CN104560150A - Tinpot heavy oil combination processing method - Google Patents
Tinpot heavy oil combination processing method Download PDFInfo
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- CN104560150A CN104560150A CN201310523051.8A CN201310523051A CN104560150A CN 104560150 A CN104560150 A CN 104560150A CN 201310523051 A CN201310523051 A CN 201310523051A CN 104560150 A CN104560150 A CN 104560150A
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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
- C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
Abstract
The invention discloses a tinpot heavy oil combination processing method which is a processing method integrating the steps of heavy oil supercritical fluid extraction, heavy oil fluid catalytic cracking, tinpot heavy oil contact cracking and gasification regeneration are organically combined. By adopting the combination mode, the tinpot heavy oil can be processed; carbon, hydrogen and sulfur in residual oil can be efficiently utilized in an environmentally friendly way, and light oil or fuel gases with a high additional value can be obtained.
Description
Technical field
The invention belongs to a kind of inferior heavy oil working method.More particularly, be a kind of fluidisation working method heavy oil supercritical fluid extraction, heavy oil fluid catalytic cracking, inferior heavy oil contact cracking and gasification regeneration organically combined.
Background technology
In recent years, petroleum resources become heavy day by day, and carbon residue, sulphur and metal content increase.From the angle of hydrocarbon balance, traditional mink cell focus complete processing is divided into hydrogenation, decarburization two kinds of technological lines.No matter be hydrogen addition technology or decarburization technique, object is all change the carbon ratio in residual oil, makes hydrocarbon reconfiguring, the light-end products becoming hydrogen content higher Residual cracking.Decarbonization process comprises catalytic cracking, delayed coking, solvent deasphalting etc.Hydrogenation technique then comprises residual hydrocracking, hydrocracking etc.Heavy, crude oil with poor quality generally have that density and viscosity are large, H/C atomic ratio is low, resin and asphalt content is high, carbon residue is high, heteroatoms and metal content high, adopt traditional mink cell focus complete processing, are all faced with different problems.Heavy oil catalytic cracking process has requirement to the carbon residue of raw material and metal content, and residual oil catalytic cracking ingredient requirement (Ni+V) <25 μ g/g, be generally 10 μ about g/g, also restricted to sulphur content, as pyrrosia lingua company RFCC processing requirement stock oil in sulphur content 0.2 ~ 2.4%(matter again).Delay coking process also exists that coke yield is high, liquid product yield is low and the Utilizing question of high sulfur petroleum coke.Solvent deasphalting also exists effective Utilizing question of the higher and de-oiled asphalt of energy consumption.Residue Hydrotreating Technology then also exists investment cost and running cost is too high and the problem such as the source of hydrogen.
Petroleum resources shortage, international oil price remains high, petroleum resources inferior, heaviness and environmental requirement increasingly stringent are that oil Refining Technologies proposes new challenge, the novel refining technology of the poor quality oil being badly in need of development efficient green especially inferior heavy oil.The efficient green of mink cell focus transforms, and requires on the one hand " to eat dry squeezing clean " as much as possible to stock oil, is exactly want environmental protection on the other hand.
For the Pros and Cons that hydrogenation technique and decarbonization process exist, disclosing one in CN 102234529 A utilizes deep vacuum distillation device to be separated classification to entering heavy oil feedstock, be cut into deep vacuum distillation wax oil and extra heavy oil inferior, extra heavy oil inferior enters solvent deasphalting unit and obtains the solution-off heavy oil after processing, deep vacuum distillation wax oil and solution-off heavy oil enter respectively there is differential responses district/section or reactor catalytic cracking reaction device in react.
CN 1844325 A discloses a kind of decarbonization process of heavy oil and the method for hydrogenation technique organic assembling, the method is by solvent de-asphalting process and coking process combination treatment by inferior heavy oil, deasphalted oil after process and wax tailings are as the raw material of heavy oil hydroprocessing units, thus improve heavy oil hydroprocessing units feed properties, relax the operational condition of heavy oil hydroprocessing units, extend operational cycle of heavy oil hydroprocessing units, the device such as catalytic cracking for downstream provides the raw material of high-quality.
Disclose a kind of combined technique for processing heavy oil in CN 1261545 C, utilize heavy oil fluidized de-charcoal (ROP), residual hydrocracking (RHT) and residual oil fluid catalytic cracking (RFCC) combination process to produce light-weight fuel oil from heavy oil.
Although played the advantage of each technique in above-mentioned prior art to a certain extent, petroleum resources also not to be accomplished efficiently completely, green utilization.Such as coke that residual oil catalytic cracking produces is high, a large amount of SO in regenerated flue gas
xneed process, need outside heat removing simultaneously; Delayed coking gained high sulfur petroleum coke outlet difficulty, solvent de-asphalting process gained de-oiled asphalt not good utilisation etc. problem.
In order to efficient, green utilization inferior heavy oil resource, be necessary to develop a kind of by inferior heavy oil feedstock conversion by maximum light Fuel simultaneously institute's product coke efficiently, the method for green utilization.
Summary of the invention
Technical problem to be solved by this invention is that inferior heavy oil raw material maximum is generated light Fuel, simultaneously produce sulfur highly effective, green utilization in coke and coke.
A kind of inferior heavy oil combinational processing method, comprises the following steps:
(1) heavy oil feedstock I carries out Component seperation at supercritical fluid extraction unit, obtains being rich in the extraction oil of saturated point and fragrance point and is rich in raffinating oil of resin and asphalt component;
(2) the extraction oil of step (1) gained enters catalytic cracking unit, react under the effect of catalytic cracking catalyst, obtain catalytic cracker gas, catalytically cracked gasoline, catalytic cracking diesel oil, catalytically cracked oil and deposit the spent agent of coke, spent agent carries out two-stage regeneration, first paragraph is that oxygen deprivation regeneration obtains semi regeneration agent and flue gas I, sulphur wherein in flue gas I mainly exists with carbonylsulfide form, second segment is oxygen enrichment regeneration, obtain the catalyzer after holomorphosis and flue gas II, the catalyzer after holomorphosis returns catalytic cracking unit;
(3) the raffinating oil to enter by a certain percentage with heavy oil feedstock II and contact Cracking Unit of step (1) gained, contact cracking reaction is carried out under the effect of contact substance, under hydro condition or under conditions of non-hydrogen, obtain contacting cracked gas, contact pressure gasoline, contact cracked fuel oil, contact cracking slurry oil and deposit the contact substance to be generated of coke, in the first gasifier, make the charcoal on contact substance to be generated and oxygen-containing gas I that incomplete combustion reaction occur, obtain semi regeneration contact substance and gasification gas I, the sulphur wherein gasified in gas I is mainly with H
2s and carbonylsulfide form exist;
(4) the semi regeneration contact substance of step (3) gained is at the second gasifier, and under oxygen-containing gas II existent condition, residual charcoal generation perfect combustion on contact substance, obtain holomorphosis contact substance and gasification gas II, the sulphur in gasification gas II is with SO
xform exists, and holomorphosis contact substance returns step (3) contact Cracking Unit;
(5) described flue gas I and gasification gas I enters carbonylsulfide and H
2s removes unit, and the gas after desulfurization uses as fuel gas, or enters converter unit hydrogen.
The carbon residue of described heavy oil feedstock I is 15 % by weight ~ 50 % by weight, and metal content is at 25 ~ 1000 μ g/g.Described heavy oil can be the mixture of one or more in oil at the bottom of heavy crude, acid-containing raw oil, super-viscous oil, long residuum, vacuum residuum, decompressed wax oil, wax tailings, deasphalted oil, oil sands bitumen, hydrocracking tail oil, coal tar, shale oil, tank, oily or other secondary processing distillate of coal liquefaction residue.
In step (1), heavy oil feedstock I carries out Component seperation at supercritical fluid extraction unit, obtains being rich in the extraction oil of saturated point and fragrance point and is rich in raffinating oil of resin and asphalt component.Described supercritical fluid extraction unit solvent for use is C
3~ C
5the mixture of one or more in alkane and alkene, the volume ratio of solvent and heavy oil feedstock I is 3 ~ 12:1.
In supercritical fluid extraction unit, extraction tower pressure is 4.0 ~ 16.0MPa, and extracting tower top temperature is 103 ~ 240 DEG C, and extracting column bottom temperature is 98 ~ 220 DEG C.
Step is extracted out in oil described in (1), saturated point and fragrant mass percentage >=70% divided, bituminous matter mass percentage≤0.5%.Gained is extracted oily yield out and is controlled 20% ~ 40%.
In step (2), the extraction oil of step (1) gained enters catalytic cracking unit, react under the effect of catalytic cracking catalyst, obtain catalytic cracker gas, catalytically cracked gasoline, catalytic cracking diesel oil, catalytically cracked oil and deposit the spent agent of coke, spent agent carries out two-stage regeneration, first paragraph is that oxygen deprivation regeneration obtains semi regeneration agent and flue gas I, sulphur wherein in flue gas I mainly exists with carbonylsulfide form, second segment is oxygen enrichment regeneration, obtains the catalyzer after holomorphosis and flue gas II.
Described catalytic cracking reaction condition is: temperature of reaction 470 ~ 550 DEG C, 0.5 ~ 5.0 second reaction times, the weight ratio 3 ~ 20 of catalytic cracking catalyst and stock oil.
Described catalytic cracking catalyst comprises zeolite, inorganic oxide and clay, and the weight percentage of each component is respectively: zeolite 5% ~ 50%, inorganic oxide 5% ~ 95%, clay 0 ~ 90%.Can be commercially various catalytic cracking catalyst.
Combustion with meagre oxygen is there is and reacts in the middle spent agent of described step (2) and air in the first revivifier, first revivifier is fluidized-bed, and the temperature in its dense bed is 550 ~ 750 DEG C, preferably 600 ~ 730 DEG C, dense bed centerline velocities 0.05 ~ 0.6m/s, gas residence time 0.5 ~ 60 second.
Obtain semi regeneration agent at the first revivifier, the carbon content in semi regeneration agent is 0.3 ~ 0.5 % by weight; Described semi regeneration agent enters Second reactivator and carries out holomorphosis, and holomorphosis temperature is 600 ~ 750 DEG C, and the oxygen content passing into gas in Second reactivator is 10 volume % ~ 50 volume %.
In step (3), the raffinating oil to enter by a certain percentage with heavy oil feedstock II of step (1) gained contacts Cracking Unit, under the effect of contact substance, under hydro condition or under conditions of non-hydrogen, carry out contact cracking reaction, obtain contacting cracked gas, contact pressure gasoline, contact cracked fuel oil, contact cracking slurry oil and deposit the contact substance to be generated of coke.
The carbon residue of described heavy oil feedstock II is 15 % by weight ~ 50 % by weight, and metal content is at 25 ~ 1000 μ g/g.Described heavy oil can be the mixture of one or more in oil at the bottom of heavy crude, acid-containing raw oil, super-viscous oil, long residuum, vacuum residuum, decompressed wax oil, wax tailings, deasphalted oil, oil sands bitumen, hydrocracking tail oil, coal tar, shale oil, tank, oily or other secondary processing distillate of coal liquefaction residue.
It is described that to raffinate oil with the weight ratio of heavy oil feedstock II be 1:9 ~ 9:1.
Under described conditions of non-hydrogen, the processing condition in contact cracking case are: temperature of reaction 450 ~ 650 DEG C, weight hourly space velocity 1 ~ 100h
-1, the mass ratio of contact substance and raw material is 1 ~ 30:1, the gas phase residence time 0.5 ~ 5.0s, and the mass ratio of water vapour and raw material is 0.05 ~ 1:1.
Under described hydro condition, the processing condition in contact cracking case are: temperature of reaction 450 ~ 650 DEG C, weight hourly space velocity 1 ~ 100h
-1, the mass ratio of contact substance and raw material is 1 ~ 30:1, and the mass ratio of water vapour and raw material is 0.05 ~ 1:1, and total pressure is 0 ~ 1MPa(gauge pressure), hydrogen dividing potential drop is 0.1 ~ 0.5MPa, and hydrogen-oil ratio is 10 ~ 1500m
3/ m
3.
Contact Cracking Unit contact substance used is selected from containing the contact substance of molecular sieve and/or not containing the contact substance of molecular sieve.
The described contact substance containing molecular sieve is be selected from the contact substance containing one or more molecular sieves in X molecular sieve, Y molecular sieve, mordenite, ZSM-5, clay molecular sieve with layer structure, SAPO.
The described contact substance not containing molecular sieve refers to the contact substance prepared for raw material with the mixture of one or more in amorphous silicon aluminium, carclazyte, kaolin, montmorillonite, rectorite leng, illite, chlorite, pseudo-boehmite, silicon-dioxide.Also one or more catalyzer prepared for raw material in pickling, roasting, the amorphous silicon aluminium of screening process, carclazyte, kaolin, montmorillonite, rectorite leng, illite, chlorite can be through.Also one or more and pseudo-boehmite in pickling, roasting, the amorphous silicon aluminium of screening process, carclazyte, kaolin, montmorillonite, rectorite leng, illite, chlorite can be through and/or silicon-dioxide is catalyzer prepared by raw material.
In the first gasifier, make the charcoal on contact substance to be generated and oxygen-containing gas I that incomplete combustion reaction occur, obtain semi regeneration contact substance and gasification gas I, the sulphur wherein gasified in gas I is mainly with H
2s and carbonylsulfide form exist.First gasifier is fluidized-bed gasifier, and the temperature in dense bed is 550 ~ 800 DEG C, preferably 600 ~ 750 DEG C, dense bed centerline velocities 0.05 ~ 0.6m/s; In described oxygen-containing gas I, oxygen mole fraction is 10% ~ 30%, all the other are water vapour, carbonic acid gas and/or nitrogen, and namely all the other are water vapour and carbonic acid gas, water vapour and nitrogen, or water vapour and carbonic acid gas and nitrogen, gas residence time 0.5 ~ 60 second.
(CO+H in the gasification gas I generated
2)/CO
2mol ratio 0.5 ~ 3.H in gasification gas I
2s and COS accounts for the 99.0%(volume of total sulfur in gasification gas I) more than.
The carbon content of the contact substance to be generated that described step (3) obtains is 0.5% ~ 5.0 % by weight; The carbon content of the semi regeneration contact substance obtained in described step (3) is 0.3 ~ 2.0 % by weight.
In step (4), the semi regeneration contact substance of step (3) gained is at the second gasifier, and under oxygen-containing gas II existent condition, residual charcoal generation perfect combustion on contact substance, obtain holomorphosis contact substance and gasification gas II, the sulphur in gasification gas II is with SO
xform exists, and holomorphosis contact substance returns step (3) contact Cracking Unit.In described second gasifier, temperature of reaction is 600 ~ 750 DEG C, and the oxygen content of oxygen-containing gas II is 10 volume % ~ 50 volume %.
In the present invention wherein a kind of embodiment, do not comprise step (4), the semi regeneration contact substance that step (3) obtains can directly or partly return step (3) contact Cracking Unit.
The flue gas I that step (2) obtains described in step (5) and step (3) obtain gasification gas I and enter carbonylsulfide and H
2s removes unit, and the gas after desulfurization uses as fuel gas, or enters converter unit hydrogen.Described COS and H
2it is that COS is converted into H that S removes device
2the further recovery sulphur of S, or absorb COS and reclaim COS.It can be organic amine absorption process, hydroconversion process, hydrolysis method, oxidation conversion method, absorption method etc. that COS removes the method that device adopts.COS can be converted into H2S by these methods.Also porous solid materials adsorption COS can be adopted to make it in solid surface enrichment, and obtain COS further.From H
2the method of S recovery sulphur refers to industrial conventional method, as claus process etc.
Flue gas I and gasification gas I by entering CO converter unit, generates and is rich in hydrogen and CO after desulfurization
2gas, the H of high density can be obtained after acid gas removal body
2.
Compared with prior art, beneficial effect of the present invention is mainly reflected in the following aspects:
First, method integration provided by the present invention heavy oil deep processing and superfluous carbonaceous resistates Appropriate application two aspects, while improving light oil yield, coke combustion with meagre oxygen in revivifier of having more than needed, is rich in (CO+H in its gas gas of gained cigarette
2), this part gas can use as fuel gas or be used for transformation and hydrogen production, obtains high added value product.
The second, method provided by the present invention decreases catalytic cracking flue gas and the SO contacted in cracking gasification gas
xdischarge, be easy to reclaim sulphur, whole technological process environmental protection.
Accompanying drawing explanation
Fig. 1 is the principle flow chart of method provided by the present invention.
Embodiment
Below by accompanying drawing, method of the present invention is further explained, but not thereby limiting the invention.
As shown in Figure 1, inferior heavy oil raw material I enters supercritical extraction unit through pipeline 1, extract oil out and enter catalytic cracking unit through pipeline 4, cracking oil gas is drawn through pipeline 5, spent agent enters the first revivifier through pipeline 6, at the first revivifier, air introduces the first revivifier through pipeline 7, and gained flue gas I enters carbonylsulfide and H through pipeline 8
2s removes unit, and enter Second reactivator from the semi regeneration agent out of the first revivifier through pipeline 9, gas introduces Second reactivator through pipeline 10, and gained flue gas II draws through pipeline 12, and holomorphosis catalyzer returns catalytic cracking unit through pipeline 11.
Raffinate oil by pipeline 3 from supercritical extraction unit gained and enter together with the inferior heavy oil raw material II from pipeline 2 and contact Cracking Unit, gained contact cracking oil gas is drawn through pipeline 13, contact substance to be generated enters the first gasifier through pipeline 14, oxygen-containing gas I introduces the first gasifier through pipeline 16 and 17 respectively, and gained gasification gas I is through pipeline 15 carbonylate sulphur and H
2s removes unit, and gained semi regeneration contact substance introduces the second gasifier through pipeline 18, and oxygen-containing gas II introduces the second gasifier through pipeline 19, and gained gasification gas II draws through pipeline 20, and holomorphosis contact substance returns contact Cracking Unit through pipeline 21.Semi regeneration contact substance is drawn can directly return contact Cracking Unit through pipeline 18.Enter carbonylsulfide and H
2the flue gas I that S removes unit draws or enters CO converter unit by pipeline 22 with gasification gas I after desulfurization, generates and is rich in hydrogen and CO
2gas, the H of high density can be obtained after acid gas removal body
2.
The present invention is described in detail below by embodiment, but the use range that embodiment is not thereby limiting the invention.
The catalyzer adopted in embodiment and comparative example or contact substance as follows:
The catalyzer that catalytic cracking unit adopts is trade names is CRC-1 catalytic cracking catalyst.
The contact substance that contact cracking adopts is containing the obtained contact substance of roasting after 10 % by weight aluminum oxide, 80 % by weight kaolinic spraying dry, is designated as MFC-1.
The feedstock property adopted in embodiment and comparative example is as following table:
Table 1 Vacuum Residue Properties
For inferior raw material shown in table 1, directly adopt catalytic cracking process to process, but delayed coking can be adopted to process.So will contrast by poor residuum working method provided by the invention and delayed coking working method, invention effect of the present invention will be described.
Embodiment 1
Vacuum residuum is carried out physical sepn at supercritical fluid extraction unit, extracting tower top temperature is 240 DEG C, at the bottom of tower 220 DEG C, solvent is mixed pentane (w (Skellysolve A): w (iso-pentane)=1:2), and pressure range is 4 ~ 12MPa.Extraction oil and 60% raffinate oil that yield is 40% is obtained after extraction terminates.Extracting the saturated point of mass percentage divided with fragrance in oil out is 82.1%, and bituminous matter mass percentage <0.1%, carbon residue 6.1%, metal (Ni+V) content is 14.1 μ g/g.
Extraction oil is entered catalytic cracking unit, and processing condition are: temperature of reaction 520 DEG C, agent-oil ratio 7, water-oil ratio 0.05, reaction times 3s, and products therefrom distribution is in table 2.After catalytic cracking reaction, gained spent agent enters in the first revivifier, carries out oxygen deprivation regeneration, and processing condition are: the temperature in dense bed is 650 DEG C, dense bed centerline velocities 0.3m/s, gas residence time 30 seconds, and gained flue gas I forms in table 2.Carbon content 0.4 % by weight in semi regeneration agent, semi regeneration agent enters Second reactivator and carries out holomorphosis, obtains flue gas II and regenerator.
To raffinate oil and enter contact Cracking Unit, processing condition are: temperature of reaction 510 DEG C, agent-oil ratio 10, water-oil ratio 0.2, gas phase residence time 2.0s, and products therefrom distribution is in table 2.After contact cracking reaction, gained contact substance to be generated enters in the first gasifier, processing condition are: the temperature in dense bed is 650 DEG C, dense bed centerline velocities 0.25m/s, gas residence time 30 seconds, oxygen mole content 20% in oxygen-containing gas, water molar content 80%, gained gasification gas I forms in table 2.Carbon content 0.72 % by weight on the semi regeneration contact substance of gained, the second gasifier that semi regeneration contact substance enters contact Cracking Unit carries out holomorphosis, obtains gasification gas II and holomorphosis contact substance.
By catalytic cracking with contact cracking semi regeneration after flue gas I and gasification gas I merge carbonylate sulphur and H
2after S removes device, enter CO changing device, after gained conversion gas carries out acid gas removal process, obtain the H that concentration is 99.2%
2.
Embodiment 2
Vacuum residuum is carried out physical sepn at supercritical fluid extraction unit, extracting tower top temperature is 230 DEG C, at the bottom of tower 210 DEG C, solvent is mixed pentane (w (Skellysolve A): w (iso-pentane)=1:1), and pressure range is 4 ~ 12MPa.Extraction oil and 62% raffinate oil that yield is 38% is obtained after extraction terminates.Extracting the saturated point of mass percentage divided with fragrance in oil out is 83.5%, and bituminous matter mass percentage <0.1%, carbon residue 5.8%, metal (Ni+V) content is 10.2 μ g/g.
Extraction oil is entered catalytic cracking unit, and processing condition are: temperature of reaction 530 DEG C, agent-oil ratio 8, water-oil ratio 0.05, reaction times 2.5s, and products therefrom distribution is in table 2.After catalytic cracking reaction, gained spent agent enters in the first revivifier, carries out oxygen deprivation regeneration, and processing condition are: the temperature in dense bed is 680 DEG C, dense bed centerline velocities 0.35m/s, gas residence time 40 seconds, and flue gas I forms in table 2.Carbon content 0.35 % by weight in semi regeneration agent, the Second reactivator that semi regeneration agent enters catalytic cracking unit carries out holomorphosis, obtains flue gas II and regenerator.
To raffinate oil and enter contact Cracking Unit, processing condition are: temperature of reaction 500 DEG C, air speed 20h
-1, agent-oil ratio 7, water-oil ratio 0.25, total pressure (gauge pressure) is 1.0MPa, and hydrogen dividing potential drop is 0.3MPa, and hydrogen-oil ratio is 100m
3/ m
3, products therefrom distribution is in table 2.After contact cracking reaction, gained contact substance to be generated enters in the first gasifier of contact Cracking Unit, processing condition are: the temperature in dense bed is 690 DEG C, dense bed centerline velocities 0.33m/s, gas residence time 50 seconds, pass into air, gained gasification gas I forms in table 2.Carbon content 0.65 % by weight on semi regeneration contact substance, the second gasifier that semi regeneration contact substance enters contact Cracking Unit carries out holomorphosis, obtains gasification gas II and holomorphosis contact substance.
By catalytic cracking with contact cracking semi regeneration after flue gas I and gasification gas I merge carbonylate sulphur and H
2after S removes device, obtain being rich in CO and H
2gas, can use as fuel gas.
Comparative example 1
Adopt delay coking process to process in vacuum residuum, processing condition are: furnace outlet temperature 500 DEG C, pressure 0.15MPa, recycle ratio 0.2, and products therefrom distribution is in table 3.
To same vacuum residuum, delayed coking products distribution is contrasted, in table 3 with distributing by the embodiment of the present invention 1,2 gained condensation products.
As can be seen from table 2,3 data, adopt the inventive method processing poor residuum, yield of light oil can be improved, increase liquid to receive, reduce coke yield, have the coke of quite a few low value (coke price is generally 1200 yuan/ton) hydrogen (20000 yuan/ton) of high added value can be converted into or be used as fuel gas simultaneously.Sulphur simultaneously in refinery coke can be converted into COS or H
2s, decreases treatment S O
xexpense.
Table 2
| Project | Embodiment 1 | Embodiment 2 |
| Catalytic cracking unit products distribution/% | ||
| Dry gas | 2.31 | 3.76 |
| Liquefied gas | 18.62 | 17.51 |
| Gasoline | 42.33 | 43.14 |
| Diesel oil | 20.14 | 22.87 |
| Slurry oil | 8.06 | 5.12 |
| Coke | 8.54 | 7.6 |
| Flue gas I mole composition (butt)/% | ||
| CO | 20.70 | 27.26 |
| CO 2 | 15.80 | 14.22 |
| N 2 | 63.50 | 58.52 |
| COS/ppm | 32 | 28 |
| H 2S/ppm | 6 | 2 |
| Contact Cracking Unit products distribution/% | ||
| H 2S | 2.78 | 3.2 |
| Dry gas | 4.26 | 4.33 |
| Liquefied gas | 9.23 | 10.52 |
| Gasoline | 10.27 | 8.77 |
| Diesel oil | 10.31 | 12.45 |
| Wax oil | 25.93 | 33.53 |
| Coke | 37.22 | 27.20 |
| Gasification I mole, gas composition (butt)/% | ||
| CO | 44.31 | 24.33 |
| CO 2 | 45.21 | 12.17 |
| H 2 | 10.12 | 0 |
| CH 4 | 0.36 | 0 |
| N 2 | 0.00 | 63.5 |
| COS/ppm | 560 | 6874 |
| H 2S/ppm | 5500 | 640 |
Table 3
| Project | Embodiment 1 | Embodiment 2 | Comparative example |
| Products collection efficiency/% | |||
| H 2S | 1.67 | 1.98 | 1.25 |
| Dry gas | 3.48 | 4.11 | 3.55 |
| Liquefied gas | 12.99 | 13.18 | 4.28 |
| Gasoline | 23.09 | 21.83 | 14.25 |
| Diesel oil | 14.24 | 16.41 | 29.19 |
| Wax oil | 18.78 | 22.73 | 20.94 |
| Coke | 25.75 | 19.75 | 26.25 |
| Be converted into H 2Coke | 11.32 | —— | |
| Be converted into the coke of fuel gas | —— | 10.85 | |
| Yield of light oil | 50.32 | 51.42 | 47.72 |
| Total liquid yield | 69.1 | 74.15 | 68.66 |
Claims (21)
1. an inferior heavy oil combinational processing method, comprises the following steps:
(1) heavy oil feedstock I carries out Component seperation at supercritical fluid extraction unit, obtains being rich in the extraction oil of saturated point and fragrance point and is rich in raffinating oil of resin and asphalt component;
(2) the extraction oil of step (1) gained enters catalytic cracking unit, react under the effect of catalytic cracking catalyst, obtain catalytic cracker gas, catalytically cracked gasoline, catalytic cracking diesel oil, catalytically cracked oil and deposit the spent agent of coke, spent agent carries out two-stage regeneration, first paragraph is that oxygen deprivation regeneration obtains semi regeneration agent and flue gas I, sulphur wherein in flue gas I mainly exists with carbonylsulfide form, second segment is oxygen enrichment regeneration, obtain the catalyzer after holomorphosis and flue gas II, the catalyzer after holomorphosis returns catalytic cracking unit;
(3) the raffinating oil to enter by a certain percentage with heavy oil feedstock II and contact Cracking Unit of step (1) gained, contact cracking reaction is carried out under the effect of contact substance, under hydro condition or under conditions of non-hydrogen, obtain the contact substance to be generated contacting cracked gas, contact pressure gasoline, contact cracked fuel oil, contact cracking slurry oil and deposit coke, in the first gasifier, make the charcoal on contact substance to be generated and oxygen-containing gas I that incomplete combustion reaction occur, obtain semi regeneration contact substance and gasification gas I, the sulphur wherein gasified in gas I is mainly with H
2s and carbonylsulfide form exist;
(4) the semi regeneration contact substance of step (3) gained is at the second gasifier, and under oxygen-containing gas II existent condition, residual charcoal generation perfect combustion on contact substance, obtain holomorphosis contact substance and gasification gas II, the sulphur in gasification gas II is with SO
xform exists, and holomorphosis contact substance returns step (3) contact Cracking Unit;
(5) described flue gas I and gasification gas I enters carbonylsulfide and H
2s removes unit, and the gas after desulfurization uses as fuel gas, or enters converter unit hydrogen.
2., according to the method for claim 1, it is characterized in that the carbon residue of described heavy oil feedstock I and heavy oil feedstock II is 15 % by weight ~ 50 % by weight, metal content is at 25 ~ 1000 μ g/g.
3., according to the method for claim 1, it is characterized in that in described step (1), supercritical fluid extraction unit solvent for use is C
3~ C
5the mixture of one or more in alkane and alkene, the volume ratio of solvent and heavy oil feedstock I is 3 ~ 12:1.
4., according to the method for claim 1, it is characterized in that in described step (1), in supercritical fluid extraction unit, extraction tower pressure is 4.0 ~ 16.0MPa, extracting tower top temperature is 103 ~ 240 DEG C, and extracting column bottom temperature is 98 ~ 220 DEG C.
5. according to the method for claim 1, it is characterized in that extracting out in oil described in described step (1), saturated point and fragrant mass percentage >=70% divided, bituminous matter mass percentage≤0.5%.
6., according to the method for claim 1, it is characterized in that described step (1) gained is extracted oily yield out and controlled 20% ~ 40%.
7. according to the method for claim 1, the catalytic cracking reaction condition described in described step (2) that it is characterized in that is: temperature of reaction 470 ~ 550 DEG C, 0.5 ~ 5.0 second reaction times, the weight ratio 3 ~ 20 of catalytic cracking catalyst and stock oil.
8. according to the method for claim 1, it is characterized in that the catalytic cracking catalyst described in described step (2) comprises zeolite, inorganic oxide and clay, the weight percentage of each component is respectively: zeolite 5% ~ 50%, inorganic oxide 5% ~ 95%, clay 0 ~ 90%.
9. according to the method for claim 1, it is characterized in that the middle spent agent of described step (2) and air combustion with meagre oxygen occur in the first revivifier and react, temperature in dense bed is 550 ~ 750 DEG C, dense bed centerline velocities 0.05 ~ 0.6m/s, gas residence time 0.5 ~ 60 second; Obtain semi regeneration agent at the first revivifier, the carbon content in semi regeneration agent is 0.3 ~ 0.5 % by weight; Described semi regeneration agent enters Second reactivator and carries out holomorphosis, and holomorphosis temperature is 600 ~ 750 DEG C, and the oxygen content passing into gas in Second reactivator is 10 volume % ~ 50 volume %.
10. according to the method for claim 1, it is characterized in that in described step (3) under conditions of non-hydrogen, the processing condition in contact cracking case are: temperature of reaction 450 ~ 650 DEG C, weight hourly space velocity 1 ~ 100h
-1, the mass ratio of contact substance and raw material is 1 ~ 30:1, the gas phase residence time 0.5 ~ 5.0s, and the mass ratio of water vapour and raw material is 0.05 ~ 1:1.
11. according to the method for claim 1, it is characterized in that in described step (3) under hydro condition, and the processing condition in contact cracking case are: temperature of reaction 450 ~ 650 DEG C, weight hourly space velocity 1 ~ 100h
-1, the mass ratio of contact substance and raw material is 1 ~ 30:1, and the mass ratio of water vapour and raw material is 0.05 ~ 1:1, and total pressure is 0 ~ 1MPa(gauge pressure), hydrogen dividing potential drop is 0.1 ~ 0.5MPa, and hydrogen-oil ratio is 10 ~ 1500m
3/ m
3.
12. according to the method for claim 1, it is characterized in that contacting Cracking Unit contact substance used is selected from containing the contact substance of molecular sieve and/or not containing the contact substance of molecular sieve.
13. according to the method for claim 12, it is characterized in that the described contact substance containing molecular sieve is be selected from the contact substance containing one or more molecular sieves in X molecular sieve, Y molecular sieve, mordenite, ZSM-5, clay molecular sieve with layer structure, SAPO.
14. according to the method for claim 12, and the contact substance not containing molecular sieve described in it is characterized in that refers to the contact substance prepared for raw material with the mixture of one or more in amorphous silicon aluminium, carclazyte, kaolin, montmorillonite, rectorite leng, illite, chlorite, pseudo-boehmite, silicon-dioxide.
15. according to the method for claim 1, and it is characterized in that in described step (3), the first gasifier is fluidized-bed gasifier, the temperature in dense bed is 550 ~ 800 DEG C, dense bed centerline velocities 0.05 ~ 0.6m/s; In described oxygen-containing gas I, oxygen mole fraction is 10% ~ 30%, and all the other are water vapour, carbonic acid gas and/or nitrogen, gas residence time 0.5 ~ 60 second.
16. according to the method for claim 1, it is characterized in that (CO+H in the gasification gas I generated in described step (3)
2)/CO
2mol ratio 0.5 ~ 3.
17. according to the method for claim 1, it is characterized in that the H in described step (3) gasification gas I
2s and COS accounts for the 99.0%(volume of total sulfur in gasification gas I) more than.
18., according to the method for claim 1, is characterized in that the carbon content of the contact substance to be generated that described step (3) obtains is 0.5% ~ 5.0 % by weight; The carbon content of the semi regeneration contact substance obtained in described step (3) is 0.3 ~ 2.0 % by weight.
19. in accordance with the method for claim 1, it is characterized in that, in described second gasifier, temperature of reaction is 600 ~ 750 DEG C, and the oxygen content of oxygen-containing gas II is 10 volume % ~ 50 volume %.
20., according to the method for claim 1, is characterized in that step (5) described COS and H
2it is that COS is converted into H that S removes device
2the further recovery sulphur of S, or absorb COS and reclaim COS.
21. in accordance with the method for claim 1, it is characterized in that, described step can not comprise step (4), and the semi regeneration contact substance that step (3) obtains can directly or partly return step (3) contact Cracking Unit.
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