CN114437768B - Method for cracking crude oil - Google Patents
Method for cracking crude oil Download PDFInfo
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- CN114437768B CN114437768B CN202011187680.4A CN202011187680A CN114437768B CN 114437768 B CN114437768 B CN 114437768B CN 202011187680 A CN202011187680 A CN 202011187680A CN 114437768 B CN114437768 B CN 114437768B
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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
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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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4006—Temperature
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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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4012—Pressure
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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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
Abstract
The invention relates to the technical field of crude oil cracking, and discloses a crude oil cracking method, which comprises the following steps: (1) Carrying out first separation on crude oil to obtain a first light fraction and a first heavy fraction; (2) Carrying out second separation on the first light fraction to obtain a second light fraction and a second heavy fraction, and respectively carrying out first pyrolysis and second pyrolysis to obtain a first pyrolysis product and a second pyrolysis product; (3) The first heavy fraction enters a coking reactor, and coke, a third light fraction and a third heavy fraction are obtained under the action of a coking catalyst and/or coke particles; (4) Subjecting the third light fraction to a third cleavage to obtain a third cleavage product, optionally subjecting the third heavy fraction to a second processing. The invention adopts a catalytic coking or coking nucleation method, and after the heavy fraction is subjected to coking treatment, the light fraction can be obtained as a cracking raw material, and the triene yield is more than 39%.
Description
Technical Field
The invention relates to the technical field of crude oil cracking, in particular to a crude oil cracking method.
Background
The cracking raw materials mainly come from ten million tons of refineries and mainly comprise ethane, propane, butane, naphtha, hydrogenated tail oil and the like. The selection of the cracking raw material has an important influence on the economic benefit of the cracking device, and meanwhile, the selection of the cracking raw material can generate larger fluctuation along with market change. When the price of crude oil is relatively high, the lightening of raw materials is first preferred. When diesel oil pressure warehouse occurs, the maximization of the raw material benefit becomes the first choice, and hydrogenated tail oil and hydrogenated diesel oil become high-quality cracking raw materials.
In order to solve the above problems, exxonMobil corporation has conducted research on a technology for producing olefins by steam cracking of crude oil (crude oil after dehydration desalting treatment). The company firstly provides a process route for directly carrying out steam cracking on crude oil, cuts the crude oil by utilizing a flash evaporation method, and sends raw materials into cracking furnaces of different types, so that the coking problem of the crude oil in the vaporization process is solved. The light crude oil (the final distillation point is not more than 593 ℃) is taken as a cracking raw material by the company to build a 100 ten thousand ton/year ethylene device and enable production, thus realizing industrialization of the technology for preparing olefin by cracking the crude oil.
Saudi Arabian Oil, which has also developed crude oil chemical technology, processes crude oil using a hydrogenation process to hydrogenate various unsaturated olefins to paraffins, and then feeds the feedstock to a steam cracker to facilitate the production of olefins. The conversion rate of the crude oil converted into chemicals reaches more than 50%, even more than 70%.
The crude oil steam cracking process of LyondellBasell company is developed from the energy-saving aspect, the components of crude oil are cut by fully utilizing the heat of a convection section of a cracking furnace and adding devices such as a vapor-liquid separator, light components enter the cracking furnace for cracking, and heavy components enter a hydrocracking or catalytic cracking device for generating components such as gasoline, diesel oil and the like.
Shell and Lummes company also consider sufficient energy conservation to divide crude oil into two fractions, namely a light fraction and a heavy fraction, wherein the heavy fraction is fed into a corresponding hydrogenation device for further treatment, and the light fraction is directly fed into a cracking furnace for cracking to generate various olefins.
In the existing crude oil cracking process, most of cracking raw materials are light fractions with higher API, but the quantity of the raw materials is limited, and the raw materials are not easy to obtain. For the heavy fraction cracking raw material, catalytic cracking or hydrocracking is firstly carried out, and the subsequent thermal cracking is carried out on the cracked product, but the process equipment investment is more, and the production cost is high.
Disclosure of Invention
The invention provides a crude oil cracking method for overcoming the technical problems. The invention firstly utilizes flash evaporation technology to separate different fractions in crude oil to obtain light fraction and heavy fraction which can be directly used as cracking raw materials, then removes naphthenes and aromatic hydrocarbons in the heavy fraction through coking treatment, and simultaneously separates the light fraction which can be used as cracking raw materials for thermal cracking, and the coke and the heavy fraction enter a subsequent hydrogenation device. The method can effectively improve the utilization rate of medium and/or heavy crude oil, improve the ethylene yield, and effectively reduce the equipment investment cost and the production cost.
In order to achieve the above object, the present invention provides a method for cracking crude oil, comprising the steps of: (1) Carrying out first separation on crude oil to obtain a first light fraction and a first heavy fraction; (2) Carrying out second separation on the first light fraction to obtain a second light fraction and a second heavy fraction, and respectively carrying out first pyrolysis and second pyrolysis to obtain a first pyrolysis product and a second pyrolysis product; (3) The first heavy fraction enters a coking reactor, and coke, a third light fraction and a third heavy fraction are obtained under the action of a coking catalyst and/or coke particles; (4) Subjecting the third light fraction to a third cleavage to obtain a third cleavage product, optionally subjecting the third heavy fraction to a second processing.
Through the technical scheme, the invention has the following beneficial effects:
(1) The invention adopts a catalytic coking or coking nucleation method, and after the heavy fraction is subjected to coking treatment, the light fraction can be obtained as a cracking raw material, and the triene yield is more than 39%; the method of the invention does not need to hydrogenate or catalytically crack the heavy fraction, reduces the production cost and reduces the equipment investment.
(2) The process of the present invention can be applied to various crude oils, and in particular, can be applied to crude oils having an API of 10 to 36, preferably 15 to 36, and more preferably 20 to 36.
Drawings
FIG. 1 is a schematic diagram of the apparatus for crude oil cracking of the present invention.
Description of the reference numerals
The method comprises the steps of a 1-flash distillation tower, a 2-rectifying tower, a 3-first cracking furnace, a 4-second cracking furnace, a 5-heating furnace, a 6-fixed bed coking reactor, a 7-third cracking furnace, an 8-hydrogenation device, 9-crude oil, a 10-first light fraction, a 11-first heavy fraction, a 12-second light fraction, a 13-second heavy fraction, a 14-heated first heavy fraction, a 15-third light fraction and a 16-third heavy fraction.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The invention provides a crude oil cracking method, which comprises the following steps: (1) Carrying out first separation on crude oil to obtain a first light fraction and a first heavy fraction; (2) Carrying out second separation on the first light fraction to obtain a second light fraction and a second heavy fraction, and respectively carrying out first pyrolysis and second pyrolysis to obtain a first pyrolysis product and a second pyrolysis product; (3) The first heavy fraction enters a coking reactor, and coke, a third light fraction and a third heavy fraction are obtained under the action of a coking catalyst and/or coke particles; (4) Subjecting the third light fraction to a third cleavage to obtain a third cleavage product, optionally subjecting the third heavy fraction to a second processing.
The method provided by the invention mainly aims at that the heavy fraction contained in crude oil can not be used for preparing olefin products by a direct cracking method, and can be used as a cracking raw material after hydrogenation, and the hydrogenation device has high equipment investment and high production cost. In the invention, the light fraction and the heavy fraction are obtained by separating the medium and/or heavy crude oil, the light fraction can be used as a high-quality cracking raw material to be cracked in a cracking furnace, the heavy fraction enters a coking reactor, coke, the light fraction and the heavy fraction are generated under the action of a coking catalyst and/or coke particles, the light fraction can directly enter the cracking furnace, and the heavy fraction and the coke enter a subsequent hydrogenation device; reduces the investment of equipment, lowers the production cost, greatly improves the utilization rate of crude oil and improves the yield of cracked ethylene.
According to the present invention, the crude oil preferably has an API of 10 to 36, preferably 15 to 36, and more preferably 20 to 36.
According to the present invention, preferably, the crude oil is a medium crude oil and/or a heavy crude oil; further preferably, the crude oil has a gum and asphaltene content of greater than 1wt%, preferably from 5wt% to 25wt%.
The first separation means may be conventional in the art according to the present invention; preferably, the first separation mode is flash evaporation, and the flash evaporation conditions include: the flash evaporation pressure is 0.09-0.11MPa, and the temperature is 340-360 ℃.
According to the present invention, in order to make the effect of the first separation better, the content of the first light fraction is increased; preferably, the first separation is carried out in a flash column, the first light fraction withdrawn from the top of the flash column being a fraction having a boiling point of less than 350 ℃, and the first heavy fraction withdrawn from the bottom of the flash column being a fraction having a boiling point of greater than 350 ℃.
According to the invention, the second separation mode is rectification, and the conditions of the rectification include: the temperature of the top of the tower is 150-250 ℃, preferably 180-220 ℃; the bottom temperature is 180-350 ℃, preferably 200-350 ℃; the number of the tower plates is 30-40, and the pressure is 0.08-0.1MPa.
According to the invention, the first cracking mode is thermal cracking; the conditions of the first cleavage may be conventional conditions in the art, preferably the conditions of the first cleavage include: the pressure of the first cracking is 0.05-0.3MPa, preferably 0.07-0.15MPa; the temperature of the first cleavage is 800-850 ℃, preferably 820-830 ℃; the residence time of the first cleavage is from 0.05 to 1s, preferably from 0.1 to 0.3s; the mass ratio of water to oil of the first pyrolysis is (0.1-2): 1, preferably (0.4-1.5): 1.
according to the present invention, the first cleavage product contains small amounts of benzene, toluene, xylene, etc., in addition to the target products of ethylene, propylene, and butadiene.
According to the invention, the second cracking mode is thermal cracking; the conditions of the second cleavage may be conventional conditions in the art, preferably the conditions of the second cleavage include: the pressure of the second cracking is 0.05-0.3MPa, preferably 0.07-0.15MPa; the second cleavage temperature is 750-850 ℃, preferably 790-810 ℃; the residence time of the second cleavage is from 0.05 to 1s, preferably from 0.1 to 0.7s; the mass ratio of water to oil of the second cracking is (0.1-2): 1, preferably (0.4-1.5): 1.
according to the invention, the second cracking product contains small amounts of benzene, toluene and xylene in addition to the target products ethylene, propylene and butadiene.
The inventor of the invention finds that the heavy fraction is subjected to a cracking reaction and a condensation reaction through coking reaction, so that macromolecules are changed into small molecules through breaking of chemical bonds, part of coke is removed, and meanwhile, the light fraction is separated out and can be used as a high-quality cracking raw material for thermal cracking to obtain low-carbon olefin, so that the utilization rate of the raw material is greatly improved.
According to the present invention, the conditions of the coking reaction may be selected within a wide range as long as the first heavy fraction is separated into light fractions, and preferably the coking reaction conditions include: the reaction temperature is 350-400 ℃, the reaction time is 5-10h, and the operating pressure is normal pressure.
According to the present invention, the contacting is performed in a coking reactor, the kind of which is not particularly limited; preferably, the coking reactor is one of a fixed bed coking reactor, a moving bed coking reactor and a fluidized bed coking reactor.
According to the present invention, the active component of the coked catalyst may be an active component of a coked catalyst commonly used in the art, preferably, the active component of the coked catalyst is a group viii metal element and/or a group vi B metal element, and more preferably, the active component of the coked catalyst is at least one of iron, nickel, and chromium.
According to the invention, the support of the coked catalyst may be a catalyst support commonly used in the art, preferably the support of the coked catalyst is a molecular sieve and/or alumina.
According to the invention, the active component is preferably present in an amount of 1 to 20g, preferably 5 to 15g, relative to 100g of coked catalyst.
The inventors of the present invention have found that coke particles are capable of accelerating the coking reaction. According to a preferred embodiment of the invention, the coke particles are milled from the coke produced by the coking reaction of the present invention, preferably the average particle diameter of the coke particles is from 10 to 1000 μm.
According to the invention, in order to make the coking reaction more efficient, the concentration of the coked catalyst and/or coke particles in the coked reactor is preferably 5-20 vol.%, more preferably 5-12 vol.% to meet the needs of the coking reaction.
The concentration of the coked catalyst and/or coke particles in the coked reactor is the volume ratio of the coked catalyst and/or coke particles to the treated material in the coked reactor.
According to the invention, the method may further comprise; heating the first heavy fraction and then contacting the first heavy fraction with coked catalyst and/or coke particles; preferably, the temperature of the heating is 350-400 ℃.
And carrying out coking reaction on the first heavy fraction to obtain a third light fraction, a third heavy fraction and coke, and carrying out third cracking on the third light fraction to obtain a third cracking product. According to the present invention, preferably, the third light fraction is a fraction having an end point of less than 350 ℃, and the third heavy fraction is a fraction having a temperature of 350 to 500 ℃.
According to the invention, the coke generated by the coking reaction can be obtained by means of hydraulic decoking.
According to the invention, the conditions of the third cleavage include: the pressure of the third cracking is 0.05-0.3MPa, preferably 0.07-0.15MPa; the temperature of the third cleavage is 800-850 ℃, preferably 820-830 ℃; the residence time for the third cleavage is from 0.05 to 1s, preferably from 0.1 to 0.3s; the mass ratio of water to oil of the third cracking is (0.1-2): 1, preferably (0.4-1.5): 1.
according to the invention, the third cracking product contains small amounts of benzene, toluene and xylene in addition to the target products of ethylene, propylene and butadiene.
According to a preferred embodiment of the present invention, in order to reduce investment in equipment and simplify the process flow, the first, second and third cleavage products are not separately separated, and preferably, the first, second and third cleavage products are collected in a separation tank and then separated to obtain target products of ethylene, propylene and butadiene, respectively.
Although the first heavy fraction obtained in the step (1) can be used as a raw material for cracking after being hydrogenated, the invention aims to reduce equipment investment and production cost. According to the present invention, preferably, no hydrogenation step is included between step (1) and step (3).
According to the present invention, in order to increase the utilization ratio of the raw material, further increase the added value of the product, it is preferable that the third heavy fraction is subjected to secondary processing to obtain gasoline, diesel oil, and naphtha.
According to the present invention, the manner of the secondary processing is not particularly limited, and preferably the secondary processing includes: hydrocracking and/or catalytic cracking.
The operation of the crude oil cracking process will be described with reference to the schematic process flow diagram of the crude oil cracking of the present invention shown in fig. 1.
Feeding crude oil 9 into a flash tower 1 for first separation to obtain a first light fraction 10 and a first heavy fraction 11, and feeding the obtained first light fraction 10 into a rectifying tower 2 for second separation to obtain a second light fraction 12 and a second heavy fraction 13; the second light fraction 12 is discharged from the top of the rectifying tower 2 and enters the first cracking furnace 3 for first cracking to obtain a first cracking product; discharging the second heavy fraction 13 from the bottom of the rectifying tower 2, and entering a second cracking furnace 4 for second cracking to obtain a second cracking product; heating the first heavy fraction 11 in a heating furnace 5 to obtain a heated first heavy fraction 14, feeding the heated first heavy fraction into a fixed bed coking reactor 6 for coking reaction, discharging a third light fraction 15 from the top of the fixed bed coking reactor after the coking reaction is finished, and discharging a third heavy fraction 16 and coke from the bottom of the fixed bed coking reactor; feeding the third light fraction 15 into a third cracking furnace 7 for third cracking to obtain a third cracking product; the third heavy fraction 16 is sent to the hydrogenation unit 8 for hydrocracking.
The present invention will be described in detail by examples.
The coked catalyst of examples 1-2 consisted of 5wt% metallic iron active component and 95wt% alumina support.
Example 1
This example is intended to illustrate a method for producing ethylene by cracking crude oil
(1) Feeding crude oil (API value is 20) containing the middle distillate and the heavy distillate into a flash tower, and carrying out first separation to obtain a first light distillate and a first heavy distillate, wherein the operation temperature of the flash tower is 350 ℃, and the operation pressure of the flash tower is 0.09MPa; then sending the obtained first light fraction into a rectifying tower for second separation, wherein the temperature of the top of the rectifying tower is 200 ℃; the bottom temperature is 350 ℃; the number of the trays was 30, and the pressure was 0.09MPa. And discharging the second light fraction from the top of the rectifying tower, and entering a first cracking furnace for first cracking to obtain a first cracking product, wherein the pressure of the first cracking furnace is 0.1MPa, the temperature of the first cracking furnace is 820 ℃, the residence time in the first cracking furnace is 0.2s, and the water-oil mass ratio is 1.2:1. And discharging the second heavy fraction from the bottom of the rectifying tower, and performing second pyrolysis in a second pyrolysis furnace to obtain a second pyrolysis product, wherein the pressure of the second pyrolysis furnace is 0.12MPa, the temperature of the second pyrolysis furnace is 800 ℃, the residence time in the second pyrolysis furnace is 0.3s, and the water-oil mass ratio is 1.1:1.
(2) Heating the first heavy fraction obtained in the step (1) in a heating furnace to 390 ℃, and then sending the heated first heavy fraction into a fixed bed coking reactor, wherein the first heavy fraction contacts with a coking catalyst to react in the coking reactor, the concentration of the coking catalyst in the fixed bed coking reactor is 10% by volume, and the operation temperature of the fixed bed coking reactor is as follows: coking reaction time is 7h at 390 ℃. After the coking reaction is finished, discharging a third light fraction with the final distillation point less than 350 ℃ from the top of the fixed bed coking reactor, and discharging coke and a third heavy fraction with the distillation range of 350-500 ℃ from the bottom of the fixed bed coking reactor.
(3) And (3) sending the third light fraction in the step (2) into a third cracking furnace for third cracking to obtain a third cracking product, wherein the pressure of the third cracking is 0.1MPa, the temperature of the third cracking is 820 ℃, the retention time of the third cracking is 0.2s, and the water-oil mass ratio is 0.8:1.
(4) Hydrocracking the third heavy fraction in step (2).
The first cleavage product, the second cleavage product and the third cleavage product were collected in a separation tank, and then separated to obtain ethylene, propylene, butene and the like, wherein the yield of ethylene was 22.5%, the yield of propylene was 12.36%, the yield of 1, 3-butadiene was 4.21%, and the yield of triene was 39.07%.
Example 2
This example is intended to illustrate a method for producing ethylene by cracking crude oil
(1) Feeding crude oil (API value is 35) containing the middle distillate and the heavy distillate into a flash tower, and carrying out first separation to obtain a first light distillate and a first heavy distillate, wherein the operation temperature of the flash tower is 350 ℃, and the operation pressure of the flash tower is 0.1MPa; then sending the obtained first light fraction into a rectifying tower for second separation, wherein the temperature of the top of the rectifying tower is 220 ℃; the bottom temperature is 350 ℃; the number of the tower plates is 38, and the pressure is normal pressure. And discharging the second light fraction from the top of the rectifying tower, and entering a first cracking furnace for first cracking to obtain a first cracking product, wherein the pressure of the first cracking furnace is 0.15MPa, the temperature of the first cracking furnace is 830 ℃, the residence time in the first cracking furnace is 0.25s, and the water-oil mass ratio is 0.9:1. And discharging the second heavy fraction from the bottom of the rectifying tower, and performing second pyrolysis in a second pyrolysis furnace to obtain a second pyrolysis product, wherein the pressure of the second pyrolysis furnace is 0.14MPa, the temperature of the second pyrolysis furnace is 810 ℃, the residence time in the second pyrolysis furnace is 0.5s, and the water-oil mass ratio is 0.85:1.
(2) Heating the first heavy fraction obtained in the step (1) in a heating furnace to 400 ℃, and then feeding the heated first heavy fraction into a fixed bed coking reactor, wherein the first heavy fraction contacts with a coking catalyst to react in the fixed bed coking reactor, the concentration of the coking catalyst in the fixed bed coking reactor is 12% by volume, and the operation temperature of the fixed bed coking reactor is as follows: coking reaction time is 9h at 400 ℃. After the coking reaction is finished, discharging a third light fraction with the final distillation point less than 350 ℃ from the top of the fixed bed coking reactor, and discharging coke and a third heavy fraction with the distillation range of 350-500 ℃ from the bottom of the fixed bed coking reactor.
(3) And (3) sending the third light fraction in the step (2) into a third cracking furnace for third cracking to obtain a third cracking product, wherein the pressure of the third cracking is 0.13MPa, the temperature of the third cracking is 825 ℃, the retention time of the third cracking is 0.28s, and the water-oil mass ratio is 0.8:1.
(4) Hydrocracking the third heavy fraction in step (3).
The first cleavage product, the second cleavage product and the third cleavage product were collected in a separation tank, and then separated to obtain ethylene, propylene, butene and the like, wherein the yield of ethylene was 22.8%, the yield of propylene was 12.54%, the yield of 1, 3-butadiene was 4.26%, and the yield of triene was 39.6%.
Comparative example 1
This comparative example is used to compare a process for producing ethylene by cracking crude oil.
Crude oil which is the same as that of the embodiment 1 is directly sent into a cracking furnace for cracking reaction, wherein the cracking temperature of the cracking furnace is 810 ℃, the cracking pressure is 0.15MPa, the residence time is 0.6s, and the mass ratio of water to oil is 1.2:1. The cleavage product was isolated with an ethylene yield of 18.49%, a propylene yield of 11.69%, a 1, 3-butadiene yield of 3.47% and a triene yield of 33.65%.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (32)
1. A method of cracking crude oil, the method comprising the steps of: (1) Carrying out first separation on crude oil to obtain a first light fraction and a first heavy fraction; (2) Carrying out second separation on the first light fraction to obtain a second light fraction and a second heavy fraction, and respectively carrying out first pyrolysis and second pyrolysis to obtain a first pyrolysis product and a second pyrolysis product; (3) The first heavy fraction enters a coking reactor, and coke, a third light fraction and a third heavy fraction are obtained under the action of a coking catalyst and/or coke particles; (4) Subjecting the third light fraction to a third cracking to obtain a third cracked product, optionally subjecting the third heavy fraction to a second processing;
the active component of the coking catalyst is a VIII family metal element and/or a VIB family metal element, and the carrier of the coking catalyst is a molecular sieve and/or alumina;
the reaction temperature of the coking reactor is 350-400 ℃ and the reaction time is 5-10h;
the concentration of the coked catalyst and/or coke particles in the coked reactor is from 5 to 20% by volume.
2. The method of claim 1, wherein the crude oil has an API of 10-36.
3. The method of claim 1, wherein the crude oil has an API of 15-36.
4. The method of claim 1, wherein the crude oil has an API of 20-36.
5. The method of claim 1, wherein the crude oil is a medium crude oil and/or a heavy crude oil.
6. The method of claim 1, wherein the crude oil has a gum and asphaltene content of greater than 1wt%.
7. The method of claim 1, wherein the crude oil has a gum and asphaltene content of 5wt% to 25wt%.
8. The method of any of claims 1-7, wherein the first separation is by flash evaporation, and the conditions of flash evaporation include: the flash evaporation pressure is 0.09-0.11MPa, and the temperature is 340-360 ℃.
9. The method of any one of claims 1-7, wherein the second separation is by rectification, and the conditions of the rectification include: the temperature of the tower top is 150-250 ℃; the temperature of the tower bottom is 180-350 ℃; the number of the tower plates is 30-40, and the pressure is 0.08-0.1MPa.
10. The process of claim 9, wherein the overhead temperature of the rectification is 180-220 ℃.
11. The method of claim 9, wherein the bottom temperature of the rectification is 200-350 ℃.
12. The method of any one of claims 1-7, wherein the first cracking is thermal cracking, and the conditions of the first cracking include: the pressure of the first cracking is 0.05-0.3MPa; the temperature of the first pyrolysis is 800-850 ℃; the residence time of the first cleavage is 0.05-1s; the mass ratio of water to oil of the first pyrolysis is (0.1-2): 1.
13. the process of any one of claims 1-7, wherein the pressure of the first cleavage is from 0.07 to 0.15MPa.
14. The method of any one of claims 1-7, wherein the temperature of the first cleavage is 820-830 ℃.
15. The process of any one of claims 1-7, wherein the residence time of the first cleavage is from 0.1 to 0.3s.
16. The process of any one of claims 1-7, wherein the first pyrolysis has a water to oil mass ratio of (0.4-1.5): 1.
17. the method of any one of claims 1-7, wherein the second cracking is thermal cracking, and the conditions of the second cracking include: the pressure of the second cracking is 0.05-0.3MPa; the second cracking temperature is 750-850 ℃; the residence time of the second cleavage is 0.05-1s; the mass ratio of water to oil of the second cracking is (0.1-2): 1.
18. the process of any one of claims 1-7, wherein the pressure of the second cleavage is from 0.07 to 0.15MPa.
19. The method of any one of claims 1-7, wherein the second cleavage temperature is 790-810 ℃.
20. The process of any one of claims 1-7, wherein the residence time of the second cleavage is from 0.1 to 0.7s.
21. The process of any one of claims 1-7, wherein the second cracked water to oil mass ratio is (0.4-1.5): 1.
22. the method of any of claims 1-7, wherein the concentration of coked catalyst and/or coke particles in the coked reactor is 5-12 vol%.
23. The method of any of claims 1-7, wherein the active component of the coked catalyst is at least one of iron, nickel, and chromium.
24. The process of any of claims 1-7, wherein the coke particles have an average particle diameter of 10-1000 μιη.
25. The method of any one of claims 1-7, wherein the third cracking is thermal cracking, and the conditions of the third cracking include: the pressure of the third cracking is 0.05-0.3MPa; the temperature of the third cracking is 800-850 ℃; the residence time of the third pyrolysis is 0.05-1s; the mass ratio of water to oil of the third cracking is (0.1-2): 1.
26. the process according to any one of claims 1 to 7, wherein the pressure of the third cleavage is from 0.07 to 0.15MPa.
27. The method of any one of claims 1-7, wherein the temperature of the third cleavage is 820-830 ℃.
28. The process according to any one of claims 1 to 7, wherein the residence time of the third cleavage is from 0.1 to 0.3s.
29. The process according to any one of claims 1 to 7, wherein the third pyrolysis has a water to oil mass ratio of (0.4 to 1.5): 1.
30. the process of any one of claims 1-7, wherein no hydrogenation step is included between step (1) and step (3).
31. The process of any one of claims 1-7, wherein the third heavy fraction is subjected to secondary processing to obtain gasoline, diesel, and naphtha.
32. The method of any of claims 1-7, wherein the secondary processing comprises: hydrocracking and/or catalytic cracking.
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