CN114686252B - Method for preparing chemicals from crude oil - Google Patents

Method for preparing chemicals from crude oil Download PDF

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Publication number
CN114686252B
CN114686252B CN202111605685.9A CN202111605685A CN114686252B CN 114686252 B CN114686252 B CN 114686252B CN 202111605685 A CN202111605685 A CN 202111605685A CN 114686252 B CN114686252 B CN 114686252B
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catalyst
oil
gas
crude oil
oxide
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CN114686252A (en
Inventor
吴青
辛利
郭春垒
王银斌
臧甲忠
范景新
靳凤英
汪洋
赵闯
李健
董子超
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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
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04—Oxides
    • C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
    • 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
    • B01J29/04—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
    • B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
    • B01J29/14—Iron group metals or copper
    • B01J29/146—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
    • B01J29/42—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 containing iron group metals, noble metals or copper
    • B01J29/46—Iron group metals or copper

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

Abstract

The invention relates to a method for preparing chemicals from crude oil, which comprises the steps of spraying the crude oil into a downstream bed reactor to perform a first catalytic reaction with a first catalyst to obtain a first oil gas product, separating the first oil gas product into a first gas phase product and a first liquid product, introducing the obtained first liquid product into the variable-diameter downstream bed reactor, performing a second catalytic reaction under the action of a second catalyst to generate a second oil gas product, and separating the second oil gas product to obtain low-carbon olefin and aromatic hydrocarbon products. The method can be used for preparing chemicals from intermediate crude oil, and has the characteristics of strong raw material adaptability and high chemical yield.

Description

Method for preparing chemicals from crude oil
Technical Field
The invention relates to a method for preparing chemicals from crude oil.
Background
In recent years, the oil refining industry in China has achieved a great deal of development, and the oil refining capability 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 surplus capacity phenomenon is serious. By 2025, new oil refining capacity of 2.1 hundred million tons/year is expected to be increased in China, and surplus productivity is more serious. On the other hand, as China gradually enters into a new economic normal state, the economy is increased in speed, the fuel oil requirements of gasoline, diesel oil and the like enter into a bottleneck period, and the development of new energy industry in China is increased, the popularization strength of electric automobiles is continuously increased, the future market space of the finished oil is limited, and the production of chemical products such as low-carbon olefins, aromatic hydrocarbons and the like from oil products in refineries tends to be great. Catalytic cracking technology is an effective method for producing chemicals from petroleum feedstocks.
Chinese patent CN110724551a proposes a method and system for catalytic cracking using dilute phase transport bed and turbulent fluidized bed, in which preheated heavy oil is transported with catalyst to react once to generate first oil gas product and semi-spent catalyst, and then the semi-spent catalyst and the first oil gas product are reacted in turbulent bed. The method can improve the reaction depth of 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 process and system for producing propylene and light aromatic hydrocarbons, which states that light raw materials are reacted with a catalyst under a dilute phase transport bed to produce a first reaction product and a semi-spent catalyst, and then the first reaction product and the semi-spent catalyst are subjected to a dense phase fluidized bed reaction; and then carrying out oil contact reaction on heavy oil in another rapid fluidized bed, and finally separating oil-gas products obtained by the reaction of light heavy oil to obtain low-carbon olefin and aromatic hydrocarbon.
Chinese patent CN200710120105 discloses a process for preparing low-carbon olefine and light aromatic hydrocarbon, which is to inject the low-carbon olefine and light aromatic hydrocarbon into different parts of reducing riser according to the degree of difficulty in cracking.
U.S. patent No. 2002195373 discloses a method for producing low-carbon olefins by catalytic cracking using a downstream reactor, wherein the method comprises the steps of carrying out rapid cracking reaction on raw oil under the conditions of low-hydrogen transfer active catalyst at 550-650 ℃, with a large catalyst-to-oil ratio (more than 15) and a short residence time (less than 0.5 s), and retaining intermediate products as much as possible, thereby obtaining higher low-carbon olefin yield.
Chinese patent CN110724558A discloses a catalytic cracking method and system for producing propylene and high-octane gasoline, in which the raw oil is separated into high-quality heavy oil and low-quality heavy oil, the high-quality heavy oil is subjected to serial reaction of dilute phase conveying bed and dense phase fluidized bed, the low-quality heavy oil is introduced into another fast fluidized bed to undergo reaction, the coke and dry gas yield of catalytic cracking by the method and system is low, and the low-carbon olefin and high-octane gasoline yield is high.
Chinese patent CN109575982A divides the raw materials into light components and heavy components, and the light raw materials are subjected to catalytic cracking reaction in different reactors, wherein the reaction temperature of the light raw materials is 600-800 ℃, and the reaction temperature of the heavy raw materials is 500-780 ℃, and the method has the characteristics of high single pass conversion rate and high olefin selectivity.
In the prior art, the existing catalytic cracking method for preparing chemicals achieves higher chemical yield by adjusting the contact state and fluidization state of a catalyst and an oil product when heavy oil is used as a raw material, and the method for separating light components from heavy components is often adopted when crude oil is used as the raw material, and the light components and the heavy components are introduced into different reactors under the same catalyst system, so that the problem of lower cracking activity of the light components is solved by using high-temperature operation conditions for the light components, and the heavy components are easily cracked and use slightly lower reaction temperature.
The catalytic cracking technology has higher requirements on raw materials, needs higher hydrogen content in the raw materials, and requires lower contents of heavy metals such as nickel, vanadium and the like, asphaltenes, carbon residues and the like in the raw materials. Therefore, the existing catalytic cracking technology and the technology for preparing chemicals from oil products using the catalytic cracking technology as the core require paraffin-based raw materials.
The raw materials with the properties of the intermediate base and the intermediate-cycloalkyl have lower hydrogen content and higher carbon residue, asphaltene and heavy metal content, and the chemical production cannot be carried out by using the catalytic cracking method represented by the patents listed above. And crude oil produced worldwide, particularly domestic crude oil, has smaller paraffin-based property, and scarce resources, and crude oil obtained by mass exploitation is crude oil with intermediate property and naphthene intermediate.
Disclosure of Invention
The invention aims to develop a method for preparing chemicals from crude oil, which can cover paraffin-based attribute raw materials, intermediate-based attribute raw materials and intermediate-cycloalkyl attribute raw materials, so that the method can meet the requirements of most oil refining enterprises taking intermediate-based crude oil and intermediate-cycloalkyl crude oil as raw materials.
To achieve this object, the present invention provides a method for preparing chemicals from crude oil, comprising:
1) Preheating crude oil to 120-320 ℃, spraying the crude oil into a downstream bed reactor from a feed atomizing nozzle without cutting, contacting the crude oil with a first catalyst, carrying out a first catalytic reaction under the condition of 380-650 ℃ under the pressure of 0.05-0.65 MPa, introducing water vapor into the reactor for 0.02-5.5 s, wherein the mass ratio of the water vapor to the crude oil is 0.05-0.6:1, the ratio of the first catalyst to the crude oil is 4.5-30:1, separating to obtain a first oil gas product and a coking deactivated first catalyst after the reaction is finished, eluting the residual oil gas product on the catalyst by the water vapor, then sending the deactivated first catalyst into a coking regenerator, introducing oxygen-containing gas or mixed gas of the water vapor and the oxygen-containing gas, carrying out coking regeneration under the condition of 635-900 ℃, and recycling the regenerated first catalyst; the first catalyst is a catalytic cracking catalyst containing rich mesoporous structures;
2) Separating the first oil gas product obtained in the step 1) to obtain a first gas product containing dry gas and liquefied gas and a first liquid product containing gasoline and the components, introducing the first liquid product into a reducing downstream bed reactor, contacting the first liquid product with an acid catalyst as a second catalyst, carrying out a second catalytic reaction at the temperature of 520-650 ℃ under the pressure of 0.04-0.65 MPa for 0.03-6.5 s, simultaneously introducing water vapor into the reactor to dilute the feed, wherein the mass ratio of the water vapor to the feed is 0.10-0.45:1, the mass ratio of the catalyst to the feed is 6.0-23:1,
after the reaction is finished, a second oil gas product and a coked deactivated second catalyst are obtained through separation, the deactivated second catalyst is used for eluting the residual oil gas product on the catalyst through water vapor, and then the residual oil gas product is sent to a coking regenerator, and the second oil gas product enters a subsequent separation device to obtain low-carbon olefin and aromatic hydrocarbon products.
In the method for preparing chemicals from crude oil, preferably, the first catalyst contains 8-50% of clay, 0.5-45% of one or more of silicon composite oxide, high-silicon molecular sieve, silicon dioxide, mesoporous silicon dioxide, aluminum oxide and titanium oxide, 0.2-10% of one or two of alumina sol or silica sol binder calculated by oxide, 0.3-45% of one or more of iron, nickel, potassium, calcium, magnesium, sodium, manganese, cerium, gallium, phosphorus and boron calculated by oxide, wherein the mesoporous volume of the catalyst accounts for 25.5-100% of the total pore volume, and the mesoporous volume accounts for 20-100% of the total pore volume.
Further preferably, the second catalyst contains 15-55% of clay, 10-45% of one or more of MFI type molecular sieve, Y type molecular sieve, silicon dioxide, aluminum oxide, ferric oxide and titanium oxide, 0.2-10% of one or two of alumina sol and silica sol binder, 0.35-10.5% of one or more of nickel, potassium, magnesium, manganese, cerium, gallium, phosphorus and boron, and the catalyst has mesoporous volume of 15-35% of total pore volume and mesoporous volume of 20-42% of total pore volume.
The raw oil comprises paraffin-based crude oil and intermediate crude oil, and the crude oil also comprises a certain amount of deasphalted oil, hydrocracking tail oil, shale oil, atmospheric residuum, vacuum residuum and vacuum wax oil.
The subsequent separation device comprises a fractionating tower and a gas separation device, and the second oil gas product is separated to obtain low-carbon olefin and aromatic hydrocarbon products, and optionally, at least one part of light gasoline components at 40-80 ℃ and heavy oil components at 320-420 ℃ in the second oil gas product is returned to the reducing downer reactor for recycling.
The downstream bed reactor in the first catalytic reaction comprises an equal-diameter downstream bed reactor and a variable-diameter downstream bed reactor.
The preparation method of the MFI molecular sieve comprises the steps of taking a conventional ZSM-5 molecular sieve with a silicon-aluminum ratio of 35-60 as a parent, adding sulfuric acid for dissolution, then taking the mixture as a seed crystal, sequentially adding macroporous pseudo-boehmite and a silicon source, and obtaining a porous molecular sieve according to n (SiO 2 )：n(Al 2 O 3 ): n (n-butylamine): n (tween): n (NaOH): n (H) 2 O) =1: 0.002-0.35: 0.19 to 0.42:0.04 to 0.06:0.20 to 0.75: 30-45, gelling at 55-65 ℃, aging at 70-82 ℃ for 2-14 h, crystallizing at 120 ℃ for 6-10 h, then crystallizing at 165-180 ℃ for 10-14 h, adopting chemical modification of Ni, P and Fe elements, wherein the content of Ni is 0.3-2.5% calculated by oxide based on molecular sieve dry basis, the content of P is 0.5-6.5% calculated by oxide, and the content of Fe is 0.75-3.5% calculated by oxide.
The Y-type molecular sieve is modified by La, ce, P, zn, la and Ce are loaded in an ion exchange form, after loading, the Y-type molecular sieve is roasted for 1 to 3.5 hours at the temperature of 450 to 550 ℃, then aged for 1.5 to 4.5 hours in an atmosphere with the water vapor content of 33 to 47 percent at the temperature of 400 to 520 ℃, loaded in a P and Zn impregnation form, and roasted for 2 to 5.5 hours at the temperature of 500 to 635 ℃ after loading.
The density range of the crude oil is 0.85-0.98 g/cm < 3 >, the carbon residue value is 0.1-10%, and the nickel and vanadium content is 1-1000 mg/kg.
The oxygen-containing gas can be one of air, oxygen-enriched air or oxygen, the catalyst regeneration mode is one of single-stage regeneration, two-stage regeneration and turbulent bed, rapid bed or conveying bed regeneration, and the mass ratio of water vapor to oxygen-containing gas is 0.01-0.45:1, preferably 0.05-0.25: 1, the regenerated gas is flue gas or contains CO 2 Is a gas mixture of (1).
According to the method, crude oil is firstly contacted with the first catalyst in the descending bed to generate a first catalytic reaction, the first catalyst does not use an acidic molecular sieve as an active component, the damage of heavy metals in the crude oil to a molecular sieve structure does not exist, and in addition, the defect that the acidic molecular sieve catalyst is quickly coked and deactivated due to asphaltene, carbon residue and the like can be avoided to a great extent, so that intermediate crude oil with high heavy metal content and asphaltene and carbon residue content can be processed.
Compared with the prior art, the method has the following beneficial effects:
heavy metals which have poisoning effect on an acid catalyst and carbon residues which easily cause coking of the acid catalyst are removed from crude oil by adopting a downlink reaction bed to carry out a first reaction, so that macromolecules in the crude oil are cracked into olefin components with medium size, and small molecules in the crude oil can generate smaller gasoline olefin molecules; the first oil gas product is contacted with a second catalyst acid catalyst in a reducing downer reactor to be converted into low-carbon olefin to the greatest extent, so that chemicals are produced from intermediate base crude oil and intermediate-cycloalkyl crude oil to the greatest extent.
Drawings
FIG. 1 is a schematic diagram of the process flow of the crude oil preparation chemicals of the present invention.
In the figure, crude oil 1, 2 downer reactor, 3 first oil gas product, 4 horizontal cyclone I, 5 first spent catalyst, 6 stripper I, 7 first spent transfer chute, 8 burnt gas, 9 first regenerator, 10 first flue gas, 11 first regenerator lift gas, 12 first regenerator transfer riser, 13 fractionation column, 14 first gas product, 15 first liquid product, 16 return component, 17 variable diameter downer reactor, 18 horizontal cyclone II, 19 second regenerated catalyst, 20 stripper II, 21 second oil gas product, 22 second spent transfer chute, 23 burnt air, 24 second regenerator, 25 second flue gas, 26 second regenerator lift gas, 27 second regenerator transfer riser
Detailed Description
Examples
The first catalyst used in this example was prepared as follows. Mixing kaolin with water, pulping, adding aluminum oxide, silicon dioxide and titanium oxide, fully mixing, adding aluminum sol binder, adding ferric nitrate, manganese nitrate, cerium nitrate, barium nitrate, calcium nitrate and vanadium nitrate, controlling the solid content at 27.5%, and spraying the mixed slurry to form the catalyst, wherein the proportion of the kaolin, the aluminum oxide, the silicon dioxide, the titanium oxide, the aluminum sol, the iron oxide, the manganese oxide, the cerium oxide, the barium oxide, the calcium oxide and the vanadium oxide is 40.5%,17.9%,16.8%, 7.1%, 5.1%, 2.1%, 1.5%, 2.8%, 2.0%, 2.4% and 1.8% based on oxide dry basis.
The molded catalyst is roasted for 2 hours at 500 ℃, and then the mixed solution of potassium nitrate and phosphoric acid is immersed on the roasted catalyst, wherein the potassium oxide and the phosphorus pentoxide respectively account for 0.3 percent and 2.1 percent of the weight of the catalyst based on the dry oxide. And drying the impregnated catalyst, and roasting at 500 ℃ for 1.5 hours to obtain the finished catalyst. The proportion of mesoporous volume to total pore volume of the catalyst is 42.1%, and the proportion of mesoporous volume to total pore volume is 63.5%.
The second catalyst was prepared as follows. Mixing kaolin and water, pulping, adding aluminum oxide, fully mixing, adding a proper amount of hydrochloric acid solution, adding aluminum sol, fully mixing, adding MFI molecular sieve and USY molecular sieve, fully mixing, adding ferric nitrate, phosphoric acid and cerium nitrate solution, controlling the solid content to be 27%, and spraying the mixed slurry to form the catalyst, wherein the proportion of the kaolin, the aluminum oxide, the aluminum sol, the MFI molecular sieve, the USY molecular sieve, the ferric oxide, the phosphorus pentoxide and the cerium oxide is 37.5%,18.2%,5.7%,26.5%,7.6% and 1.0%, 2.1% and 1.4% based on oxide dry basis.
The preparation method of the MFI molecular sieve comprises the steps of taking a conventional ZSM-5 molecular sieve with a silicon-aluminum ratio of 43 as a matrix, adding sulfuric acid for dissolution, then taking the mixture as a seed crystal, sequentially adding macroporous pseudo-boehmite and a silicon source, and obtaining a porous silica gel according to n (SiO 2 )：n(Al 2 O 3 ): n (n-butylamine): n (tween): n (NaOH): n (H) 2 O) =1: 0.15:0.33:0.05:0.55:40, gelling at 60deg.C for 2h, aging at 75deg.C for 4h, crystallizing at 120deg.C for 8h, and crystallizing at 175 deg.C for 11h, and chemically modifying Ni, P and Fe elements to obtain the final productThe content of Ni is 0.4% calculated by oxide, the content of P is 5.2% calculated by oxide, and the content of Fe is 0.96% calculated by oxide.
The Y-type molecular sieve is modified by La, ce, P, zn, is loaded in an ion exchange mode by nitrate of La and Ce, is roasted for 3 hours at 460 ℃ after loading, is aged for 2.5 hours in an atmosphere with water vapor content of 38% at 450 ℃, is loaded in a nitrate impregnation mode by P and Zn, and is roasted for 3 hours at 540 ℃ after loading.
The raw materials are intermediate crude oil, and the oil properties are shown in the table 1.
TABLE 1
Project Numerical value
Density, g/cm3 at 20 DEG C 0.9314
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, μg/g
Nickel (Ni) 10.4
Vanadium (V) 3.5
Distillation range, DEG C
10％ 195
30％ 315
50％ 406
70％ 489
90％ 681
Crude oil 1 with the properties shown in Table 1 is preheated to 254 ℃, then is sprayed from a feeding nozzle of a downer reactor 2, the crude oil is contacted with a first catalyst under the pressure of 0.25MPa, the reaction is carried out for 0.6s at the outlet temperature of the downer reactor of 502 ℃, steam is simultaneously introduced into the reactor, the mass ratio of the steam to the raw oil is 0.21:1, the mass ratio of the catalyst to the raw oil is 15.4:1, after the reaction is finished, the oil is separated, a first oil gas product 3 and a coked first catalyst to be regenerated 5 are obtained, the first catalyst to be regenerated 5 is sent to a first regenerator 9 after the residual oil gas product on the catalyst is eluted by the steam, the burnt regeneration is carried out by introducing air at the temperature of 686 ℃, and the regenerated first catalyst is recycled.
The obtained first oil gas product 3 is sent to a fractionating tower 13 to obtain a first gas product 14 containing dry gas and liquefied gas and a first liquid product 15 containing gasoline and the components, the collected first liquid product 15 is preheated to 225 ℃, then the first liquid product 15 is introduced into a reducing downstream bed reactor 17 to be contacted with a second catalyst, under the conditions of a reaction pressure of 0.34MPa, a reaction temperature of 562 ℃ and a reaction time of 0.8s, a water-oil ratio of 0.22:1 and a catalyst-oil ratio of 13.5:1, a second catalytic reaction occurs, after the reaction is finished, the second oil gas product 21 and a coked deactivated second catalyst are obtained through separation, the deactivated second catalyst is sent to a second regenerator 24 after the residual oil gas product on the catalyst is eluted by steam, the regenerated second catalyst is circularly used under the condition of 685 ℃ by introducing air, and the second oil gas product 21 enters a subsequent separation device to obtain low-carbon olefin and aromatic hydrocarbon products. The aromatic hydrocarbon product comprises light aromatic hydrocarbon and heavy aromatic hydrocarbon, wherein the light aromatic hydrocarbon is C6-C9 light aromatic hydrocarbon, the heavy aromatic hydrocarbon is 2-4 ring aromatic hydrocarbon, and the prepared heavy aromatic hydrocarbon can be used as a raw material for preparing needle coke or carbon materials.
Table 2 shows the product distribution results of the intermediate crude oil as raw material, and it can be seen from the table that the ethylene yield reaches 5.2%, the yields of propylene and butene reach 15.6% and 13.8%, the yield of light aromatic hydrocarbon in gasoline is 22.6%, and the yield of 2-4 cycloaromatic hydrocarbon is 14.5%. Under the method provided by the invention, the intermediate crude oil is taken as a raw material, and the chemical yield of 71.7% can be obtained.
TABLE 2
Product distribution Yield, wt.%
Dry gas 9.5
Wherein ethylene is 5.2
Liquefied gas 35.1
Wherein propylene is 15.6
Wherein the butene is 13.8
C5+ gasoline 28.3
Wherein the C6-C9 light aromatic hydrocarbon 22.6
Cracking heavy oil diesel oil 19.2
Wherein the ring aromatic hydrocarbon is 2-4 14.5
Coke 7.9
Totals to 100
Yield of light olefins and light aromatics 71.7
The above examples are representative embodiments of the present invention, the present invention is not limited to the specific details of the above examples, and simple modifications and catalyst formulation adjustments may be made to the technical route of the present invention within the scope of the technical concept of the present invention, and these simple modifications and adjustments are all within the scope of the present invention.

Claims (9)

1. A method for directly producing chemicals from crude oil, the method comprising:
1) Preheating crude oil to 120-320 ℃, spraying the crude oil into a downlink bed reactor from a feeding atomizing nozzle, contacting the crude oil with a first catalyst, performing coke burning regeneration at a reaction pressure of 0.05-0.65 MPa, a reaction temperature of 380-650 ℃ and a reaction time of 0.02-5.5 s under the conditions of a water-oil ratio of 0.05-0.6:1 and a catalyst-oil ratio of 4.5-30:1, separating to obtain a first oil gas product and a coking deactivated first catalyst after the reaction is finished, feeding the deactivated first catalyst into a coke burning regenerator after steam stripping, introducing oxygen-containing gas or a mixed gas of steam and the oxygen-containing gas, and performing coke burning regeneration at 635-900 ℃ for recycling the regenerated first catalyst; the first catalyst is a catalytic cracking catalyst containing rich mesoporous structures;
2) The first oil gas product obtained in the step 1) is sent to a fractionating tower to obtain a first gas product containing dry gas and liquefied gas and a first liquid product containing gasoline and the components, the first liquid product is introduced into a reducing downstream bed reactor to be contacted with an acid catalyst serving as a second catalyst, and the second catalytic reaction is carried out under the conditions that the reaction pressure is 0.04-0.65 MPa, the reaction temperature is 520-650 ℃, the reaction time is 0.03-6.5 s, the water-oil ratio is 0.10-0.45:1 and the catalyst-oil ratio is 6.0-23:1, and after the reaction is finished, the second oil gas product and the coked deactivated second catalyst are obtained through separation; the deactivated second catalyst is sent to a burning regenerator after the residual oil gas product on the catalyst is eluted by steam, and the second oil gas product enters a subsequent separation device to obtain low-carbon olefin and aromatic hydrocarbon products;
the first catalyst comprises 8-50% of clay, 0.5-45% of one or more of silicon composite oxide, high-silicon molecular sieve, silicon dioxide, mesoporous silicon dioxide, aluminum oxide and titanium oxide, 0.2-10% of one or two of aluminum sol and silicon sol binders calculated by oxide, 0.3-45% of one or more of iron, nickel, potassium, calcium, magnesium, sodium, manganese, cerium, gallium, phosphorus and boron calculated by oxide, wherein the mesoporous volume of the catalyst accounts for 25.5-100% of the total pore volume, and the mesoporous volume accounts for 20-100% of the total pore volume;
the second catalyst comprises, on a dry basis, 15-55% of clay, 10-45% of one or more of MFI type molecular sieve, Y type molecular sieve, silicon dioxide, aluminum oxide, ferric oxide and titanium oxide, 0.2-10% of one or two of aluminum sol and silica sol binders, 0.35-10.5% of one or more of nickel, potassium, magnesium, manganese, cerium, gallium, phosphorus and boron, wherein the mesoporous volume of the catalyst accounts for 15-35% of the total pore volume, and the mesoporous volume accounts for 20-42% of the total pore volume.
2. The method of claim 1, wherein the crude oil comprises paraffinic crude oil and intermediate crude oil.
3. The method of claim 1, wherein the crude oil is further blended with one or more of deasphalted oil, hydrocracked tail oil, shale oil, atmospheric residuum, vacuum residuum, or vacuum wax oil.
4. The method of claim 1, wherein the second oil and gas product has a primary distillation point of 30-60% of the total amount of components at 80 ℃ and 25-55% of the total amount of components at 320-420 ℃, and at least a portion of the total amount of components is returned to the variable diameter downer reactor for recycling.
5. The method of claim 1, wherein the downer reactor in the first catalytic reaction comprises an equal diameter downer reactor and a variable diameter downer reactor.
6. The method according to claim 1, wherein the MFI-type molecular sieve is prepared by using a conventional ZSM-5 molecular sieve having a silica-alumina ratio of 35 to 60 as a matrix, adding sulfuric acid to dissolve the matrix, then adding macroporous pseudo-boehmite and a silicon source in sequence, and obtaining a solution according to n (SiO 2 )：n(Al 2 O 3 ): n (n-butylamine): n (tween): n (NaOH): n (H) 2 O) =1: 0.002-0.35: 0.19 to 0.42:0.04 to 0.06: 0.20-0.75: 30-45, performing glue forming at 55-65 ℃, aging at 70-82 ℃ for 2-14 h, crystallizing at 120 ℃ for 6-10 h, crystallizing at 165-180 ℃ for 10-14 h, adopting chemical modification of Ni, P and Fe elements, wherein the content of Ni is 0.3-2.5% in terms of oxide, the content of P is 0.5-6.5% in terms of oxide, and the content of Fe is 0.75-3.5% in terms of oxide based on the dry basis of a molecular sieve.
7. The method of claim 1, wherein the Y-type molecular sieve is modified by La, ce, P, zn, la and Ce are loaded in an ion exchange form, after loading, the Y-type molecular sieve is baked for 1 to 3.5 hours at 450 to 550 ℃, then aged for 1.5 to 4.5 hours in an atmosphere with a water vapor content of 33 to 47% at 400 to 520 ℃, loaded in a p and Zn impregnation form, and then baked for 2 to 5.5 hours at 500 to 635 ℃.
8. The method of claim 1, wherein the crude oil density ranges from 0.85 to 0.98g/cm 3 The carbon residue value is 0.1-10%, and the nickel and vanadium content is 1-1000 mg/kg.
9. The method according to claim 1, wherein the oxygen-containing gas is one of air, oxygen-enriched air or oxygen, the catalyst regeneration mode is one of single-stage regeneration, two-stage regeneration and turbulent bed, rapid bed or transport bed regeneration, the mass ratio of water vapor to oxygen-containing gas is 0.01-0.45:1, and the regenerated gas is flue gas or CO-containing gas 2 Is a gas mixture of (1).
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