CN109722306A - The processing method of inferior heavy oil - Google Patents
The processing method of inferior heavy oil Download PDFInfo
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Abstract
The present invention relates to hydrocarbon oil conversion fields, disclose the processing method of inferior heavy oil, comprising: heavy oil feedstock and contact agent are carried out contact cracking, obtain dry gas, liquefied gas, gasoline fraction, recycle oil and spent agent；Dry gas and liquefied gas separation are obtained into hydrogen, ethylene, propylene, butylene and butane；Gasoline fraction is subjected to hydrofinishing, liquid phase stream is stripped the rich virtue extraction oil of acquisition and poor virtue is raffinated oil；Fu Fang extraction oil separation obtains benzene, toluene and dimethylbenzene；Recycle oil carries out solvent deasphalting and handles to obtain deasphalted oil and de-oiled asphalt；De-oiled asphalt carries out hydrogenation reaction；Spent agent and oxygen-containing gas carry out gasification reaction, the contact agent after obtaining synthesis gas and regeneration；Deasphalted oil and hydrogenation material circulation are subjected to contact cracking reaction.In this way, heavy charge maximum can be converted to rich in ethylene, propylene, butylene, the unstrpped gas of butane and rich in the triphens such as benzene,toluene,xylene, while producing the gasoline fraction of low arene content.
Description
Technical field
The present invention relates to hydrocarbon oil conversion fields, and in particular to a kind of processing method of inferior heavy oil.
Background technique
Heavy oil, especially decompression residuum generally take delay coking process to carry out lighting production naphtha and diesel oil, stone
Cerebrol enters reformer after adding hydrogen and produces aromatic hydrocarbons, is used as derv fuel after diesel oil hydrogenation.But with the market demand
Variation, diesel oil is superfluous in the market, and diesel and gasoline ratio requires lower and lower.Meanwhile decompression residuum is processed using delay coking process, is being removed
The environmental issues such as exhaust gas, waste water can be generated during burnt, also (sulfur content is more than 3% by environmental requirement for the utilization of high sulfur petroleum coke
It cannot sell).
In addition, auto-pollution is increasingly becoming the main next of urban air pollution with the rising of car ownership in city
One of source.To reduce motor vehicle emission, various countries have formulated increasingly strict automobile emission regulation.
To keep motor vehicle exhaust emission up to standard, major measure first is that formulate stringent vehicle fuel standard, realize that fuel is clear
Clean.Countries in the world do not formulate unified clean fuel standards, and country variant and area are according to economic and technical developing water
Flat, the structure of oil refining apparatus and different times environmental requirement, formulates different clean fuel standards.
Aromatic hydrocarbons and alkene octane number all with higher in motor petrol.If motor petrol arene content is excessively high, meeting
Increase the deposit in combustion chamber, a degree of influence is generated on discharge, European Union requirements were from 2005 thus, in gasoline
Arene content be not higher than 35% (volume fraction).And olefin(e) centent it is excessively high will cause fuel injector coking, it is spraying deteriorate, thus shadow
It rehearses with musical accompaniment and puts.
China's motor petrol standard is by state IV grades to state V, and aromatic hydrocarbons volume content is of less demanding in 40%, alkene volume content
24% is reduced to by 28%.Gasoline state VI standard will be implemented in 2019, further limit in standard aromatic hydrocarbons and olefin(e) centent,
Olefin(e) centent is not more than 15% or 18%, and arene content is not more than 35%.
At present in Chinese gasoline pool average composition, blend component is still with catalytically cracked gasoline and catalytic reforming gasoline
Main, the two total amount is more than 85%, and is used as the alkylation or isomerization gasoline proportionality that formula reconciles as most peace and quiet, most suitable
Very little.This is barrel-shaped with American-European countries gasoline pool catalytically cracked gasoline, Reformed Gasoline, gasoline alkylate and isomerization gasoline composition
Structure forms biggish difference.
Chinese motor petrol standard is increasingly strict, constantly limits alkene and aromatic hydrocarbons, will generate to the structure of gasoline pool
It influences.Gasoline alkylate, isomerization gasoline, methyl tertiary butyl ether(MTBE) (MTBE) etc. will be gradually increased in gasoline harmonic proportion.
Therefore, the raw materials requirement of the following production gasoline alkylate, isomerization gasoline and MTBE can increasingly increase.
Raw material for alkylation is mainly iso-butane and butylene, and MTBE is also using isobutene and methanol as raw material.Therefore future is to different
The demand of butane and butylene will constantly enhance.And current technology all emphasizes the industrial chemicals such as production ethylene, propylene, butadiene.
Following C_4 hydrocarbon class is possible to will appear shortage.China's catalytic cracking will also be made to the limitation of aromatic hydrocarbons in six gasoline standard of state
Aromatic Hydrocarbon in Gasoline is superfluous.
Dimethylbenzene (BTX) is level-one basic chemical raw materials, and it is to come to urge that benzene needed for the whole world, toluene, BTX, which have nearly 70%,
Change and reform, the raw material of catalytic reforming is naphtha (mainly direct steaming gasoline), and the price of naphtha is relatively high.Naphtha is also raw
The primary raw material of low-carbon alkene is produced, therefore occasionally there are the situations that two covering devices are contended over raw materials in refinery.
CN105087047A discloses a kind of heavy oil catalytic cracking process of voluminous weight aromatic hydrocarbon product, with heavy oil (wax
Oil, residual oil and its mixture) it is raw material, produce the heavy oil catalytic cracking process of weight aromatic hydrocarbon product.Heavy oil feedstock passes through catalysis
Cracking reaction, under the action of catalyst, 85% or more, the product is subsequent to be passed through the arene content in weight aromatic hydrocarbon product
Selective hydrogenation, solvent extraction unit operate to obtain the aroamtic hydrocarbon raw material of a large amount of preciousnesses.
Shanghai Lu Yi petrochemical industry Science and Technology Ltd. (CN1490383A) discloses a kind of heavy oil industrial chemicals coproduction
The catalytic cracking process of aromatic hydrocarbons, abbreviation MCC technique are realized to greatest extent under the reaction condition relatively mitigated by raw material of heavy oil
Production light olefin and light aromatic hydrocarbons, liquefied gas yield maximum can reach 60%, propylene and butylene account for about 80% in liquefied gas.And
Its aromatic hydrocarbons produced changes with the variation of raw material, and lightweight material can produce light aromatic hydrocarbons to greatest extent, and heavy charge can be with
Aromatic hydrocarbons and heavy aromatics are produced simultaneously.
From it is aforementioned in the prior art as can be seen that at present production low-carbon alkene and aromatic hydrocarbons raw material sources both be from lighter hydrocarbons or
The good wax oil of quality, if naphtha steam cracking produces ethylene, propylene, naphtha reforming produces aromatic hydrocarbons, and straight-run gas oil passes through
DCC technique produces propylene etc..And the price of heavy oil especially decompression residuum is lower, especially depressurizes how to efficiently use heavy oil
Residual oil is refinery's upgrading synergy importance in need of consideration.Residual oil is the mixture rich in aromatic hydrocarbons, from the angle of refinery economics
Degree considers, generally all considers " suitable alkene then alkene, the processing route of suitable Fang Zefang ".
In addition, being rich in aromatic hydrocarbons, containing largely urge simultaneously for a part can be produced in the contact cracking process of inferior heavy oil
The low value products of agent powder, the further processing of this portion of product are usually taken out with very low price using relatively difficult,
Or the part material as coking.
Summary of the invention
Inferior heavy oil is processed using fluidization, continuous closed method the object of the present invention is to provide a kind of, by heavy original
Material maximum is converted into rich in ethylene, propylene, butylene, the unstrpped gas of butane and side rich in triphens such as benzene,toluene,xylenes
Method provides a processing approach for the production of triphen, reduces production triphen to solve the problems, such as the raw material of production antiknock component
Expense of raw materials, while the gasoline fraction of low arene content is produced, in addition, the coke that method of the invention generates being capable of original position portion
The gas for dividing oxidation production to be rich in CO, for steam to occur into CO boiler.
To achieve the goals above, the present invention provides a kind of processing method of inferior heavy oil, this method comprises:
(1) heavy oil feedstock is introduced in contact cracking reaction area to carry out contact cracking reaction with contact agent, and will connect
Material after touching cracking reaction is introduced in separation system and is separated, obtain dry gas, liquefied gas, gasoline fraction, recycle oil and
Spent agent；
(21) dry gas and the liquefied gas are introduced in gas separation unit and are separated to obtain hydrogen, second
Alkene, propylene, butylene and butane；
(22) gasoline fraction is introduced in the first hydrogenation unit and carries out hydrofining reaction, and hydrofinishing is anti-
Liquid phase stream after answering, which is introduced in Aromatics Extractive Project unit, to be stripped to obtain rich virtue extraction oil and poor virtue respectively and raffinate oil；So
The rich virtue extraction oil is separated to obtain benzene, toluene and dimethylbenzene afterwards；
(23) recycle oil is introduced in Solvent deasphalting unit and carries out solvent deasphalting processing to obtain depitching
Oil and de-oiled asphalt；The de-oiled asphalt, which enters in the second hydrogenation unit, carries out hydrogenation reaction；
(24) spent agent is introduced in gasification reaction unit and carries out gasification reaction with oxygen-containing gas, and by gasified reverse
Should after obtained product separated to obtain the contact agent after the gas containing CO and regeneration；
(3) step is returned by the Matter Transfer that second hydrogenation unit obtains by the deasphalted oil and at least partly
(1) contact cracking reaction is carried out in contact cracking reaction area.
Method of the invention can convert heavy charge maximum to rich in ethylene, propylene, butylene, butane unstripped gas
Body and rich in the triphens such as benzene,toluene,xylene, while producing the gasoline fraction of low arene content.
Further, the present invention use solvent deasphalting and slurry bed system Combined machining method, can by low value, contain
Having the cracking heavy distillat of catalyst fines not need sedimentation, filtering will be enriched in the group of saturated hydrocarbons only by Solvent deasphalting unit
Point extraction, return contact the further cracking of Cracking Unit, will be enriched in aromatic hydrocarbons and the de-oiled asphalt containing catalyst fines directly into
Row slurry bed hydroprocessing.
Further, the coke original position partial oxidation of production can be generated the gas containing CO by the present invention, in CO
Steam occurs for boiler, solves the problems, such as that Coke of Delayed Coking utilizes.
Detailed description of the invention
Fig. 1 is a kind of process flow chart of preferred embodiment of the processing method of inferior heavy oil of the invention.
Description of symbols
1, cracking reaction area is contacted
2, gas separation unit
3, the first hydrogenation unit
4, Aromatics Extractive Project unit
5, Solvent deasphalting unit
6, the 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 be pipeline
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
As previously mentioned, the present invention provides a kind of processing methods of inferior heavy oil, this method comprises:
(1) heavy oil feedstock is introduced in contact cracking reaction area to carry out contact cracking reaction with contact agent, and will connect
Material after touching cracking reaction is introduced in separation system and is separated, obtain dry gas, liquefied gas, gasoline fraction, recycle oil and
Spent agent；
(21) dry gas and the liquefied gas are introduced in gas separation unit and are separated to obtain hydrogen, second
Alkene, propylene, butylene and butane；
(22) gasoline fraction is introduced in the first hydrogenation unit and carries out hydrofining reaction, and hydrofinishing is anti-
Liquid phase stream after answering, which is introduced in Aromatics Extractive Project unit, to be stripped to obtain rich virtue extraction oil and poor virtue respectively and raffinate oil；So
The rich virtue extraction oil is separated to obtain benzene, toluene and dimethylbenzene afterwards；
(23) recycle oil is introduced in Solvent deasphalting unit and carries out solvent deasphalting processing to obtain depitching
Oil and de-oiled asphalt；The de-oiled asphalt, which enters in the second hydrogenation unit, carries out hydrogenation reaction；
(24) spent agent is introduced in gasification reaction unit and carries out gasification reaction with oxygen-containing gas, and by gasified reverse
Should after obtained product separated to obtain the contact agent after the gas containing CO and regeneration；
(3) step is returned by the Matter Transfer that second hydrogenation unit obtains by the deasphalted oil and at least partly
(1) contact cracking reaction is carried out in contact cracking reaction area.
Not necessarily there is sequencing between step (21) of the invention, step (22), step (23) and step (24),
Those skilled in the art should not be construed as the limitation to method of the invention.
According to a kind of preferred embodiment, in step (1), the contact cracking reaction area includes at least two
Reaction member, and wherein at least one is fluidized-bed reaction unit, at least another is riser reaction member.
In above-mentioned preferred embodiment, in the fluidized-bed reaction unit, it is preferable that bed density is
100~700kg/m3, and it is 450~620 DEG C that the reaction condition in the fluidized-bed reaction unit, which includes: reaction temperature, is stopped
Time is 3~8s.
In above-mentioned preferred embodiment, in the riser reaction member, it is preferable that bed density 10
~100kg/m3, and it is 490~580 DEG C that the reaction condition in the riser reaction member, which includes: reaction temperature, the residence time
For 0.5~2.0s.
Under preferable case, in the present invention, in step (1), the cut point of the gasoline fraction and recycle oil is 140~
170 DEG C, more preferably 145~160 DEG C；Particularly preferably 150~160 DEG C, such as can be 150 DEG C, 151 DEG C, 152 DEG C, 153
DEG C, 154 DEG C, 155 DEG C, 156 DEG C, 157 DEG C, 158 DEG C, 159 DEG C or 160 DEG C.
Under preferable case, in step (22) of the invention, the solvent in the Aromatics Extractive Project unit is selected from N- methyl pyrrole
In pyrrolidone, tetraethylene glycol, diethylene glycol ether, triethylene glycol ether, sulfolane, dimethyl sulfoxide and N- formyl-morpholine extremely
Few one kind.
Under preferable case, in step (22) of the invention, in the Aromatics Extractive Project unit, the solvent that uses with it is described
The volume ratio of liquid phase stream after hydrofining reaction is 3~12.
Under preferable case, Hydrobon catalyst is contained in first hydrogenation unit, the Hydrobon catalyst is
Catalyst I, the catalyst I is the catalyst for hydro-upgrading with hydro-upgrading function and/or enable to octane value recovering
Octane value recovering catalyst.
Preferably, your non-gold of group VIB be selected from containing at least one zeolite, at least one in the catalyst for hydro-upgrading
Belong to the hydrogenation active component of element and group VIII non-noble metal j element, and contains alumina host.It is highly preferred that described
In catalyst for hydro-upgrading, the zeolite is selected from least one of HY zeolite, Beta zeolite and ZSM-5 zeolite.
Preferably, containing the zeolite and aluminium oxide as carrier in the octane value recovering catalyst, and contain load
Base metal active component on the carrier, the base metal active component are at least one in cobalt, nickel, molybdenum and tungsten
Kind.It is highly preferred that the zeolite is selected from faujasite, Beta zeolite, ZSM-5 zeolite in the octane value recovering catalyst
At least one of with SAPO-11 zeolite.
Preferably, in first hydrogenation unit, the condition for carrying out the hydrofining reaction includes: that hydrogen partial pressure is
0.3~6.0MPa, reaction temperature are 100~480 DEG C, and volume space velocity is 0.3~6.0h-1, hydrogen to oil volume ratio be 100~
1200Nm3/m3。
Preferably, in step (23) of the invention, the solvent in the Solvent deasphalting unit is C4~C6Hydro carbons.
Under preferable case, in step (23) of the invention, the condition of the solvent deasphalting processing includes: extraction temperature
It is 110~230 DEG C, extraction pressure is 3~6MPa.
In the step (23) of the invention, second hydrogenation unit can be fixed bed hydrogenation unit, ebullated bed
Hydrogenation unit or slurry bed system hydrogenation unit.
In order to obtain the expense of raw materials for reducing production triphen, while the gasoline fraction of more low arene content is produced, according to one
Kind preferred embodiment, in step (23), second hydrogenation unit is slurry bed system hydrogenation unit.
Under preferable case, in step (23), catalyst II is contained in second hydrogenation unit, the catalyst II is
Composite nano-catalyst containing metallic element and nonmetalloid.
Preferably, in the catalyst II, the nonmetalloid is in IVA race and Group VIA nonmetalloid
At least one, the metallic element are selected from least one of VB race, group vib, IVA race and group VIII metal element；And it is excellent
The average grain diameter for selecting the catalyst II is 10~50nm.
It is highly preferred that the metallic element is in Cr, V, Mo, W, Ni, Fe, Co and Sn in the catalyst II
It is at least one.
The catalyst II of the invention is preferably class two-dimensional and/or two-dimensional structure nanocatalyst.
Preferably, it is 10.0~25.0MPa, reaction temperature that the reaction condition in second hydrogenation unit, which includes: hydrogen partial pressure,
Degree is 350~470 DEG C, and volume space velocity is 0.1~2.0h-1, the volume ratio of hydrogen and de-oiled asphalt is (500~5000): 1, and
On the basis of the total weight of the de-oiled asphalt, the content of the catalyst in second hydrogenation unit is 100~10000 μ g/
g.It is highly preferred that it is 12.0~20.0MPa that the reaction condition in second hydrogenation unit, which includes: hydrogen partial pressure, reaction temperature is
380~440 DEG C, volume space velocity is 0.1~0.8h-1, the volume ratio of hydrogen and de-oiled asphalt is (1000~2000): 1, and with institute
On the basis of the total weight for stating de-oiled asphalt, the content of the catalyst in second hydrogenation unit is 500~3000 μ g/g.
Under preferable case, in the step (3), catalysis will be contained in the material obtained by second hydrogenation unit
The heavy constituent of agent is recycled back in second hydrogenation unit, and the contact that remaining light component is recycled back to step (1) is split
Change in reaction zone and carries out contact cracking reaction.
Under preferable case, in step (24) of the invention, the gasification reaction carries out in a fluidized bed reactor, and close
Temperature in phase bed is 550~800 DEG C, and the linear velocity in dense bed is 0.05~0.6m/s, and gas mean residence time is 0.5
~60s.It is highly preferred that the temperature in the dense bed is 600~750 DEG C.
Preferably, in step (24), the oxygen mole fraction in the oxygen-containing gas is 10~30%.Preferably, institute
It states and also contains carbon dioxide and/or nitrogen in oxygen-containing gas.
Under preferable case, in step (24), the contact that the contact agent after the regeneration is recycled back to step (1) is split
Change in reaction zone and carries out contact cracking reaction.
Preferably, the contact agent is siliceous and/or aluminium material.
It can contain in the contact agent of the invention or without containing molecular sieve, under preferable case, in the contact agent
Also contain molecular sieve.
Preferably, for the carbon residue content in the heavy oil feedstock less than 40 weight %, tenor is 1~1000 μ g/g.And
The carbon residue content is measured according to method specified in GB/T 17144, and the tenor in RIPP 124-90 according to providing
Method measurement.
Preferably, the heavy oil feedstock is selected from heavy crude, acid-containing raw oil, super-viscous oil, reduced crude, decompression residuum, subtracts
Press wax oil, wax tailings, deasphalted oil, oil sands bitumen, hydrocracking tail oil, coal tar, shale oil, tank bottom oil and coal liquefaction residual
At least one of residual oil.
It is highly preferred that the heavy oil feedstock is decompression residuum, and the boiling point of 5% recovered (distilled) temperature is greater than 500 DEG C.
A kind of work of preferred embodiment of the processing method of inferior heavy oil of the invention is provided below in conjunction with Fig. 1
Skill process:
(1) heavy oil feedstock is introduced in contact cracking reaction area 1 through pipeline 17 to carry out contact cracking reaction with contact agent,
And the material after contact cracking reaction is introduced in separation system and is separated, it obtains dry gas, liquefied gas, gasoline fraction, follow
Ring oil and spent agent；
(21) dry gas and the liquefied gas enter in gas separation unit 2 through pipeline 8 separated with obtain hydrogen,
Ethylene, propylene, butylene and butane, the hydrogen, ethylene, propylene, butylene and butane respectively through pipeline 22, pipeline 23, pipeline 24,
Pipeline 25 and pipeline 26 are drawn；
(22) gasoline fraction enters in the first hydrogenation unit 3 through pipeline 9 carries out hydrofining reaction, and adds hydrogen essence
Liquid phase stream after system reaction enters in Aromatics Extractive Project unit 4 through pipeline 10 to be stripped to obtain rich virtue extraction oil and poor respectively
Virtue is raffinated oil, and the poor virtue is raffinated oil draws through pipeline 12；The rich virtue extraction oil is separated through the extraction of pipeline 11 to obtain
Benzene, toluene and dimethylbenzene；
(23) recycle oil enters in Solvent deasphalting unit 5 through pipeline 13 carries out solvent deasphalting processing to be taken off
Coal tar and de-oiled asphalt, the deasphalted oil are drawn through pipeline 14；The de-oiled asphalt enters second plus hydrogen list through pipeline 15
Hydrogenation reaction is carried out in member 6；
(24) spent agent enters in gasification reaction unit 7 through pipeline 20 carries out gas with the oxygen-containing gas from pipeline 18
Change reaction, and the product obtained after gasification reaction is separated to obtain the synthesis gas drawn through pipeline 19 and follow through pipeline 21
Contact agent after ring to the regeneration in contact cracking reaction area 1；
(3) at least partly add hydrogen list by described second by the deasphalted oil and from pipeline 16 from pipeline 14
Contact cracking reaction is carried out in the contact cracking reaction area 1 for the Matter Transfer time step (1) that member 6 obtains.
The processing method of inferior heavy oil provided by the invention also has the advantages that following specific compared with the existing technology:
1) inferior heavy oil raw material is made full use of, mass production of chemical materials triphen reduces conventional using naphtha as raw material
Produce the expense of raw materials of triphen；
2) four hydro carbons of material carbon of maximum production antiknock component；
3) the efficient Utilizing question of the fragrant heavy oil of the richness containing catalyst fines is solved；
4) C is solved9Aromatic hydrocarbons not good utilisation the problem of；
5) the gasoline reconciliation fraction of low arene content can be obtained.
The present invention will be described in detail by way of examples below.
Contact agent employed in embodiment is as follows: with the total weight of contact agent, the mesoporous silica-alumina materials of 50 weight %,
The kaolin of 45 weight %, the Aluminum sol of 5 weight % are denoted as MFC-1 as binder.
It is that CRC-1 catalytic cracking is urged that contact agent containing molecular sieve employed in contact cracking reaction unit, which is trade names,
Agent.
Contact cracking experimental rig employed in embodiment is riser middle- scale device, and the second hydrogenation reaction is in small-sized height
It is completed in pressure kettle.
Feedstock property employed in embodiment is as shown in table 1.
For solvent volume in table 2 than indicating in the Aromatics Extractive Project unit, the solvent and the hydrofinishing used is anti-
The volume ratio of liquid phase stream after answering.
Embodiment 1
Embodiment 1 is carried out according to process flow shown in FIG. 1.Specifically:
Heavy crude B enters contact cracker, is in contact cracking reaction with contact agent MFC-1, and contact is split
Material after changing reaction, which is introduced in separation system, to be separated, and products therefrom includes dry gas, liquefied gas, boiling point lower than 153 DEG C
Gasoline fraction, boiling point be higher than 153 DEG C of recycle oil and spent agent, spent agent enters gasification reaction unit；Dry gas and liquefied gas
It is separated into gas separation unit, obtains hydrogen, ethylene, propylene, butylene, butane.Boiling point is lower than 153 DEG C of gasoline fraction
Into the first hydrogenation unit, gasoline fraction is carried out hydrofinishing, and (used catalyst is the hydrofinishing that trade names are CH-18
Catalyst), and the liquid phase stream after hydrofining reaction is introduced in Aromatics Extractive Project unit and is stripped, obtain poor fragrant raffinate
Oily and richness virtue extraction oil rich in aromatic hydrocarbons, Fu Fang extract oil further isolated benzene, toluene and dimethylbenzene out.Boiling point >=153 DEG C
Recycle oil enter Solvent deasphalting unit carry out solvent deasphalting processing, obtain deasphalted oil and de-oiled asphalt, deasphalted oil
Into further converting in contact cracker, de-oiled asphalt, which enters the second hydrogenation unit, to be carried out suitably plus hydrogen, by described the
The light component that two hydrogenation units obtain enters contact cracker and further converts.In gasification reaction unit, in 700 DEG C of temperature
Under degree, the charcoal on contact agent and the gasifying agent containing 15 moles of % oxygen occur partial oxidation and generate the synthesis gas for being rich in CO.
The process conditions of each unit are shown in Table 2, and the product yield of entire processing flow is shown in Table 3.
Also, the arene content in the gasoline fraction obtained in the present embodiment is 32.5 weight %.
Embodiment 2
Embodiment 2 is carried out according to process flow shown in FIG. 1.Specifically:
Subtract slag A and enter contact cracker, is in contact cracking reaction with contact agent CRC-1, and it is anti-to contact cracking
Material after answering, which is introduced in separation system, to be separated, and products therefrom includes the vapour of dry gas, liquefied gas, boiling point lower than 153 DEG C
Oil distillate, boiling point are higher than 153 DEG C of recycle oil and spent agent, and spent agent enters gasification reaction unit；Dry gas and liquefied gas enter
Gas separation unit is separated, and hydrogen, ethylene, propylene, butylene, butane are obtained.Gasoline fraction of the boiling point lower than 153 DEG C enters
First hydrogenation unit, gasoline fraction is carried out hydrofinishing, and (catalyst used is that the hydrofinishing that trade names are CH-18 is urged
Agent and trade names are RIDOS-1 octane value recovering catalyst), and the liquid phase stream after hydrofining reaction is introduced to virtue
Be stripped in hydrocarbon extraction unit, obtain poor virtue raffinate oil and rich in aromatic hydrocarbons richness virtue extraction oil, Fu Fang extraction oil further divides
From obtaining benzene, toluene and dimethylbenzene.The recycle oil of boiling point >=153 DEG C, which enters Solvent deasphalting unit, to carry out at solvent deasphalting
Reason obtains deasphalted oil and de-oiled asphalt, and deasphalted oil, which enters in contact cracker, further to be converted, and de-oiled asphalt enters
Second hydrogenation unit carries out suitably adding hydrogen, enters contact cracker into one by the light component that second hydrogenation unit obtains
Step conversion.In gasification reaction unit, at a temperature of 730 DEG C, the charcoal on contact agent and the gasifying agent containing 19 moles of % oxygen
Partial oxidation occurs and generates the synthesis gas for being rich in CO.
The process conditions of each unit are shown in Table 2, and the product yield of entire processing flow is shown in Table 3.
Also, the arene content in the gasoline fraction obtained in the present embodiment is 39.2 weight %.
Embodiment 3
The present embodiment is carried out using method similar to Example 1, except that:
The paste state bed reactor used in second hydrogenation unit of the present embodiment, it is specific as shown in table 2, as a result such as table 3
Shown in.
Also, the arene content in the gasoline fraction obtained in the present embodiment is 32.5 weight %.Table 1
| Subtract slag A | Heavy crude B | |
| Density (20 DEG C) (gcm-3) | 1.011 | 0.9401 |
| Carbon residue/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
| Embodiment 1 | Embodiment 2 | Embodiment 3 | |
| W (mass yield)/% | |||
| H2 | 0.96 | 1.68 | 1.00 |
| Ethylene | 1.09 | 1.23 | 1.30 |
| Propylene | 5.18 | 5.47 | 6.12 |
| Butylene | 4.58 | 3.30 | 4.87 |
| Iso-butane | 2.69 | 6.65 | 2.80 |
| Normal butane | 0.98 | 2.25 | 1.00 |
| Triphen | 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 |
It is low, rich to can make full use of mink cell focus hydrogen content for method provided by the invention it can be seen from the result of above-mentioned table 3
The characteristics of containing aromatic hydrocarbons, produces triphen yield up to 20% or more, while efficiently utilizing petroleum resources, and the heavy charge of low value is turned
The low-carbon alkene and iso-butane of high added value are turned to, provides raw material for chemical industry and isomerization, reduces refinery to lighter hydrocarbons such as naphthas
Consumption, additionally it is possible to produce gasoline fraction, further increase the utilization of resource.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (14)
1. a kind of processing method of inferior heavy oil, this method comprises:
(1) heavy oil feedstock is introduced in contact cracking reaction area to carry out contact cracking reaction with contact agent, and contact is split
Material after changing reaction is introduced in separation system and is separated, and obtains dry gas, liquefied gas, gasoline fraction, recycle oil and to be generated
Agent；
(21) dry gas and the liquefied gas are introduced in gas separation unit and are separated to obtain hydrogen, ethylene, third
Alkene, butylene and butane；
(22) gasoline fraction is introduced in the first hydrogenation unit and carries out hydrofining reaction, and will be after hydrofining reaction
Liquid phase stream be introduced in Aromatics Extractive Project unit and be stripped to obtain rich virtue extraction oil and poor virtue respectively and raffinate oil；Then will
The rich virtue extraction oil is separated to obtain benzene, toluene and dimethylbenzene；
(23) by the recycle oil be introduced in Solvent deasphalting unit carry out solvent deasphalting processing with obtain deasphalted oil and
De-oiled asphalt；The de-oiled asphalt, which enters in the second hydrogenation unit, carries out hydrogenation reaction；
(24) spent agent is introduced in gasification reaction unit and carries out gasification reaction with oxygen-containing gas, and will be after gasification reaction
Obtained product is separated to obtain the contact agent after the gas containing CO and regeneration；
(3) step (1) is returned by the Matter Transfer that second hydrogenation unit obtains by the deasphalted oil and at least partly
Contact cracking reaction is carried out in the contact cracking reaction area.
2. according to the method described in claim 1, wherein, in step (1), the contact cracking reaction area includes at least two
Reaction member, and wherein at least one is fluidized-bed reaction unit, at least another is riser reaction member.
3. according to the method described in claim 2, wherein, in the fluidized-bed reaction unit, bed density is 100~
700kg/m3, and it is 450~620 DEG C that the reaction condition in the fluidized-bed reaction unit, which includes: reaction temperature, the residence time is
3~8s；Preferably,
In the riser reaction member, bed density is 10~100kg/m3, and the reaction in the riser reaction member
Condition includes: that reaction temperature is 490~580 DEG C, and the residence time is 0.5~2.0s.
4. method described in any one of -3 according to claim 1, wherein in step (1), the gasoline fraction and circulation
The cut point of oil is 140~170 DEG C, preferably 145~160 DEG C.
5. method described in any one of -3 according to claim 1, wherein in step (22), the Aromatics Extractive Project unit
In solvent be selected from N-Methyl pyrrolidone, tetraethylene glycol, diethylene glycol ether, triethylene glycol ether, sulfolane, dimethyl sulfoxide
At least one of with N- formyl-morpholine；Preferably,
In the Aromatics Extractive Project unit, the volume ratio of the liquid phase stream after the solvent and the hydrofining reaction that use is 3
~12.
6. method described in any one of -3 according to claim 1, wherein in step (23), the solvent deasphalting list
Solvent in member is C4~C6Hydro carbons；Preferably,
It is 110~230 DEG C that the condition of the solvent deasphalting processing, which includes: extraction temperature, and extraction pressure is 3~6MPa.
7. method described in any one of -3 according to claim 1, wherein in step (23), second hydrogenation unit
For slurry bed system hydrogenation unit；Preferably,
Contain catalyst II in second hydrogenation unit, the catalyst II is answering containing metallic element and nonmetalloid
Close nanocatalyst.
8. according to the method described in claim 7, wherein, the reaction condition in second hydrogenation unit includes: that hydrogen partial pressure is
10.0~25.0MPa, reaction temperature are 350~470 DEG C, and volume space velocity is 0.1~2.0h-1, the volume of hydrogen and de-oiled asphalt
Than for (500~5000): 1, and on the basis of the total weight of the de-oiled asphalt, catalyst in second hydrogenation unit
Content is 100~10000 μ g/g；Preferably,
Reaction condition in second hydrogenation unit includes: that hydrogen partial pressure is 12.0~20.0MPa, and reaction temperature is 380~440
DEG C, volume space velocity is 0.1~0.8h-1, the volume ratio of hydrogen and de-oiled asphalt is (1000~2000): 1, and with de-oiling drip
On the basis of green total weight, the content of the catalyst in second hydrogenation unit is 500~3000 μ g/g.
9. according to the method described in claim 7, wherein, in the catalyst II, the nonmetalloid be selected from IVA race and
At least one of Group VIA nonmetalloid, the metallic element are selected from VB race, group vib, IVA race and group VIII metal element
At least one of；Preferably,
The metallic element is selected from least one of Cr, V, Mo, W, Ni, Fe, Co and Sn.
10. according to the method described in claim 1, wherein, in step (24), the gasification reaction is in a fluidized bed reactor
It carries out, and the temperature in dense bed is 550~800 DEG C, the linear velocity in dense bed is 0.05~0.6m/s, gas residence time
For 0.5~60s；Preferably,
Temperature in the dense bed is 600~750 DEG C.
11. according to claim 1 or method described in 10, wherein the oxygen mole in step (24), in the oxygen-containing gas
Score is 10~30%.
12. according to the method described in claim 1, wherein, in step (24), the contact agent after the regeneration is recycled back to step
Suddenly contact cracking reaction is carried out in the contact cracking reaction area of (1).
13. according to the method described in claim 1, wherein, the contact agent is siliceous and/or aluminium material；Preferably,
Also contain molecular sieve in the contact agent.
14. according to the method described in claim 1, wherein, the carbon residue content in the heavy oil feedstock is less than 40 weight %, metal
Content is 1~1000 μ g/g；Preferably,
The heavy oil feedstock is selected from heavy crude, acid-containing raw oil, super-viscous oil, reduced crude, decompression residuum, decompressed wax oil, coking
In wax oil, deasphalted oil, oil sands bitumen, hydrocracking tail oil, coal tar, shale oil, tank bottom oil and coal liquefaction residue oil extremely
Few one kind；Preferably,
The heavy oil feedstock is decompression residuum, and the boiling point of 5% recovered (distilled) temperature is greater than 500 DEG C.
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| CN112745952A (en) * | 2019-10-31 | 2021-05-04 | 中国石油化工股份有限公司 | Method and system for processing aromatic-rich distillate oil |
| CN114437792A (en) * | 2020-10-30 | 2022-05-06 | 中国石油化工股份有限公司 | Method and apparatus for processing residual oil |
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| CN114437792B (en) * | 2020-10-30 | 2023-07-14 | 中国石油化工股份有限公司 | Method and device for processing residual oil |
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