spent catalyst, and then carrying out a turbulent bed reaction on the semi-spent catalyst and the first oil-gas product. The method can improve the reaction depth of the heavy oil and the catalyst, and has the characteristics of low yield of dry gas and coke and good product distribution.
Chinese patent CN110724561a discloses a catalytic cracking method and system for producing propylene and light aromatic hydrocarbons, which indicates that a light raw material and a catalyst react under a dilute phase transport bed to generate a first reaction product and a semi-spent catalyst, and then the first reaction product and the semi-spent catalyst undergo a dense-phase fluidized bed reaction; then the heavy oil is subjected to oil agent contact reaction in another fast fluidized bed, and finally the low-carbon olefin and the aromatic hydrocarbon are separated from the oil gas product obtained by the light heavy oil reaction.
Chinese patent CN200710120105 discloses a method for preparing low-carbon olefin and light aromatic hydrocarbon, which can obtain higher yields of ethylene, propylene and light aromatic hydrocarbon by injecting the low-carbon olefin and light aromatic hydrocarbon into different parts of a reducing riser according to the original cracking difficulty degree.
The US patent 2002195373 discloses a method for producing low-carbon olefin by catalytic cracking with a descending reactor, which is characterized in that raw oil is subjected to rapid cracking reaction under the condition of a low-hydrogen transfer activity catalyst at 550-650 ℃, a large catalyst-oil ratio (more than 15) and a short retention time (less than 0.5 s), and intermediate products are remained as much as possible, so that a high yield of the low-carbon olefin is obtained.
Chinese patent CN110724558a discloses a catalytic cracking method and system for producing propylene and high-octane gasoline, in which raw oil is divided into high-quality heavy oil and low-quality heavy oil, the high-quality heavy oil is subjected to a series reaction of a dilute phase conveying bed and a dense phase fluidized bed, the low-quality heavy oil is introduced into another fast fluidized bed for reaction, the yield of coke and dry gas produced by catalytic cracking in the method and system is low, and the yield of low-carbon olefin and high-octane gasoline is high.
Chinese patent CN109575982A divides the raw material into light component and heavy component, and carries out catalytic cracking reaction in different reactors respectively, the reaction temperature of the light raw material is 600-800 ℃, the reaction temperature of the heavy raw material is 500-780 ℃, and the method has the characteristics of high conversion per pass and high selectivity of olefin.
In the prior art, when heavy oil is used as a raw material, the contact state and the fluidization state of a catalyst and an oil product are adjusted to achieve higher yield of the low-carbon olefin and the aromatic hydrocarbon.
The catalytic cracking technology has high requirements on raw materials, requires high hydrogen content in the raw materials, and requires low contents of heavy metals such as nickel and vanadium and impurities such as asphaltene and carbon residue in the raw materials. Therefore, the existing catalytic cracking technology and the technology for preparing low-carbon olefin and aromatic hydrocarbon from oil products taking the catalytic cracking technology as a core both need paraffin-based raw materials.
For the raw materials with the intermediate base property, the hydrogen content is low, the contents of carbon residue, asphaltene and heavy metal are high, and the production of low-carbon olefin and aromatic hydrocarbon cannot be carried out by using the catalytic cracking method represented by the patents listed above. The crude oil produced in the world, particularly in China, has small proportion of the yield of the paraffin-based crude oil and scarce resources, and the crude oil obtained by mass production is the crude oil with intermediate-based attribute and naphthenic intermediate-based crude oil. Therefore, it is necessary to develop a method suitable for preparing light olefins and aromatics from middle-base crude oil, so that the method can meet the requirements of most oil refineries using middle-base crude oil as raw material.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for preparing low-carbon olefin and aromatic hydrocarbon from intermediate base crude oil.
In order to realize the purpose, the invention adopts the following technical scheme to realize the purpose:
a method for preparing low-carbon olefin and aromatic hydrocarbon from crude oil comprises the following steps:
1) Preheating crude oil to 120-300 ℃, spraying the crude oil from a feeding nozzle of a riser reactor, contacting the crude oil with a first catalyst, carrying out a first catalytic reaction under the conditions of reaction pressure of 0.04-0.7 MPa, reaction temperature of 420-520 ℃, reaction time of 0.3-18.5 s, water-oil ratio (0.03-0.55): 1 and agent-oil ratio (3.8-15.0): 1, separating oil after the reaction is finished, obtaining a first oil-gas product and a coked and inactivated first catalyst, carrying out steam stripping on the inactivated first catalyst, sending the first catalyst into a first regenerator, introducing oxygen-containing gas for coke burning regeneration, obtaining first flue gas, and recycling the first catalyst;
2) Introducing the obtained first oil gas product into a descending bed reactor in a gas phase state, contacting with a second catalyst, carrying out a second catalytic reaction under the conditions that the reaction pressure is 0.04-0.65 MPa, the reaction temperature is 520-660 ℃, the reaction time is 0.2-3.0 s, the water-oil ratio is 0.10-0.55: 1 and the agent-oil ratio is 5.0-21.0: 1, separating oil after the reaction is finished, obtaining a second oil gas product and a coked and inactivated second catalyst, carrying out steam stripping on the inactivated second catalyst, sending the second oil gas product and the coked and inactivated second catalyst into a second regenerator, introducing air, burning and regenerating to obtain second flue gas, recycling the second catalyst, and sending the second oil gas product into a subsequent separation device to obtain low-carbon olefin, light aromatic hydrocarbon and heavy aromatic hydrocarbon;
the first catalyst is composed of a substrate, a carrier, a binder and an active component, wherein the substrate is one or more of kaolin, diatomite and halloysite and accounts for 8-50% of dry basis, the carrier is one or more of amorphous aluminum silicate oxide, silicon oxide, aluminum oxide and titanium oxide and accounts for 5-45%, the binder is one or two of aluminum sol and silica sol binder and accounts for 2-14%, the active component is one or more of iron oxide, nickel oxide, potassium oxide, calcium oxide, magnesium oxide, sodium oxide, manganese oxide, cerium oxide, gallium oxide, vanadium oxide, a high-silicon molecular sieve and a mesoporous molecular sieve and accounts for 10-30% of oxide, the ratio of the mesoporous volume to the total pore volume of the catalyst is 25.5-100%, and the ratio of the mesoporous volume to the total pore volume of the catalyst is 20-100%;
the second catalyst takes one or more of kaolin, montmorillonite and halloysite as a matrix with the content of 15-55%, one or more of pseudo-boehmite, silica sol and alumina sol as a binder with the content of 10-25%, one or more of an MFI molecular sieve, a Y-type molecular sieve, a Beta molecular sieve and an ALPO-5 molecular sieve as active components, the content of the MFI molecular sieve is 10-30%, and the content of the rest molecular sieves is 2-15%.
In the method for preparing the low-carbon olefin and the aromatic hydrocarbon from the crude oil, the crude oil is the intermediate base crude oil, and particularly, the intermediate base crude oil is the crude oil of which any one of a first key component and a second key component in the crude oil belongs to the intermediate base property.
The crude oil may further include incorporation of an amount of deasphalted oil, hydrocracked tail oil, shale oil, atmospheric residue, vacuum wax oil.
Preferably, the crude oil has a density in the range of 0.80 to 0.98g/cm 3 The carbon residue value is 0.1-15%, and the content of nickel and vanadium is 0-1000 mg/kg.
Preferably, the subsequent separation device comprises a fractionating tower, a gas separation device and an aromatic extraction device, and the first oil gas product is a fraction with the initial boiling point of 80 ℃, preferably a fraction with the temperature of 45-65 ℃, and the second oil gas product is a fraction with the temperature of 170-280 ℃, preferably a fraction with the temperature of 185-245 ℃, and the second oil gas product is a fraction with the temperature of 35-75%, preferably 45-65%, of the total amount.
Preferably, either one or a mixture of both of the first and second recycle components is fed to the downer reactor for recycling.
Preferably, the ascending bed reactor comprises a dilute phase transport bed riser reactor, a dense phase transport bed riser reactor, and a riser reactor with equal diameter or expanded diameter.
Preferably, the preparation method of the MFI type molecular sieve comprises the steps of taking a ZSM-5 molecular sieve with the silica-alumina ratio of 30-80 as a seed crystal, wherein the seed crystal accounts for 0.5-3.0% of the dry basis weight of the synthesized molecular sieve, sequentially adding macroporous pseudo-boehmite, n-butylamine and water glass, and preparing a mixture according to the weight ratio of (SiO 2): n (Al 2O 3): n (n-butylamine): n (NaOH): n (H2O) =1:0.01 to 0.35:0.19 to 0.42: 0.05-0.50: 30, preparing glue at 55-65 ℃, aging for 2-14 h at 70-85 ℃, crystallizing for 6-10 h at 120 ℃, then crystallizing for 10-14 h at 165-180 ℃, and chemically modifying the molecular sieve by adopting Ni, P and Fe elements, wherein the content of Ni is 0.3-1.2 percent by oxide, the content of P is 1.0-4.5 percent by oxide, and the content of Fe is 0.8-2.5 percent by oxide, calculated on a dry basis.
Preferably, the Y-type molecular sieve is modified by La, ce, P and Zn, the La and Ce are loaded in an ion exchange mode, after loading, the roasting is carried out for 1 to 3.5 hours at the temperature of 450 to 550 ℃, then the aging is carried out for 1.5 to 4.5 hours in the atmosphere with the water vapor content of 33 to 47 percent at the temperature of 400 to 520 ℃, the P and Zn are loaded in an impregnation mode, after loading, the roasting is carried out for 2 to 5.5 hours at the temperature of 500 to 635 ℃, the content of La is 1.1 to 4.8 percent by oxide, the content of Ce is 0.8 to 3.5 percent by oxide, the content of P is 0.3 to 2.2 percent by oxide, and the content of Zn is 0.5 to 1.7 percent by oxide.
Preferably, the oxygen-containing gas introduced into the first regenerator is one of air, oxygen-enriched air or oxygen, and the catalyst is regenerated by one of single-stage regeneration, two-stage regeneration and turbulent bed, fast bed or transport bed regeneration.
Preferably, the mass ratio of the water vapor to the oxygen-containing gas is 0-0.45, and the first resurgence gas is conventional gas or gas containing CO 2 The synthesis gas of (2).
Compared with the prior art, the method of the invention has the following beneficial effects:
1) The method of the invention contacts the crude oil with the first catalyst in the lift pipe, the first catalyst does not take the strongly acidic Y molecular sieve as an active component, the damage effect of heavy metal in the crude oil on the molecular sieve structure is greatly reduced, in addition, the defects of rapid coking and activity loss of the acidic molecular sieve catalyst caused by asphaltene, carbon residue and the like can be greatly avoided, simultaneously, the mesoporous structure containing abundant mesoporous structure meets the requirement of macromolecular diffusion, and the method is suitable for processing the intermediate base crude oil with high heavy metal content and high asphaltene and carbon residue content.
2) The method of the invention firstly carries out shallow cracking on macromolecules in the crude oil so as to generate a large amount of oil gas products rich in olefin, and then the oil gas products react with a second catalyst for a second catalytic reaction. The first oil gas product does not contain heavy metal and carbon residue basically, so that the catalyst function of the second catalyst can be exerted to the maximum extent; the reaction temperature of the second catalytic reaction is higher, which is beneficial to the first oil gas product to produce low-carbon olefin and aromatic hydrocarbon products to the maximum extent. In addition, the macromolecules in the crude oil are reacted by the first catalyst, most of the macromolecules are converted into components in the molecular weight range of gasoline or diesel oil, the diffusion eliminating effect of the second catalyst is facilitated, and the first oil gas product is converted into low-carbon olefin and aromatic hydrocarbon products to the maximum extent.
Drawings
FIG. 1 is a schematic view of a process flow for preparing low-carbon olefins and aromatics from crude oil according to the present invention.
In the figure, 1 crude oil, 2 riser reactor, 3 pre-lift gas, 4 settler, 5 stripper i, 6 first spent transport chute, 7 first regenerator, 8 oxygen-containing gas, 9 first regenerant transport chute, 10 first flue gas, 11 first oil gas product, 12 recycle component feed, 13 downer reactor, 14 horizontal cyclone separator, 15 second spent, 16 stripper ii, 17 second oil gas product, 18 lift gas, 19 second regenerant transport riser, 20 second spent transport chute, 21 second regenerator, 22 coke-fired air, 23 second flue gas
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples.
Examples
The first catalyst used in this example was prepared as follows. Mixing kaolin and water, pulping, adding alumina, silica and titanium oxide, fully mixing, adding an aluminum sol binder, adding ferric nitrate, cerium nitrate, calcium nitrate and vanadium nitrate, controlling the solid content to be 28%, wherein the proportions of kaolin, alumina, silica, titanium oxide and aluminum sol, iron oxide, cerium oxide, calcium oxide and vanadium oxide are 41.0%,17.1%,19.2%, 5.1% and 4.5% and 2.2%, 5.0%, 3.9% and 2.0% in terms of dry basis of oxides, and spraying and molding the mixed slurry to obtain the catalyst.
The formed catalyst is roasted for 2 hours at 520 ℃, and then a mixed solution of potassium nitrate, manganese nitrate and phosphoric acid is impregnated on the roasted catalyst, wherein the potassium oxide, the manganese oxide and the phosphorus pentoxide respectively account for 1.4 percent, 1.8 percent and 2.3 percent of the weight of the catalyst on a dry basis of oxides. And drying the impregnated catalyst, and roasting at 500 ℃ for 1.5h to obtain the finished catalyst. The proportion of mesopore volume to the total pore volume of the prepared catalyst was 46.3%, and the proportion of mesopore volume to the total pore volume was 63.1%.
The second catalyst was prepared as follows. Mixing kaolin and water, pulping, adding pseudo-boehmite, fully mixing, adding a proper amount of hydrochloric acid solution, then adding alumina sol, fully mixing, adding an MFI type molecular sieve, a Y type molecular sieve and an ALPO-5 molecular sieve, fully mixing, and controlling the solid content to be 25%. Calculated by oxide dry basis, the proportions of kaolin, pseudo-boehmite, alumina sol, MFI type molecular sieve, Y molecular sieve and ALPO-5 molecular sieve are 39.0%,19.7%,5.2%,23.5%,5.0% and 7.6%, and the mixed slurry is sprayed and molded into the catalyst.
The preparation process of the MFI molecular sieve comprises the following steps: using a ZSM-5 molecular sieve with the silica-alumina ratio of 60 as a seed crystal, wherein the seed crystal accounts for 1.5 percent of the dry basis weight of the synthesized molecular sieve, sequentially adding macroporous pseudo-boehmite, n-butylamine and water glass according to the weight ratio of (SiO 2): n (Al 2O 3): n (n-butylamine): n (NaOH): n (H2O) =1:0.25:0.25:0.35:30, preparing glue at 58 ℃, aging for 5h at 80 ℃, crystallizing for 8h at 120 ℃, crystallizing for 12h at 175 ℃, and chemically modifying the molecular sieve by adopting Ni, P and Fe elements, wherein the content of Ni is 1.0 percent by oxide, the content of P is 1.5 percent by oxide and the content of Fe is 1.8 percent by oxide on a dry basis.
The Y-type molecular sieve is modified by La, ce, P and Zn, the La and Ce are loaded in an ion exchange mode, after loading, the roasting is carried out for 1 to 3.5 hours at the temperature of 450 to 550 ℃, then the aging is carried out for 1.5 to 4.5 hours in the atmosphere with the water vapor content of 33 to 47 percent at the temperature of 400 to 520 ℃, the P and Zn are loaded in an impregnation mode, after loading, the roasting is carried out for 2 to 5.5 hours at the temperature of 500 to 635 ℃, the La content is 1.5 percent by dry basis, the Ce content is 3.0 percent by oxide, the P content is 1.5 percent by oxide, and the Zn content is 1.2 percent by oxide.
The properties of the crude oils used are shown in Table 1, which belong to the middle base crude oils.
TABLE 1
Item Numerical value
Density, 20 ℃ g/cm 3 0.9334
Carbon residue, m% 4.6
Carbon content, m% 86.70
Hydrogen content, m% 12.42
Nitrogen content, m% 0.31
Sulfur content, m% 0.57
Heavy Metal content, μ g/g
Nickel (II) 10.4
Vanadium oxide 3.5
Distillation range, deg.C
10％ 195
30％ 314
50％ 406
70％ 489
90％ 681
Preheating crude oil 1 with the properties shown in table 1 to 221 ℃, then spraying the crude oil into a riser reactor 2 from a riser feeding nozzle, enabling the crude oil to contact with a first catalyst, performing a first catalytic reaction under the conditions of reaction pressure of 0.25MPa, reaction temperature of 475 ℃, reaction time of 2.2s, water-oil ratio of 0.12 and catalyst-oil ratio of 6.5, separating oil after the reaction is finished, obtaining a first oil-gas product 11 and a coking inactivated first to-be-generated catalyst, performing steam stripping on the first to-be-generated catalyst in a stripper I5, removing the oil-gas product remaining on the catalyst, then sending the first to-be-generated catalyst into a first regenerator 7 through a first to-be-generated agent conveying inclined pipe 6, introducing oxygen-containing gas, performing coking regeneration at 731 ℃, obtaining a first flue gas 10, and recycling the first catalyst after regeneration.
The oxygen-containing gas introduced into the first regenerator 10 is a mixed gas of air and steam, the mass ratio of the steam to the oxygen-containing gas is 0.1. Obtaining the first flue gas containing CO 2 The synthesis gas of (2).
Introducing the obtained first oil gas product 11 into a descending bed reactor 13 in a gas phase state, contacting with a second catalyst, carrying out a second catalytic reaction under the conditions that the reaction pressure is 0.31MPa, the reaction temperature is 645 ℃, the reaction time is 0.7s, the water-oil ratio is 0.18, and the agent-oil ratio is 14.2.
And the second oil gas product 17 is sent to a subsequent separation device, and is fractionated into a gas component containing ethylene, propylene and butylene, a gasoline component rich in C6-C9 light aromatic hydrocarbons and heavy components rich in 2-4 ring heavy aromatic hydrocarbons in a fractionating tower, the gasoline component rich in the light aromatic hydrocarbons is refined and then aromatic hydrocarbon extraction is carried out to obtain a light aromatic hydrocarbon product, and the heavy components are refined to obtain a 2-4 ring heavy aromatic hydrocarbon product capable of being used for producing carbon materials.
Mixing the components with the temperature of 43-70 ℃ and the components with the temperature of 180-240 ℃ obtained in the fractionating tower, and feeding the mixture into a descending bed reactor for recycling.
Table 2 results of product distribution using this intermediate base crude oil as a raw material, table 2
Figure BDA0003434180270000071
Figure BDA0003434180270000081
As can be seen from the table, the yield of ethylene reached 5.8%, the yields of propylene and butene reached 16.3% and 14.6%, the yield of light aromatics in gasoline was 21.4%, and the yield of heavy aromatics was 14.5%. Under the method provided by the invention, the yield of low-carbon olefin and aromatic hydrocarbon of 72.8 percent can be obtained by taking the middle base crude oil in the Bohai as a raw material.
The above examples are representative embodiments of the present invention, the present invention is not limited to the details in the above examples, and simple modifications and adjustments of the catalyst formulation can be made in the technical route of the present invention within the scope of the technical idea of the present invention, and these simple modifications and adjustments are within the scope of the present invention.

Claims (10)

1. A method for directly preparing low-carbon olefin and aromatic hydrocarbon from crude oil comprises the following steps:
1) Preheating crude oil to 120-300 ℃, spraying the crude oil from a feeding nozzle of a riser reactor, contacting the crude oil with a first catalyst, carrying out a first catalytic reaction under the conditions of reaction pressure of 0.04-0.7 MPa, reaction temperature of 420-520 ℃, reaction time of 0.3-18.5 s, water-oil ratio (0.03-0.55): 1 and agent-oil ratio (3.8-15.0): 1, separating oil after the reaction is finished, obtaining a first oil-gas product and a coked and inactivated first catalyst, carrying out steam stripping on the inactivated first catalyst, sending the first catalyst into a first regenerator, introducing oxygen-containing gas for coke burning regeneration, obtaining first flue gas, and recycling the first catalyst;
2) Introducing the first oil gas product obtained in the step 1) into a descending bed reactor in a gas phase state, contacting with a second catalyst, carrying out a second catalytic reaction under the conditions that the reaction pressure is 0.04-0.65 MPa, the reaction temperature is 520-660 ℃, the reaction time is 0.2-3.0 s, the water-oil ratio is 0.10-0.55: 1 and the agent-oil ratio is 5.0-21.0: 1, separating oil after the reaction is finished to obtain a second oil gas product and a coked and inactivated second catalyst, stripping the inactivated second catalyst by steam, sending the second catalyst into a second regenerator, introducing air for coke burning and regeneration to obtain second flue gas, recycling the second catalyst after regeneration, and sending the second oil gas product into a subsequent separation device to obtain low-carbon olefin, light aromatic hydrocarbon and heavy aromatic hydrocarbon;
the first catalyst comprises a substrate, a carrier, a binder and an active component, wherein the substrate is one or more of kaolin, diatomite and halloysite with the content of 8-50% on a dry basis, the carrier is one or more of amorphous aluminum silicate oxide, silicon oxide, aluminum oxide and titanium oxide with the content of 5-45%, the binder is one or two of alumina sol and silica sol binder with the content of 2-14%, the active component is one or more of iron oxide, nickel oxide, potassium oxide, calcium oxide, magnesium oxide, sodium oxide, manganese oxide, cerium oxide, gallium oxide, vanadium oxide, a high-silicon molecular sieve and a mesoporous molecular sieve, and the mesoporous molecular sieve accounts for 10-30% by oxide, the ratio of the mesoporous volume to the total pore volume of the catalyst is 25.5-100%, and the ratio of the mesoporous volume to the total pore volume of the catalyst is 20-100%;
the second catalyst takes one or more of kaolin, montmorillonite and halloysite as a matrix, and the content of the second catalyst is 15-55%; one or more of pseudo-boehmite, silica sol and aluminum sol are used as a binder, and the content is 10-25%; using MFI molecular sieve, its content is 10-30%; and one or more of Y-type molecular sieve, beta molecular sieve and ALPO-5 molecular sieve as active component in the content of 2-15%.
2. The method of claim 1, wherein the crude oil is a middle base crude oil.
3. The method of claim 2, wherein the mesobase crude oil is a crude oil having a mesobase property to which either of the first key component and the second key component of the crude oil belongs.
4. The method of claim 1, wherein the crude oil density ranges from 0.80 to 0.98g/cm 3 The carbon residue value is 0.1-15%, and the content of nickel and vanadium is 0-1000 mg/kg.
5. The method of claim 1, wherein the subsequent separation device comprises a fractionating tower, a gas separation device and an aromatic extraction device, and the first oil gas product is a fraction with a boiling point of 80 ℃ to 30-80% of the total amount, and the second oil gas product is a first recycle component, and the second oil gas product is a fraction with a boiling point of 170-280 ℃ to 35-75% of the total amount, and is a second recycle component.
6. The method of claim 5, wherein either one of the first remix component and the second remix component or a mixture of both components is fed to the downer reactor for remix; the subsequent separation device comprises a fractionating tower, a gas separation device and an aromatic extraction device, wherein 45-70% of the total amount of 45-65 ℃ fractions in the second oil gas product are selected as first remilling components, and 185-245 ℃ fractions are selected as second remilling components, wherein 45-65% of the total amount of the 185-245 ℃ fractions are selected.
7. The method of claim 1 wherein said riser reactor comprises a dilute phase transport bed riser reactor, a dense phase transport bed riser reactor, a constant diameter or expanded diameter riser reactor.
8. The method of claim 1, wherein the MFI-type molecular sieve is prepared by using ZSM-5 molecular sieve having a silica-alumina ratio of 30-80 as a seed crystal, the seed crystal accounting for 0.5-3.0% of the dry basis weight of the synthesized molecular sieve, sequentially adding macroporous pseudo-boehmite, n-butylamine and water glass,according to n (SiO) 2 )：n(Al 2 O 3 ): n (n-butylamine): n (NaOH): n (H) 2 O) =1:0.01 to 0.35:0.19 to 0.42:0.05 to 0.50:30, preparing glue at 55-65 ℃, aging for 2-14 h at 70-85 ℃, crystallizing for 6-10 h at 120 ℃, then crystallizing for 10-14 h at 165-180 ℃, and chemically modifying the molecular sieve by adopting Ni, P and Fe elements, wherein the content of Ni is 0.3-1.2 percent by oxide, the content of P is 1.0-4.5 percent by oxide, and the content of Fe is 0.8-2.5 percent by oxide, calculated on a dry basis.
9. The method of claim 1, wherein the Y-type molecular sieve is modified by La, ce, P, zn, the La and Ce are loaded in an ion exchange form, the loaded Y-type molecular sieve is calcined at 450-550 ℃ for 1-3.5 h, then aged at 400-520 ℃ for 1.5-4.5 h in an atmosphere with a water vapor content of 33-47%, the loaded Y-type molecular sieve is loaded in a P and Zn impregnation form, the loaded Y-type molecular sieve is calcined at 500-635 ℃ for 2-5.5 h, the La content is 1.1-4.8% in terms of oxide, the Ce content is 0.8-3.5% in terms of oxide, the P content is 0.3-2.2% in terms of oxide, and the Zn content is 0.5-1.7% in terms of oxide on a dry basis.
10. The method of claim 1, wherein the oxygen-containing gas introduced into the first regenerator is one of air, oxygen-enriched air or oxygen, wherein the mass ratio of water vapor to oxygen-containing gas is 0 to 0.45; the catalyst regeneration mode is one of single-stage regeneration, two-stage regeneration and turbulent bed, fast bed or conveying bed regeneration.
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