CN109722306B - Processing method of inferior heavy oil - Google Patents
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Abstract
The invention relates to the field of hydrocarbon oil conversion, and discloses a processing method of inferior heavy oil, which comprises the following steps: the heavy oil raw material is cracked by contact with a contact agent to obtain dry gas, liquefied gas, gasoline fraction, circulating oil and a spent agent; separating the dry gas and the liquefied gas to obtain hydrogen, ethylene, propylene, butylene and butane; carrying out hydrofining on the gasoline fraction, and extracting a liquid-phase material flow to obtain aromatic-rich extract oil and aromatic-poor raffinate oil; separating the aromatic-rich extract oil to obtain benzene, toluene and xylene; performing solvent deasphalting treatment on the circulating oil to obtain deasphalted oil and deoiled asphalt; carrying out hydrogenation reaction on the deoiled asphalt; carrying out gasification reaction on the spent catalyst and oxygen-containing gas to obtain synthesis gas and a regenerated contact agent; and (3) recycling the deasphalted oil and the hydrogenated material for contact cracking reaction. By the method, the heavy raw material can be converted into raw material gas rich in ethylene, propylene, butylene and butane and triphen rich in benzene, toluene, xylene and the like in maximum, and meanwhile, the gasoline fraction with low aromatic hydrocarbon content is produced.
Description
Technical Field
The invention relates to the field of hydrocarbon oil conversion, in particular to a processing method of inferior heavy oil.
Background
Heavy oil, especially vacuum residue, is generally subjected to light conversion by a delayed coking process to produce naphtha and diesel, the naphtha is hydrogenated and then enters a reforming device to produce aromatic hydrocarbon, and the diesel is hydrogenated and then serves as automotive diesel. However, with the change of market demands, diesel oil on the market is excessive, and the requirements of diesel-gasoline ratio are lower and lower. Meanwhile, the vacuum residue is processed by a delayed coking process, so that the environmental protection problems of waste gas, waste water and the like can be generated in the decoking process, and the utilization of the high-sulfur petroleum coke is also subjected to the environmental protection requirement (the sulfur content is more than 3 percent and cannot be sold).
In addition, as the amount of automobile reserves in cities increases, automobile pollution is becoming one of the main sources of urban air pollution. In order to reduce the emission of automobiles, increasingly strict automobile emission regulations are set by all countries.
In order to make the automobile exhaust emission reach the standard, one of the main measures is to establish a strict automobile fuel standard and realize the fuel cleanness. Unified clean fuel standards are not established in countries of the world, and different countries and regions establish different clean fuel standards according to economic and technical development levels, the structure of oil refining devices and environmental protection requirements in different periods.
The aromatic hydrocarbon and olefin in the motor gasoline have higher octane number. If the aromatic hydrocarbon content of the motor gasoline is too high, the deposit in a combustion chamber can be increased, and the emission is influenced to a certain extent, so that the European Union requires that the aromatic hydrocarbon content of the gasoline is not higher than 35 percent (volume fraction) from 2005. And the high olefin content can cause coking and spray deterioration of the oil injector, thereby influencing the emission.
The automotive gasoline standard in China is from national IV grade to national V, the requirement on the volume content of aromatic hydrocarbon is not higher than 40%, and the volume content of olefin is reduced from 28% to 24%. The national gasoline VI standard is implemented in 2019, and the aromatic hydrocarbon and olefin content is further limited in the standard, wherein the olefin content is not more than 15% or 18%, and the aromatic hydrocarbon content is not more than 35%.
At present, in the average composition of Chinese gasoline pool, the blending component still uses catalytic cracking gasoline and catalytic reforming gasoline as main components, the total amount of the catalytic cracking gasoline and the catalytic reforming gasoline is over 85 percent, and the proportion of the alkylation gasoline or the isomerization gasoline which is the cleanest and most suitable for blending by the formula is very small. The gasoline pool has a great difference with the barrel-shaped structure consisting of gasoline pool catalytic cracking gasoline, reformed gasoline, alkylated gasoline and isomerized gasoline in Europe and America.
The gasoline standard for the Chinese automobile is increasingly strict, and the structure of a gasoline pool is influenced by continuously limiting olefin and aromatic hydrocarbon. Alkylated gasolines, isomerized gasolines, Methyl Tertiary Butyl Ether (MTBE), etc. will gradually increase in gasoline blending proportions.
Thus, there will be an increasing demand for feedstocks for the production of alkylate gasoline, isomerate gasoline, and MTBE in the future.
The alkylation raw material mainly comprises isobutane and butylene, and the MTBE also takes isobutene and methanol as raw materials. So the demand for isobutane and butenes will increase in the future. The current technology emphasizes the production of chemical raw materials such as ethylene, propylene, butadiene and the like. There is a potential for future shortages of hydrocarbons. The limitation to aromatic hydrocarbon in the national six-gasoline standard also leads the aromatic hydrocarbon in the catalytic cracking gasoline in China to be surplus.
Xylene (BTX) is a primary basic chemical raw material, nearly 70% of benzene, toluene and BTX required all over the world are from catalytic reforming, the raw material for catalytic reforming is naphtha (mainly straight-run gasoline), and the price of the naphtha is higher. Naphtha is also the main feedstock for the production of lower olefins, so there are sometimes two units competing for feedstock in refineries.
CN105087047A discloses a heavy oil catalytic cracking process for producing heavy and light aromatic hydrocarbon products, which uses heavy oil (wax oil, residual oil and their mixture) as raw material to produce heavy and light aromatic hydrocarbon products. Heavy oil raw material is subjected to catalytic cracking reaction, under the action of a catalyst, the content of aromatic hydrocarbon in light and heavy aromatic hydrocarbon products is more than 85%, and the products can be subsequently subjected to selective hydrogenation and solvent extraction unit operation to obtain a large amount of precious aromatic hydrocarbon raw material.
Shanghai Luyi petrochemical engineering science and technology Limited (CN1490383A) discloses a catalytic cracking process for co-producing aromatic hydrocarbon from heavy oil chemical raw materials, called MCC process for short, which realizes the maximum production of light olefin and light aromatic hydrocarbon by using heavy oil as raw materials under mild reaction conditions, the maximum yield of liquefied gas can reach 60%, and the propylene and butylene in the liquefied gas account for about 80%. The produced aromatic hydrocarbon changes along with the change of the raw materials, the light raw materials can produce light aromatic hydrocarbon to the maximum extent, and the heavy raw materials can simultaneously produce aromatic hydrocarbon and heavy aromatic hydrocarbon.
It can be seen from the foregoing prior art that the raw materials for producing low-carbon olefins and aromatics are all from light hydrocarbons or wax oil with good quality, such as ethylene and propylene produced by steam cracking of naphtha, aromatic hydrocarbons produced by reforming naphtha, propylene produced by DCC process from straight-run wax oil, and so on. The price of heavy oil, especially vacuum residue, is low, and how to efficiently utilize heavy oil, especially vacuum residue, is an important aspect to be considered for improving the quality and efficiency of refineries. The residual oil is a mixture rich in aromatic hydrocarbon, and from the viewpoint of oil refining economy, a processing route of 'preferably alkene, preferably arene' is generally considered.
In addition, during the contact cracking of low quality heavy oil, a portion of the low value product, which is rich in aromatics and contains a large amount of catalyst fines, is difficult to further process and utilize, and is usually sold at a low price or used as part of the feedstock for coking.
Disclosure of Invention
The invention aims to provide a method for processing inferior heavy oil by adopting a fluidized and continuous closed method, converting heavy raw materials into raw material gas rich in ethylene, propylene, butylene and butane and triphen rich in benzene, toluene, xylene and the like in maximum, solving the raw material problem of producing high-octane components, providing a processing way for the production of the triphen, reducing the raw material cost for producing the triphen, and simultaneously producing gasoline fraction with low aromatic hydrocarbon content.
In order to achieve the above object, the present invention provides a method for processing inferior heavy oil, comprising:
(1) introducing a heavy oil raw material into a contact cracking reaction zone to perform contact cracking reaction with a contact agent, and introducing the material subjected to the contact cracking reaction into a separation system to separate so as to obtain dry gas, liquefied gas, gasoline fraction, circulating oil and a spent agent;
(21) introducing the dry gas and the liquefied gas into a gas separation unit for separation to obtain hydrogen, ethylene, propylene, butenes, and butanes;
(22) introducing the gasoline fraction into a first hydrogenation unit for carrying out hydrofining reaction, and introducing a liquid phase material flow after the hydrofining reaction into an aromatic hydrocarbon extraction unit for extraction so as to respectively obtain aromatic-rich extract oil and aromatic-poor raffinate oil; then separating the aromatic-rich extract oil to obtain benzene, toluene and xylene;
(23) introducing the circulating oil into a solvent deasphalting unit for solvent deasphalting treatment to obtain deasphalted oil and deoiled asphalt; the deoiled asphalt enters a second hydrogenation unit to carry out hydrogenation reaction;
(24) introducing the spent agent into a gasification reaction unit to carry out gasification reaction with oxygen-containing gas, and separating a product obtained after the gasification reaction to obtain CO-containing gas and a regenerated contact agent;
(3) recycling the deasphalted oil and at least part of the material obtained from the second hydrogenation unit to the contact cracking reaction zone of the step (1) for contact cracking reaction.
The method can convert the heavy raw material into raw material gas rich in ethylene, propylene, butylene and butane and triphen rich in benzene, toluene, xylene and the like in maximum, and simultaneously produce gasoline fraction with low aromatic hydrocarbon content.
Furthermore, the method of combined processing of solvent deasphalting and slurry bed is adopted, so that the low-value heavy cracking fraction containing catalyst powder does not need to be settled and filtered, the component rich in saturated hydrocarbon is extracted only through the solvent deasphalting unit and returns to the contact cracking unit for further cracking, and the deoiled asphalt rich in aromatic hydrocarbon and containing catalyst powder is directly subjected to slurry bed hydrogenation.
Furthermore, the invention can partially oxidize the produced coke in situ to generate gas containing CO, which is used for generating steam in a CO boiler, thereby solving the problem of delayed coking petroleum coke utilization.
Drawings
FIG. 1 is a process flow diagram of a preferred embodiment of the process for processing inferior heavy oil of the present invention.
Description of the reference numerals
1. Contact cracking reaction zone
2. Gas separation unit
3. First hydrogenation unit
4. Aromatic extraction unit
5. Solvent deasphalting unit
6. Second hydrogenation unit
7. Gasification reaction unit
8. 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26 are all pipelines
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
As described above, the present invention provides a method for processing inferior heavy oil, comprising:
(1) introducing a heavy oil raw material into a contact cracking reaction zone to perform contact cracking reaction with a contact agent, and introducing the material subjected to the contact cracking reaction into a separation system to separate so as to obtain dry gas, liquefied gas, gasoline fraction, circulating oil and a spent agent;
(21) introducing the dry gas and the liquefied gas into a gas separation unit for separation to obtain hydrogen, ethylene, propylene, butenes, and butanes;
(22) introducing the gasoline fraction into a first hydrogenation unit for carrying out hydrofining reaction, and introducing a liquid phase material flow after the hydrofining reaction into an aromatic hydrocarbon extraction unit for extraction so as to respectively obtain aromatic-rich extract oil and aromatic-poor raffinate oil; then separating the aromatic-rich extract oil to obtain benzene, toluene and xylene;
(23) introducing the circulating oil into a solvent deasphalting unit for solvent deasphalting treatment to obtain deasphalted oil and deoiled asphalt; the deoiled asphalt enters a second hydrogenation unit to carry out hydrogenation reaction;
(24) introducing the spent agent into a gasification reaction unit to carry out gasification reaction with oxygen-containing gas, and separating a product obtained after the gasification reaction to obtain CO-containing gas and a regenerated contact agent;
(3) recycling the deasphalted oil and at least part of the material obtained from the second hydrogenation unit to the contact cracking reaction zone of the step (1) for contact cracking reaction.
The steps (21), (22), (23) and (24) of the present invention do not necessarily have a sequential order therebetween, and those skilled in the art should not be construed as limiting the method of the present invention.
According to a preferred embodiment, in step (1), said contact cracking reaction zone comprises at least two reaction units, and at least one of them is a fluidized bed reaction unit and at least another one is a riser reaction unit.
In the above preferred embodiment, in the fluidized bed reaction unit, the bed density is preferably 100 to 700kg/m3And the reaction conditions in the fluidized bed reaction unit include: the reaction temperature is 450-620 ℃, and the retention time is 3-8 s.
In the above preferred embodiment, in the riser reaction unit, the bed density is preferably 10 to 100kg/m3And the reaction conditions in the riser reaction unit include: the reaction temperature is 490-580 ℃, and the retention time is 0.5-2.0 s.
Preferably, in the invention, in the step (1), the fractionation point of the gasoline fraction and the cycle oil is 140-170 ℃, and more preferably 145-160 ℃; particularly preferably 150 to 160 ℃, for example, 150 ℃, 151 ℃, 152 ℃, 153 ℃, 154 ℃, 155 ℃, 156 ℃, 157 ℃, 158 ℃, 159 ℃ or 160 ℃.
Preferably, in step (22) of the present invention, the solvent in the aromatic extraction unit is at least one selected from the group consisting of N-methylpyrrolidone, tetraethylene glycol ether, diethylene glycol ether, triethylene glycol ether, sulfolane, dimethyl sulfoxide, and N-formyl morpholine.
Preferably, in the step (22) of the present invention, the volume ratio of the solvent used in the aromatic extraction unit to the liquid-phase material stream after the hydrorefining reaction is 3 to 12.
Preferably, the first hydrogenation unit contains a hydrorefining catalyst, the hydrorefining catalyst is a catalyst I, and the catalyst I is a hydro-upgrading catalyst having a hydro-upgrading function and/or an octane number recovery catalyst capable of recovering an octane number.
Preferably, the hydro-upgrading catalyst comprises at least one zeolite, at least one hydrogenation active component selected from the group consisting of group VIB non-noble metal elements and group VIII non-noble metal elements, and an alumina matrix. More preferably, in the hydro-upgrading catalyst, the zeolite is selected from at least one of HY zeolite, zeolite Beta and ZSM-5 zeolite.
Preferably, the octane number recovery catalyst contains zeolite and alumina as carriers, and a non-noble metal active component supported on the carriers, wherein the non-noble metal active component is at least one of cobalt, nickel, molybdenum and tungsten. More preferably, in the octane number recovery catalyst, the zeolite is selected from at least one of faujasite, zeolite Beta, ZSM-5 zeolite and SAPO-11 zeolite.
Preferably, in the first hydrogenation unit, the conditions under which the hydrofinishing reaction is carried out include: the hydrogen partial pressure is 0.3-6.0 MPa, the reaction temperature is 100-480 ℃, and the volume space velocity is 0.3-6.0 h-1The volume ratio of hydrogen to oil is 100-1200 Nm3/m3。
Preferably, in step (23) of the present invention,the solvent in the solvent deasphalting unit is C4～C6The hydrocarbon of (1).
Preferably, in step (23) of the present invention, the solvent deasphalting treatment conditions include: the extraction temperature is 110-230 ℃, and the extraction pressure is 3-6 MPa.
In the step (23) of the present invention, the second hydrogenation unit may be a fixed bed hydrogenation unit, an ebullated bed hydrogenation unit, or a slurry bed hydrogenation unit.
In order to obtain a reduction in the cost of the feedstock for the production of triphenyl while producing a gasoline fraction with a lower aromatic content, according to a preferred embodiment, in step (23), the second hydrogenation unit is a slurry bed hydrogenation unit.
Preferably, in the step (23), the second hydrogenation unit contains a catalyst II, and the catalyst II is a composite nano-catalyst containing a metal element and a nonmetal element.
Preferably, in the catalyst II, the non-metallic element is selected from at least one of non-metallic elements of groups IVA and VIA, and the metallic element is selected from at least one of metallic elements of groups VB, VIB, IVA and VIII; and preferably, the average particle size of the catalyst II is 10-50 nm.
More preferably, in the catalyst II, the metal element is at least one selected from Cr, V, Mo, W, Ni, Fe, Co, and Sn.
The catalyst II of the invention is preferably a two-dimensional and/or two-dimensional structure-like nano catalyst.
Preferably, the reaction conditions in the second hydrogenation unit include: the hydrogen partial pressure is 10.0-25.0 MPa, the reaction temperature is 350-470 ℃, and the volume space velocity is 0.1-2.0 h-1The volume ratio of the hydrogen to the deoiled asphalt is (500-5000): and 1, the total weight of the deoiled asphalt is taken as a reference, and the content of the catalyst in the second hydrogenation unit is 100-10000 mug/g. More preferably, the reaction conditions in the second hydrogenation unit include: the hydrogen partial pressure is 12.0-20.0 MPa, the reaction temperature is 380-440 ℃, and the volume space velocity is 0.1-0.8 h-1The volume ratio of hydrogen to deoiled asphalt is (10)00-2000): and 1, the content of the catalyst in the second hydrogenation unit is 500-3000 mu g/g by taking the total weight of the deoiled asphalt as a reference.
Preferably, in the step (3), heavy components containing the catalyst in the material obtained from the second hydrogenation unit are recycled to the second hydrogenation unit, and the rest light components are recycled to the contact cracking reaction zone of the step (1) for contact cracking reaction.
Preferably, in step (24) of the present invention, the gasification reaction is carried out in a fluidized bed reactor, and the temperature in the dense bed is 550 to 800 ℃, the linear velocity in the dense bed is 0.05 to 0.6m/s, and the average gas residence time is 0.5 to 60 s. More preferably, the temperature in the dense bed is 600 to 750 ℃.
Preferably, in the step (24), the oxygen-containing gas has an oxygen mole fraction of 10 to 30%. Preferably, the oxygen-containing gas further comprises carbon dioxide and/or nitrogen.
Preferably, in step (24), the regenerated contact agent is recycled to the contact cracking reaction zone of step (1) to carry out the contact cracking reaction.
Preferably, the contact agent is a silicon and/or aluminum containing material.
The contact agent of the present invention may or may not contain a molecular sieve, and preferably, the contact agent further contains a molecular sieve.
Preferably, the carbon residue content in the heavy oil raw material is less than 40 wt%, and the metal content is 1-1000 mug/g. The content of the carbon residue is determined according to the method specified in GB/T17144, and the content of the metal is determined according to the method specified in RIPP 124-90.
Preferably, the heavy oil feedstock is selected from at least one of heavy crude oil, acid-containing crude oil, ultra-heavy oil, atmospheric residuum, vacuum wax oil, coker wax oil, deasphalted oil, oil sand bitumen, hydrocracked tail oil, coal tar, shale oil, tank bottoms, and coal liquefaction residuum.
More preferably, the heavy oil feedstock is a vacuum residuum and the 5% point distillate temperature has a boiling point greater than 500 ℃.
The process flow of a preferred embodiment of the method for processing inferior heavy oil of the present invention is provided below with reference to fig. 1:
(1) introducing a heavy oil raw material into the contact cracking reaction zone 1 through a pipeline 17 to perform contact cracking reaction with a contact agent, and introducing the material after the contact cracking reaction into a separation system for separation to obtain dry gas, liquefied gas, gasoline fraction, circulating oil and a spent agent;
(21) the dry gas and the liquefied gas enter a gas separation unit 2 through a line 8 to be separated to obtain hydrogen, ethylene, propylene, butylene and butane, and the hydrogen, ethylene, propylene, butylene and butane are led out through a line 22, a line 23, a line 24, a line 25 and a line 26 respectively;
(22) the gasoline fraction enters a first hydrogenation unit 3 through a pipeline 9 for carrying out hydrofining reaction, and a liquid phase substance after the hydrofining reaction flows through a pipeline 10 and enters an aromatic extraction unit 4 for extraction so as to respectively obtain aromatic-rich extract oil and aromatic-poor raffinate oil, and the aromatic-poor raffinate oil is led out through a pipeline 12; the aromatic-rich extract oil is led out through a pipeline 11 to be separated so as to obtain benzene, toluene and xylene;
(23) the circulating oil enters a solvent deasphalting unit 5 through a pipeline 13 to be subjected to solvent deasphalting treatment to obtain deasphalted oil and deoiled asphalt, and the deasphalted oil is led out through a pipeline 14; the deoiled asphalt enters a second hydrogenation unit 6 through a pipeline 15 for hydrogenation reaction;
(24) the spent catalyst enters the gasification reaction unit 7 through a line 20 to perform gasification reaction with the oxygen-containing gas from a line 18, and the product obtained after the gasification reaction is separated to obtain the synthesis gas led out through a line 19 and the regenerated contact agent which is circulated to the contact cracking reaction zone 1 through a line 21;
(3) the deasphalted oil from line 14 and at least part of the feed from the second hydrogenation unit 6 from line 16 are recycled to the catalytic cracking reaction zone 1 of step (1) for catalytic cracking reactions.
Compared with the prior art, the processing method of the inferior heavy oil provided by the invention also has the following specific advantages:
1) the inferior heavy oil raw material is fully utilized, the chemical raw material triphenyl is produced to the maximum extent, and the raw material cost for producing the triphenyl by taking naphtha as the raw material is reduced;
2) maximum production of feedstock carbon tetrahydrocarbons of high octane components;
3) the problem of high-efficiency utilization of aromatic-rich heavy oil containing catalyst powder is solved;
4) solution C9The problem of poor utilization of aromatic hydrocarbon;
5) can obtain gasoline blending fraction with low aromatic hydrocarbon content.
The present invention will be described in detail below by way of examples.
The contact agents used in the examples are as follows: based on the total weight of the contact agent, 50 wt% of mesoporous silicon-aluminum material, 45 wt% of kaolin and 5 wt% of alumina sol are taken as binders and are marked as MFC-1.
The contact agent containing the molecular sieve adopted in the contact cracking reaction unit is a catalytic cracking catalyst with the trade mark of CRC-1.
The contact cracking test apparatus used in the examples was a riser medium-sized apparatus, and the second hydrogenation reaction was carried out in a small autoclave.
The properties of the raw materials used in the examples are shown in table 1.
The solvent volume ratio in table 2 represents the volume ratio of the solvent used in the aromatics extraction unit to the liquid-phase stream after the hydrofinishing reaction.
Example 1
Example 1 was carried out according to the process scheme shown in figure 1. Specifically, the method comprises the following steps:
the heavy crude oil B enters a contact cracking reactor, is subjected to contact cracking reaction with a contact agent MFC-1, and is introduced into a separation system for separation, the obtained product comprises dry gas, liquefied gas, gasoline fraction with the boiling point of less than 153 ℃, circulating oil with the boiling point of more than 153 ℃ and a spent agent, and the spent agent enters a gasification reaction unit; and the dry gas and the liquefied gas enter a gas separation unit for separation to obtain hydrogen, ethylene, propylene, butylene and butane. And (2) feeding the gasoline fraction with the boiling point lower than 153 ℃ into a first hydrogenation unit, carrying out hydrofining on the gasoline fraction (the catalyst is a hydrofining catalyst with a trade mark of CH-18), introducing the liquid-phase material flow after the hydrofining reaction into an aromatic hydrocarbon extraction unit for extraction to obtain aromatic-poor raffinate oil and aromatic-rich extract oil rich in aromatic hydrocarbon, and further separating the aromatic-rich extract oil to obtain benzene, toluene and xylene. And (2) the circulating oil with the boiling point of more than or equal to 153 ℃ enters a solvent deasphalting unit to be subjected to solvent deasphalting treatment to obtain deasphalted oil and deoiled asphalt, the deasphalted oil enters a contact cracking reactor to be further converted, the deoiled asphalt enters a second hydrogenation unit to be properly hydrogenated, and light components obtained by the second hydrogenation unit enter the contact cracking reactor to be further converted. In the gasification reaction unit, at the temperature of 700 ℃, the carbon on the contact agent and the gasification agent containing 15 mol percent of oxygen are partially oxidized to generate synthesis gas rich in CO.
The process conditions for each unit are shown in table 2 and the product yields for the entire process are shown in table 3.
Also, the aromatic content of the gasoline fraction obtained in this example was 32.5 wt%.
Example 2
Example 2 was carried out according to the process scheme shown in figure 1. Specifically, the method comprises the following steps:
the slag reduction A enters a contact cracking reactor, is subjected to contact cracking reaction with a contact agent CRC-1, and the material after the contact cracking reaction is introduced into a separation system for separation, wherein the obtained product comprises dry gas, liquefied gas, gasoline fraction with the boiling point lower than 153 ℃, circulating oil with the boiling point higher than 153 ℃ and a spent agent, and the spent agent enters a gasification reaction unit; and the dry gas and the liquefied gas enter a gas separation unit for separation to obtain hydrogen, ethylene, propylene, butylene and butane. And (2) feeding the gasoline fraction with the boiling point lower than 153 ℃ into a first hydrogenation unit, carrying out hydrofining on the gasoline fraction (the used catalysts are a hydrofining catalyst with a trade mark of CH-18 and a RIDOS-1 octane number recovery catalyst with a trade mark), introducing the liquid phase material flow after the hydrofining reaction into an aromatic hydrocarbon extraction unit for extraction to obtain aromatic-poor raffinate oil and aromatic-rich extract oil rich in aromatic hydrocarbon, and further separating the aromatic-rich extract oil to obtain benzene, toluene and xylene. And (2) the circulating oil with the boiling point of more than or equal to 153 ℃ enters a solvent deasphalting unit to be subjected to solvent deasphalting treatment to obtain deasphalted oil and deoiled asphalt, the deasphalted oil enters a contact cracking reactor to be further converted, the deoiled asphalt enters a second hydrogenation unit to be properly hydrogenated, and light components obtained by the second hydrogenation unit enter the contact cracking reactor to be further converted. In the gasification reaction unit, carbon on the contact agent and a gasification agent containing 19 mol percent of oxygen are partially oxidized at the temperature of 730 ℃ to generate synthesis gas rich in CO.
The process conditions for each unit are shown in table 2 and the product yields for the entire process are shown in table 3.
Also, the aromatic content of the gasoline fraction obtained in this example was 39.2 wt%.
Example 3
This example was carried out in a similar manner to example 1, except that:
the slurry bed reactor used in the second hydrogenation unit of this example is shown in table 2, and the results are shown in table 3.
Also, the aromatic content of the gasoline fraction obtained in this example was 32.5 wt%. TABLE 1
| Slag reduction A | Heavy crude oil B | |
| Density (20 ℃ C.) (g. cm-3) | 1.011 | 0.9401 |
| Carbon residue value/weight% | 18.62 | 13.13 |
| Ni+V//(μg·g-1) | 245 | 110 |
| Element composition/weight% | ||
| C | 86.10 | 85.75 |
| H | 10.60 | 11.32 |
TABLE 2
TABLE 3
| Example 1 | Example 2 | Example 3 | |
| w (mass yield)/%) | |||
| H2 | 0.96 | 1.68 | 1.00 |
| Ethylene | 1.09 | 1.23 | 1.30 |
| Propylene (PA) | 5.18 | 5.47 | 6.12 |
| Butene (butylene) | 4.58 | 3.30 | 4.87 |
| Isobutane | 2.69 | 6.65 | 2.80 |
| N-butane | 0.98 | 2.25 | 1.00 |
| Benzene, toluene and xylene | 22.74 | 24.15 | 23.40 |
| Gasoline fraction | 33.20 | 7.73 | 33.50 |
| Coke | 17.81 | 32.50 | 16.17 |
| Other gases | 10.76 | 15.03 | 9.84 |
The results in table 3 show that the method provided by the invention can fully utilize the characteristics of low hydrogen content and rich aromatic hydrocarbon of heavy oil, the yield of produced triphenyl can reach more than 20%, and simultaneously, petroleum resources are efficiently utilized, so that low-value heavy raw materials are converted into low-carbon olefin and isobutane with high additional values, raw materials are provided for chemical engineering and isomerization, the consumption of light hydrocarbons such as naphtha by refineries is reduced, gasoline fractions can also be produced, and the utilization of resources is further improved.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (25)
1. A method for processing inferior heavy oil, comprising:
(1) introducing a heavy oil raw material into a contact cracking reaction zone to perform contact cracking reaction with a contact agent, and introducing the material subjected to the contact cracking reaction into a separation system to separate so as to obtain dry gas, liquefied gas, gasoline fraction, circulating oil and a spent agent;
(21) introducing the dry gas and the liquefied gas into a gas separation unit for separation to obtain hydrogen, ethylene, propylene, butenes, and butanes;
(22) introducing the gasoline fraction into a first hydrogenation unit for carrying out hydrofining reaction, and introducing a liquid phase material flow after the hydrofining reaction into an aromatic hydrocarbon extraction unit for extraction so as to respectively obtain aromatic-rich extract oil and aromatic-poor raffinate oil; then separating the aromatic-rich extract oil to obtain benzene, toluene and xylene;
(23) introducing the circulating oil into a solvent deasphalting unit for solvent deasphalting treatment to obtain deasphalted oil and deoiled asphalt; the deoiled asphalt enters a second hydrogenation unit to carry out hydrogenation reaction;
(24) introducing the spent agent into a gasification reaction unit to carry out gasification reaction with oxygen-containing gas, and separating a product obtained after the gasification reaction to obtain CO-containing gas and a regenerated contact agent;
(3) recycling the deasphalted oil and at least part of the material obtained from the second hydrogenation unit to the contact cracking reaction zone of the step (1) for contact cracking reaction.
2. The process of claim 1 wherein in step (1), said contact cracking reaction zone comprises at least two reaction units, and at least one of which is a fluidized bed reaction unit and at least one other of which is a riser reaction unit.
3. The method as claimed in claim 2, wherein, in the fluidized bed reaction unit, the bed density is 100 to 700kg/m3And the reaction conditions in the fluidized bed reaction unit include: the reaction temperature is 450-620 ℃, and the retention time is 3-8 s.
4. The process according to claim 2, wherein in the riser reaction unit the bed density is 10-100 kg/m3And the reaction conditions in the riser reaction unit include: the reaction temperature is 490-580 ℃, and the retention time is 0.5-2.0 s.
5. The process according to any one of claims 1 to 4, wherein the fractionation point of the gasoline fraction and the cycle oil in step (1) is 140 to 170 ℃.
6. The method according to claim 5, wherein in the step (1), the fractionation point of the gasoline fraction and the cycle oil is 145-160 ℃.
7. The method according to any one of claims 1 to 4, wherein, in step (22), the solvent in the aromatic extraction unit is selected from at least one of N-methylpyrrolidone, tetraethylene glycol ether, diethylene glycol ether, triethylene glycol ether, sulfolane, dimethyl sulfoxide and N-formyl morpholine.
8. The method of claim 7, wherein the volume ratio of the solvent used in the aromatics extraction unit to the liquid phase stream after the hydrofining reaction is 3-12.
9. The process of any one of claims 1-4, wherein in step (23), the solvent in the solvent deasphalting unit is C4～C6The hydrocarbon of (1).
10. The method of claim 9, wherein the conditions of the solvent deasphalting process comprise: the extraction temperature is 110-230 ℃, and the extraction pressure is 3-6 MPa.
11. The process of any one of claims 1-4, wherein in step (23), the second hydrogenation unit is a slurry bed hydrogenation unit.
12. The process of claim 11, wherein the second hydrogenation unit contains catalyst II, and the catalyst II is a composite nanocatalyst containing a metal element and a nonmetal element.
13. The method of claim 11, wherein the reaction conditions in the second hydrogenation unit comprise: the hydrogen partial pressure is 10.0-25.0 MPa, the reaction temperature is 350-470 ℃, and the volume space velocity is 0.1-2.0 h-1The volume ratio of the hydrogen to the deoiled asphalt is (500-5000): and 1, the total weight of the deoiled asphalt is taken as a reference, and the content of the catalyst in the second hydrogenation unit is 100-10000 mug/g.
14. The method of claim 13, wherein the reaction conditions in the second hydrogenation unit comprise: the hydrogen partial pressure is 12.0-20.0 MPa, the reaction temperature is 380-440 ℃, and the volume space velocity is 0.1-0.8 h-1The volume ratio of the hydrogen to the deoiled asphalt is (1000-2000): and 1, the content of the catalyst in the second hydrogenation unit is 500-3000 mu g/g by taking the total weight of the deoiled asphalt as a reference.
15. The process according to claim 12, wherein in the catalyst II, the non-metallic element is selected from at least one of non-metallic elements of groups IVA and VIA, and the metallic element is selected from at least one of metallic elements of groups VB, VIB, IVA and VIII.
16. The method according to claim 15, wherein the metal element is at least one selected from Cr, V, Mo, W, Ni, Fe, Co, and Sn.
17. The process of claim 1, wherein in step (24), the gasification reaction is carried out in a fluidized bed reactor, and the temperature in the dense bed is 550 to 800 ℃, the linear velocity in the dense bed is 0.05 to 0.6m/s, and the gas residence time is 0.5 to 60 s.
18. The process of claim 17, wherein in step (24), the gasification reaction is carried out in a fluidized bed reactor and the temperature in the dense bed is 600-750 ℃.
19. The method according to claim 1, wherein in step (24), the oxygen-containing gas has an oxygen mole fraction of 10 to 30%.
20. The process of claim 1 wherein in step (24) said regenerated contact agent is recycled to said contact cracking reaction zone of step (1) for contact cracking reactions.
21. The method of claim 1, wherein the contact agent is a silicon and/or aluminum containing material.
22. The method of claim 21, wherein the contacting agent further comprises a molecular sieve.
23. The method of claim 1, wherein the heavy oil feedstock has a carbon residue content of less than 40 wt% and a metal content of 1 to 1000 μ g/g.
24. The method of claim 23, wherein the heavy oil feedstock is selected from at least one of heavy crude oil, acid-containing crude oil, ultra heavy oil, atmospheric resid, vacuum wax oil, coker wax oil, deasphalted oil, oil sands bitumen, hydrocracked tail oil, coal tar, shale oil, tank bottoms, and coal liquefaction resid.
25. The method of claim 24 wherein the heavy oil feedstock is a vacuum residuum and the 5% point distillate temperature has a boiling point greater than 500 ℃.
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