CN104560150B - Tinpot heavy oil combination processing method - Google Patents
Tinpot heavy oil combination processing method Download PDFInfo
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- CN104560150B CN104560150B CN201310523051.8A CN201310523051A CN104560150B CN 104560150 B CN104560150 B CN 104560150B CN 201310523051 A CN201310523051 A CN 201310523051A CN 104560150 B CN104560150 B CN 104560150B
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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
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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 processing method.More specifically, be a kind of by heavy oil supercritical fluid extraction,
RFCC, inferior heavy oil contact the fluidisation processing method that cracking and gasification regeneration organically combine.
Background technology
In recent years, petroleum resources increasingly become weight, and carbon residue, sulphur and tenor increase.From the perspective of hydrocarbon balance, pass
The mink cell focus processing technology of system is divided into hydrogenation, two kinds of technology paths of decarburization.Either hydrogen addition technology or decarburization technique, purpose is all
Be change residual oil in carbon ratio, make hydrocarbon reconfigure, Residual cracking is become the higher light-end products of hydrogen content.Decarburization work
Skill includes catalytic cracking, delayed coking, solvent deasphalting etc..Hydrogenation technique then includes residual hydrocracking, is hydrocracked.Weight
Matter, crude oil with poor quality typically have that density and viscosity are big, h/c atomic ratio is low, resin and asphalt content high, carbon residue is high, miscellaneous former
The features such as son and tenor are high, using traditional mink cell focus processing technology, all suffers from different problems.RFCC
Technique requires to the carbon residue of raw material and tenor, and RFCC ingredient requirement (ni+v) < 25 μ g/g, generally
10 μ g/g, also restricted to sulfur content, such as pyrrosia lingua company in the feedstock oil of rfcc technological requirement sulfur content again 0.2~
2.4%(matter).Delay coking process has that coke yield is high, liquid product yield is low and the Utilizing question of high sulfur petroleum coke.
Solvent deasphalting has that energy consumption is higher and the effectively utilizes problem of de-oiled asphalt.Residue Hydrotreating Technology then has capital cost
The problems such as with the source of and hydrogen too high with running cost.
Petroleum resources shortage, international oil price remain high, petroleum resources are inferior, heaviness and environmental requirement increasingly stringent are
Oil Refining Technologies propose new challenge, are badly in need of the new refining technology of the poor oil especially inferior heavy oil of development efficient green.
The efficient green conversion of mink cell focus, on the one hand requires " to eat dry squeezing net " as far as possible to feedstock oil, on the other hand seeks to environmental protection.
The Pros and Cons existing for hydrogenation technique and decarbonization process, disclose a kind of utilization in cn 102234529 a
Deep vacuum distillation device separates classification to entering heavy oil feedstock, is cut into deep vacuum distillation wax oil and extra heavy oil inferior, inferior super
Heavy oil enters the solution-off heavy oil after solvent deasphalting unit is processed, and deep vacuum distillation wax oil and solution-off heavy oil respectively enter and has
Reacted in the catalytic cracking reaction device of differential responses area/section or reactor.
A kind of method that cn 1844325 a discloses decarbonization process of heavy oil and hydrogenation technique organic assembling, the method is
Inferior heavy oil is passed through solvent de-asphalting process and coking process Combined Treatment, the deasphalted oil after process and wax tailings conduct
The raw material of heavy oil hydroprocessing units, thus improving heavy oil hydroprocessing units feed properties, relaxes heavy oil hydroprocessing units
Operating condition, extend the operation cycle of heavy oil hydroprocessing units, the device such as catalytic cracking for downstream provides the former of high-quality
Material.
Disclose a kind of combined technique for processing heavy oil in cn 1261545 c, added using heavy oil fluidized de- charcoal (rop), residual oil
Hydrogen processes (rht) and residual oil fluid catalytic cracking (rfcc) group technology produces light-weight fuel oil from heavy oil.
Although the advantage having played each technique in above-mentioned prior art to a certain extent, also not complete to petroleum resources
Entirely accomplish efficient, green utilization.The produced coke of such as RFCC is high, a large amount of so in regenerated flue gasxNeed to process, simultaneously
Need outside heat removing;Delayed coking gained high sulfur petroleum coke outlet is difficult, solvent de-asphalting process gained de-oiled asphalt not good utilisation
Deng the problems such as.
For efficient, green utilization inferior heavy oil resource it is necessary to inferior heavy oil raw material is converted into maximum by exploitation one kind
Produced coke is efficient simultaneously for amount light Fuel, the method for green utilization.
Content of the invention
The technical problem to be solved is that inferior heavy oil raw material maximum is generated light Fuel, is produced Jiao simultaneously
Sulfur highly effective in charcoal and coke, green utilization.
A kind of inferior heavy oil combinational processing method, comprises the following steps:
(1) heavy oil feedstock i carries out Component seperation in supercritical fluid extraction unit, obtains dividing and fragrance point rich in saturation
Tapped oil and raffinating oil rich in resin and asphalt component;
(2) tapped oil of step (1) gained enters catalytic cracking unit, carries out anti-in the presence of catalytic cracking catalyst
Should, obtaining catalytic cracker gas, catalytically cracked gasoline, catalytic cracking diesel oil, catalytic cracked oil pulp and deposition has the to be generated of coke
Agent, spent agent carries out two-stage regeneration, and first paragraph obtains semi regeneration agent and flue gas i for oxygen deprivation regeneration, and the sulphur in wherein flue gas i is main
Existed with cos form, second segment is oxygen enrichment regeneration, the catalyst after being regenerated completely and flue gas ii, after regenerating completely
Catalyst returns catalytic cracking unit;
(3) the raffinating oil to enter by a certain percentage with heavy oil feedstock ii and contact Cracking Unit, in contact agent of step (1) gained
In the presence of, carry out under hydro condition or under conditions of non-hydrogen contact cracking reaction, obtain contact cracked gas, contact
Cracking gasoline, contact cracked diesel oil, contact cracking slurry oil and deposition have the contact agent to be generated of coke, in the first gasifier, make
There is imperfect combustion reaction in the charcoal on contact agent to be generated and oxygen-containing gas i, obtain semi regeneration contact agent and gasification gas i, wherein
Sulphur in gasification gas i is mainly with h2S and cos form exist;
(4) the semi regeneration contact agent of step (3) gained, in the second gasifier, under conditions of oxygen-containing gas ii exists, connects
In tactile agent, residual charcoal occurs to burn completely, is regenerated contact agent and gasification gas ii completely, the sulphur in gasification gas ii is with soxForm
Exist, completely regeneration contact agent return to step (3) contact Cracking Unit;
(5) described flue gas i and gasification gas i enters cos and h2S removal unit, the gas after desulfurization makes as fuel gas
With, or enter converter unit hydrogen.
The carbon residue of described heavy oil feedstock i is 15 weight %~50 weight %, and tenor is in 25~1000 μ g/g.Described weight
Oil can be heavy crude, acid-containing raw oil, super-viscous oil, reduced crude, decompression residuum, decompressed wax oil, wax tailings, depitching
Oil, oil sands bitumen, hydrocracking tail oil, coal tar, shale oil, tank bottom are oily, coal liquefaction residue is oily or other secondary operation cut
The mixture of one or more of oil.
In step (1), heavy oil feedstock i carries out Component seperation in supercritical fluid extraction unit, obtains dividing rich in saturation
With the tapped oil of fragrance point and raffinating oil rich in resin and asphalt component.Described supercritical fluid extraction unit solvent for use
It is c3~c5The mixture of one or more of alkane and alkene, solvent is 3~12:1 with the volume ratio of heavy oil feedstock i.
In supercritical fluid extraction unit, extracting pressure tower is 4.0~16.0mpa, and extracting tower top temperature is 103~240
DEG C, extracting column bottom temperature is 98~220 DEG C.
In tapped oil described in step (1), weight/mass percentage composition >=70% that saturation is divided and fragrance divides, asphalitine quality hundred
Divide content≤0.5%.Gained is extracted oil yield out and is controlled 20%~40%.
In step (2), the tapped oil of step (1) gained enters catalytic cracking unit, in the work of catalytic cracking catalyst
With under reacted, obtaining catalytic cracker gas, catalytically cracked gasoline, catalytic cracking diesel oil, catalytic cracked oil pulp and deposition has
The spent agent of coke, spent agent carries out two-stage regeneration, and first paragraph obtains semi regeneration agent and flue gas i, wherein flue gas i for oxygen deprivation regeneration
In sulphur mainly with cos form exist, second segment be oxygen enrichment regeneration, the catalyst after being regenerated completely and flue gas ii.
Described catalytic cracking reaction condition is: 470~550 DEG C of reaction temperature, and in 0.5~5.0 second reaction time, catalysis is split
Change the weight ratio 3~20 of catalyst and feedstock oil.
Described catalytic cracking catalyst includes zeolite, inorganic oxide and clay, and the weight percentage of each component divides
It is not: zeolite 5%~50%, inorganic oxide 5%~95%, clay 0~90%.Can be commercially various catalytic cracking catalysts.
In described step (2), spent agent and air occur combustion with meagre oxygen to react in the first regenerator, and the first regenerator is
Fluid bed, 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 in the first regenerator, the carbon content in semi regeneration agent is 0.3~0.5 weight %;Described semi regeneration
Agent enters Second reactivator and is regenerated completely, and complete regeneration temperature is 600~750 DEG C, is passed through gas in Second reactivator
Oxygen content is 10 volume %~50 volumes %.
In step (3), the raffinating oil to enter by a certain percentage with heavy oil feedstock ii and contact cracking list of step (1) gained
Unit, carries out contacting cracking reaction in the presence of contact agent, under hydro condition or under conditions of non-hydrogen, obtains contacting cracking
Gas, contact cracking gasoline, contact cracked diesel oil, contact cracking slurry oil and deposition have the contact agent to be generated of coke.
The carbon residue of described heavy oil feedstock ii is 15 weight %~50 weight %, and tenor is in 25~1000 μ g/g.Described
Heavy oil can be heavy crude, acid-containing raw oil, super-viscous oil, reduced crude, decompression residuum, decompressed wax oil, wax tailings, depitching
Oil, oil sands bitumen, hydrocracking tail oil, coal tar, shale oil, tank bottom are oily, coal liquefaction residue is oily or other secondary operation cut
The mixture of one or more of oil.
Described raffinate oil with the weight of heavy oil feedstock ii than for 1:9~9:1.
Under described conditions of non-hydrogen, the process conditions in contact cracker are: 450~650 DEG C of reaction temperature, during weight
Air speed 1~100h-1, contact agent is 1~30:1 with the mass ratio of raw material, the gas phase time of staying 0.5~5.0s, vapor and raw material
Mass ratio be 0.05~1:1.
Under described hydro condition, the process conditions in contact cracker are: 450~650 DEG C of reaction temperature, weigh space-time
Fast 1~100h-1, contact agent is 1~30:1 with the mass ratio of raw material, and vapor is 0.05~1:1 with the mass ratio of raw material, stagnation pressure
Power is 0~1mpa(gauge pressure), hydrogen dividing potential drop is 0.1~0.5mpa, and hydrogen-oil ratio is 10~1500m3/m3.
Contact agent used by contact Cracking Unit is selected from the contact agent containing molecular sieve and/or the contact agent without molecular sieve.
The described contact agent containing molecular sieve is to divide selected from molecular sieve containing x, y molecular sieve, modenite, zsm-5, laminated clay column
The contact agent of one or more of son sieve, sapo molecular sieve.
The described contact agent without molecular sieve refers to amorphous silicon aluminium, carclazyte, kaolin, montmorillonite, rectorite, Erie
The contact agent that the mixture of one or more of stone, chlorite, boehmite, silica is prepared for raw material.Can also
It is through overpickling, roasting, the amorphous silicon aluminium of screening process, carclazyte, kaolin, montmorillonite, rectorite, illite, chlorite
One or more of for raw material preparation catalyst.Can also be through overpickling, roasting, the amorphous silicon aluminium of screening process,
One or more of carclazyte, kaolin, montmorillonite, rectorite, illite, chlorite and boehmite and/or titanium dioxide
The catalyst that silicon is prepared for raw material.
In the first gasifier, make the charcoal on contact agent to be generated and oxygen-containing gas i that imperfect combustion reaction to occur, obtain half
Sulphur in regeneration contact agent and gasification gas i, wherein gasification gas i is mainly with h2S and cos form exist.First gasifier is stream
Change bed gasifier, 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%, and remaining is vapor, carbon dioxide and/or nitrogen,
Be remaining be vapor and carbon dioxide, vapor and nitrogen, or vapor and carbon dioxide and nitrogen, when gas stops
Between 0.5~60 second.
(co+h in the gasification gas i being generated2)/co2Mol ratio 0.5~3.H in gasification gas i2S and cos accounts for gasification
The 99.0%(volume of total sulfur in gas i) more than.
The carbon content of the contact agent to be generated that described step (3) obtains is in 0.5%~5.0 weight %;Obtain in described step (3)
Semi regeneration contact agent carbon content in 0.3~2.0 weight %.
In step (4), the semi regeneration contact agent of step (3) gained, in the second gasifier, exists in oxygen-containing gas ii
Under the conditions of, on contact agent, residual charcoal occurs to burn completely, is regenerated contact agent and gasification gas ii, the sulphur in gasification gas ii completely
With soxForm exists, completely regeneration contact agent return to step (3) contact Cracking Unit.In described second gasifier, reaction temperature
For 600~750 DEG C, the oxygen content of oxygen-containing gas ii is 10 volume %~50 volumes %.
In one of which embodiment of the present invention, do not include step (4), the semi regeneration contact agent that step (3) obtains can
Cracking Unit is contacted with direct or part return to step (3).
The flue gas i that step (2) obtains described in step (5) and step (3) obtain gasify gas i entrance cos and h2s
Removal unit, the gas after desulfurization uses as fuel gas, or enters converter unit hydrogen.Described cos and h2S removing dress
Put is that cos is converted into h2The further Recovered sulphur of s, or absorb cos and reclaim cos.The side that cos removing means is adopted
Method can be organic amine absorption process, hydroconversion process, hydrolysis method, oxidation conversion method, absorption method etc..These methods can be by
Cos is converted into h2s.It can also be made to be enriched with the surface of solids using porous solid material absorption cos, and obtain further
cos.From h2The method of s Recovered sulphur refers to industrial conventional method, such as claus process etc..
Flue gas i and gasification gas i passes through to enter co converter unit after desulfurization, generates and is rich in hydrogen and co2Gas
Body, can obtain the h of high concentration after de- sour gas2.
Compared with prior art, the beneficial effects are mainly as follows the following aspects:
First, method integration provided by the present invention heavy oil deep processing and superfluous carbonaceous residue rationally utilize two sides
Face, improve light oil yield while, by coke more than needed in regenerator combustion with meagre oxygen, in its gas gas of gained cigarette be rich in (co+
h2), this portion gas can use as fuel gas or be used for transformation and hydrogen production, obtain high added value product.
Second, method provided by the present invention decrease catalytic cracking flue gas with contact cracking gasification gas in soxRow
Put it is easy to reclaim sulphur, whole technical process environmental protection.
Brief description
Fig. 1 is the principle flow chart of method provided by the present invention.
Specific embodiment
Below by accompanying drawing, the method for the present invention is explained further, but not thereby limiting the invention.
As shown in figure 1, inferior heavy oil raw material i enters supercritical extract unit through pipeline 1, tapped oil enters through pipeline 4 and urges
Change Cracking Unit, cracking oil gas is drawn through pipeline 5, spent agent enters the first regenerator through pipeline 6, in the first regenerator, air
Introduce the first regenerator through pipeline 7, gained flue gas i enters cos and h through pipeline 82S removal unit, goes out from the first regenerator
The semi regeneration agent coming enters Second reactivator through pipeline 9, and gas introduces Second reactivator through pipeline 10, and gained flue gas ii is through pipeline
12 extractions, complete regenerated catalyst returns catalytic cracking unit through pipeline 11.
From supercritical extract unit gained raffinate oil by pipeline 3 and with from pipeline 2 inferior heavy oil raw material ii together with
Enter contact Cracking Unit, gained contact cracking oil gas is drawn through pipeline 13, and contact agent to be generated enters the first gasification through pipeline 14
Device, oxygen-containing gas i introduces the first gasifier through pipeline 16 and 17 respectively, and gained gasification gas i introduces cos and h through pipeline 152s
Removal unit, gained semi regeneration contact agent introduces the second gasifier through pipeline 18, and oxygen-containing gas ii introduces the second gas through pipeline 19
Change device, gained gasification gas ii draws through pipeline 20, and regeneration contact agent returns contact Cracking Unit through pipeline 21 completely.Semi regeneration connects
Tactile agent is drawn through pipeline 18 and can directly be returned contact Cracking Unit.Enter cos and h2The flue gas i of s removal unit and gasification
Gas i is drawn or is entered by pipeline 22 co converter unit after desulfurization, generates and is rich in hydrogen and co2Gas, through depickling
The h of high concentration can be obtained after property gas2.
Describe the present invention below with embodiment in detail, but embodiment use model not thereby limiting the invention
Enclose.
Catalyst employed in embodiment and comparative example or contact agent are as follows:
The catalyst that catalytic cracking unit is adopted is product designation crc-1 catalytic cracking catalyst.
The contact agent that contact cracking is adopted is containing roasting after 10 weight % aluminum oxide, the kaolinic spray drying of 80 weight %
Prepared contact agent, is designated as mfc-1.
Feedstock property employed in embodiment and comparative example is as follows:
Table 1 Vacuum Residue Properties
For inferior raw material shown in table 1, directly cannot be processed using catalytic cracking process, but can be entered using delayed coking
Row processing.So being contrasted the poor residuum processing method being provided with the present invention and delayed coking processing method, to illustrate
The invention effect of the present invention.
Embodiment 1
Decompression residuum is carried out physical separation in supercritical fluid extraction unit, extracting tower top temperature is 240 DEG C, bottom of towe
220 DEG C, solvent is mixed pentane (w (pentane): w (isopentane)=1:2), and pressure limit is 4~12mpa.Extraction obtains after terminating
Yield is 40% tapped oil and 60% raffinates oil.In tapped oil, saturation is divided and the weight/mass percentage composition of fragrance point is 82.1%, drip
Blue or green matter weight/mass percentage composition < 0.1%, carbon residue 6.1%, metal (ni+v) content is 14.1 μ g/g.
Tapped oil is entered catalytic cracking unit, process conditions are: 520 DEG C of reaction temperature, oil ratio 7, water-oil factor 0.05,
Reaction time 3s, products therefrom distribution is shown in Table 2.After catalytic cracking reaction, gained spent agent enters in the first regenerator, carries out lean
Oxygen regenerates, and process conditions are: the temperature in dense bed is 650 DEG C, dense bed centerline velocities 0.3m/s, gas residence time 30
Second, gained flue gas i composition is shown in Table 2.Carbon content 0.4 weight % in semi regeneration agent, semi regeneration agent enters Second reactivator and carries out completely
Regeneration, obtains flue gas ii and regenerative agent.
Entrance of raffinating oil contacts Cracking Unit, and process conditions are: 510 DEG C of reaction temperature, oil ratio 10, water-oil factor 0.2,
Gas phase time of staying 2.0s, products therefrom distribution is shown in Table 2.After contact cracking reaction, gained contact agent to be generated enters the first gasifier
Interior, process conditions are: the temperature in dense bed is 650 DEG C, dense bed centerline velocities 0.25m/s, and gas residence time 30 seconds contains
Oxygen mole content 20% in carrier of oxygen, water molar content 80%, gained gasification gas composition is shown in Table 2.The semi regeneration contact agent of gained
Upper carbon content 0.72 weight %, the second gasifier that semi regeneration contact agent enters contact Cracking Unit is regenerated completely, obtains gas
Change gas ii and regenerate contact agent completely.
Catalytic cracking is merged with the flue gas contacting after cracking semi regeneration and gasification gas and introduces cos and h2S removing dress
Postpone, enter co converting means, gained conversion gas obtains, after carrying out de- Acidic Gas Treating, the h that concentration is 99.2%2.
Embodiment 2
Decompression residuum is carried out physical separation in supercritical fluid extraction unit, extracting tower top temperature is 230 DEG C, bottom of towe
210 DEG C, solvent is mixed pentane (w (pentane): w (isopentane)=1:1), and pressure limit is 4~12mpa.Extraction obtains after terminating
Yield is 38% tapped oil and 62% raffinates oil.In tapped oil, saturation is divided and the weight/mass percentage composition of fragrance point is 83.5%, drip
Blue or green matter weight/mass percentage composition < 0.1%, carbon residue 5.8%, metal (ni+v) content is 10.2 μ g/g.
Tapped oil is entered catalytic cracking unit, process conditions are: 530 DEG C of reaction temperature, oil ratio 8, water-oil factor 0.05,
Reaction time 2.5s, products therefrom distribution is shown in Table 2.After catalytic cracking reaction, gained spent agent enters in the first regenerator, carries out
Oxygen deprivation regenerates, and process conditions are: the temperature in dense bed is 680 DEG C, dense bed centerline velocities 0.35m/s, gas residence time
40 seconds, flue gas i composition was shown in Table 2.Carbon content 0.35 weight % in semi regeneration agent, semi regeneration agent enters the second of catalytic cracking unit
Regenerator is regenerated completely, obtains flue gas ii and regenerative agent.
Entrance of raffinating oil contacts Cracking Unit, and process conditions are: 500 DEG C of reaction temperature, air speed 20h-1, oil ratio 7, water
Oil compares 0.25, and gross pressure (gauge pressure) is 1.0mpa, and hydrogen dividing potential drop is 0.3mpa, and hydrogen-oil ratio is 100m3/m3, products therefrom distribution be shown in Table
2.After contact cracking reaction, gained contact agent to be generated enters in the first gasifier of contact Cracking Unit, and process conditions are: close phase
Temperature in bed is 690 DEG C, dense bed centerline velocities 0.33m/s, gas residence time 50 seconds, is passed through air, gained gasification gas
Composition is shown in Table 2.Carbon content 0.65 weight % on semi regeneration contact agent, semi regeneration contact agent enters the second gas of contact Cracking Unit
Change device to be regenerated completely, obtain gasifying gas ii and regenerate contact agent completely.
Catalytic cracking is merged with the flue gas contacting after cracking semi regeneration and gasification gas and introduces cos and h2S removing dress
Postpone, obtain rich in co and h2Gas, can use as fuel gas.
Comparative example 1
Decompression residuum is processed using delay coking process, process conditions are: 500 DEG C of furnace outlet temperature, pressure
Power 0.15mpa, recycle ratio 0.2, products therefrom distribution is shown in Table 3.
To same decompression residuum, the distribution of delayed coking product is divided with by the embodiment of the present invention 1,2 gained condensation products
Cloth is contrasted, and is shown in Table 3.
Can be seen that and poor residuum is processed using the inventive method from table 2,3 data, yield of light oil can be improved, increase
Liquid feeding is received, and reduces coke yield, has the coke (generally 1200 yuan/ton of coke price) of quite a few low value permissible simultaneously
It is converted into the hydrogen (20000 yuan/ton) of high added value or be used as fuel gas.Simultaneously the sulphur in petroleum coke can be converted into cos or
h2S, decreases process soxExpense.
Table 2
Project | Embodiment 1 | Embodiment 2 |
Catalytic cracking unit product 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 mole forms (butt)/% | ||
co | 20.70 | 27.26 |
co2 | 15.80 | 14.22 |
n2 | 63.50 | 58.52 |
cos/ppm | 32 | 28 |
h2s/ppm | 6 | 2 |
Contact Cracking Unit product distribution/% | ||
h2s | 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 gas mole composition (butt)/% | ||
co | 44.31 | 24.33 |
co2 | 45.21 | 12.17 |
h2 | 10.12 | 0 |
ch4 | 0.36 | 0 |
n2 | 0.00 | 63.5 |
cos/ppm | 560 | 6874 |
h2s/ppm | 5500 | 640 |
Table 3
Project | Embodiment 1 | Embodiment 2 | Comparative example |
Products collection efficiency/% | |||
h2s | 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 |
It is converted into h2Coke | 11.32 | —— | |
It is 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. a kind of inferior heavy oil combinational processing method, comprises the following steps:
(1) heavy oil feedstock i carries out Component seperation in supercritical fluid extraction unit, obtains the extraction dividing and fragrance divides rich in saturation
Oil and raffinating oil rich in resin and asphalt component;
(2) tapped oil of step (1) gained enters catalytic cracking unit, is reacted in the presence of catalytic cracking catalyst,
Obtaining catalytic cracker gas, catalytically cracked gasoline, catalytic cracking diesel oil, catalytic cracked oil pulp and deposition has the spent agent of coke,
Spent agent carries out two-stage regeneration, first paragraph for oxygen deprivation regeneration obtain semi regeneration agent and flue gas i, the sulphur in wherein flue gas i mainly with
Cos form exists, and second segment is oxygen enrichment regeneration, the catalyst after being regenerated completely and flue gas ii, urging after regenerating completely
Agent returns catalytic cracking unit;
(3) the raffinating oil to enter by a certain percentage with heavy oil feedstock ii and contact Cracking Unit, in the work of contact agent of step (1) gained
With under, carry out under hydro condition or under conditions of non-hydrogen contact cracking reaction, obtain contact cracked gas, contact cracking vapour
Oil, contact cracked diesel oil, contact cracking slurry oil and deposition have the contact agent to be generated of coke, in the first gasifier, make to be generated connecing
There is imperfect combustion reaction in the charcoal in tactile agent and oxygen-containing gas i, obtain semi regeneration contact agent and gasification gas i, and wherein gasify gas i
In sulphur mainly with h2S and cos form exist;
(4) the semi regeneration contact agent of step (3) gained is in the second gasifier, under conditions of oxygen-containing gas ii exists, contact agent
Upper residual charcoal occurs to burn completely, is regenerated contact agent and gasification gas ii completely, the sulphur in gasification gas ii is with soxForm is deposited
In regeneration contact agent return to step (3) contact Cracking Unit completely;
(5) described flue gas i and gasification gas i enters cos and h2S removal unit, the gas after desulfurization uses as fuel gas, or
Person enters converter unit hydrogen.
2. according to claim 1 method it is characterised in that described heavy oil feedstock i and heavy oil feedstock ii carbon residue be 15 weight %
~50 weight %, tenor is in 25~1000 μ g/g.
3. according to claim 1 method it is characterised in that in described step (1) supercritical fluid extraction unit solvent for use be
c3~c5The mixture of one or more of alkane and alkene, solvent is 3~12:1 with the volume ratio of heavy oil feedstock i.
4. according to claim 1 method it is characterised in that extraction tower pressure in supercritical fluid extraction unit in described step (1)
Power 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.
5. according to claim 1 method it is characterised in that in tapped oil described in described step (1), saturation is divided and fragrance point
Weight/mass percentage composition >=70%, asphalitine weight/mass percentage composition≤0.5%.
6. according to claim 1 method it is characterised in that described step (1) gained extract out oil yield control 20%~
40%.
7. according to claim 1 method it is characterised in that the catalytic cracking reaction condition described in described step (2) is: anti-
Answer 470~550 DEG C of temperature, 0.5~5.0 second reaction time, the weight ratio 3~20 of catalytic cracking catalyst and feedstock oil.
8. according to claim 1 method it is characterised in that the catalytic cracking catalyst described in described step (2) include boil
Stone, inorganic oxide and clay, the weight percentage of each component is respectively as follows: zeolite 5%~50%, inorganic oxide 5%~
95%, clay 0~90%.
9. according to claim 1 method it is characterised in that in described step (2) spent agent and air send out in the first regenerator
Raw combustion with meagre oxygen reaction, the temperature in dense bed is 550~750 DEG C, dense bed centerline velocities 0.05~0.6m/s, and gas stops
0.5~60 second time;Obtain semi regeneration agent in the first regenerator, the carbon content in semi regeneration agent is 0.3~0.5 weight %;Institute
State semi regeneration agent entrance Second reactivator to be regenerated completely, complete regeneration temperature is 600~750 DEG C, logical in Second reactivator
The oxygen content entering gas is 10 volume %~50 volumes %.
10. according to claim 1 method it is characterised in that under conditions of non-hydrogen in described step (3), contact cracker
Interior process conditions are: 450~650 DEG C of reaction temperature, weight (hourly) space velocity (WHSV) 1~100h-1, the mass ratio of contact agent and raw material is 1~
30:1, the gas phase time of staying 0.5~5.0s, vapor is 0.05~1:1 with the mass ratio of raw material.
11. according to claim 1 method it is characterised in that under hydro condition in described step (3), in contact cracker
Process conditions be: 450~650 DEG C of reaction temperature, weight (hourly) space velocity (WHSV) 1~100h-1, contact agent is 1~30 with the mass ratio of raw material:
1, vapor is 0.05~1:1 with the mass ratio of raw material, and gross pressure is 0~1mpa gauge pressure, and hydrogen dividing potential drop is 0.1~0.5mpa, hydrogen
Oil ratio is 10~1500m3/m3.
12. are selected from the contact containing molecular sieve according to the method for claim 1 it is characterised in that contacting contact agent used by Cracking Unit
Agent and/or the contact agent without molecular sieve.
13. according to claim 12 method it is characterised in that the described contact agent containing molecular sieve is to divide selected from molecular sieve containing x, y
The contact agent of one or more of sub- sieve, modenite, zsm-5, clay molecular sieve with layer structure, sapo molecular sieve.
14. according to claim 12 method it is characterised in that the described contact agent without molecular sieve refer to amorphous silicon aluminium,
One or more of carclazyte, kaolin, montmorillonite, rectorite, illite, chlorite, boehmite, silica mixed
The contact agent that compound is prepared for raw material.
15. according to claim 1 method it is characterised in that in described step (3) the first gasifier be fluidized-bed gasifier, close
Temperature in phase bed is 550~800 DEG C, dense bed centerline velocities 0.05~0.6m/s;In described oxygen-containing gas i, oxygen mole divides
Number is 10%~30%, and remaining is vapor, carbon dioxide and/or nitrogen, gas residence time 0.5~60 second.
16. according to claim 1 method it is characterised in that (co+h in the gasification gas i that generates in described step (3)2)/co2
Mol ratio 0.5~3.
17. according to claim 1 method it is characterised in that the h that gasifies in gas i of described step (3)2S and cos account for gasification
More than 99.0 volumes % of total sulfur in gas i.
18. according to claim 1 method it is characterised in that the carbon content of contact agent to be generated that described step (3) obtains exists
0.5%~5.0 weight %;The carbon content of the semi regeneration contact agent obtaining in described step (3) is in 0.3~2.0 weight %.
19. in accordance with the method for claim 1 it is characterised in that in described second gasifier, reaction temperature is 600~750
DEG C, the oxygen content of oxygen-containing gas ii is 10 volume %~50 volumes %.
20. according to claim 1 method it is characterised in that the described cos of step (5) and h2S removal unit is by cos
It is converted into h2The further Recovered sulphur of s, or absorbing carbonyl sulfur reclaim cos.
21. in accordance with the method for claim 1 it is characterised in that do not include step (4), and the semi regeneration that step (3) obtains connects
Tactile agent is directly or part return to step (3) contacts Cracking Unit.
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CN103055959A (en) * | 2011-10-24 | 2013-04-24 | 中国石油化工股份有限公司 | Catalyst regeneration method |
CN103305273A (en) * | 2012-03-16 | 2013-09-18 | 中国石油化工股份有限公司 | Catalytic conversion method for reducing yields of cokes and dry gases |
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US7033486B2 (en) * | 2002-04-01 | 2006-04-25 | Exxonmobil Research And Engineering Company | Residuum conversion process |
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JPS60133088A (en) * | 1983-12-22 | 1985-07-16 | Res Assoc Residual Oil Process<Rarop> | Catalytic cracking of heavy oil and production of hydrogen |
US5152886A (en) * | 1990-10-31 | 1992-10-06 | Laboratorios Paris, C.A. | Method for improving heavy crude oils by reducing the asphaltene content of crude oils and oil-containing tar sands |
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