CN104593040B - Heavy oil lightening method capable of simultaneously removing metals on contact agent - Google Patents
Heavy oil lightening method capable of simultaneously removing metals on contact agent Download PDFInfo
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- CN104593040B CN104593040B CN201310526754.6A CN201310526754A CN104593040B CN 104593040 B CN104593040 B CN 104593040B CN 201310526754 A CN201310526754 A CN 201310526754A CN 104593040 B CN104593040 B CN 104593040B
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Abstract
The invention discloses a heavy oil lightening method capable of simultaneously removing metals on a contact agent. The heavy oil lightening method utilizes a contact cracking unit, a gasification unit, a carbonylation unit, a metal recovery unit and a contact agent regeneration unit. According to the heavy oil lightening method, in heavy oil lightening, a contact cracking-gasification product reduces metal oxides deposited on the contact agent into simple substance metals and then the metals are removed by carbonylation. The heavy oil lightening method has mild technical conditions and no pollution on the environment.
Description
Technical field
The present invention relates to a kind of method of heavy oil lighting processing, more particularly, it relates to one kind adds in heavy oil lighting
The method of the deposited metal on Removal of catalyst simultaneously during work.
Background technology
During by heavy oil lighting, catalytic cracking because it is economical, rationally and can produce high-quality product and
By refining, enterprise is paid attention to.Increasingly become weight with petroleum resources, carbon residue, sulfur and tenor increase, more residual oil and/or
Heavy oil becomes the raw material of secondary operations.But, in residual oil and/or heavy oil, it is enriched in crude oil most of metal, enters in heavy oil
During row catalyzed cracking processing, these metals mostly deposit on a catalyst, and produce poisoning effect to catalyst, change it
Property, thus affect product slates.RFCC requirement catalyst can be under conditions of more harmful metal pollutions
Keep certain activity, therefore RFCC ingredient requirement (ni+v) < 25 μ g g-1, generally 10 μ g g-1Left and right, that is,
Just such, for keeping the certain activity of catalyst, need to periodically draw off the too high catalyst of tenor, and supplement fresh catalyst
Agent, this not only adds operating cost, and dead catalyst also will cause problem of environmental pollution.
Us4293403 discloses a kind of wet treatment dead catalyst, the metal in Removal of catalyst such as nickel, ferrum and/or vanadium
Method, using sulfuration, oxidation, acid elution is by metal removal, but can produce scrub raffinate, causes secondary pollution to environment, with
When damage catalyst activity.Cn1198366a discloses the dry method demetalization of a kind of residual oil and/or catalyst for heavy oil catalytic cracking
Regeneration techniques, dead catalyst is reduced after sulfur activation, is then contacted generation gaseous metal carbonyl compound and solid-state with co gas
Catalyst separates.Due to removing metal using this chemical reaction, activating and reducing process needs to introduce hydrogen sulfide and hydrogen, carbonylation
Course of reaction needs to introduce co gas, can only carry out demetalization regeneration after drawing off catalyst.Chinese patent cn1398792a carries
The method having gone out synthesizing carbonyl nickel, when in co contain a small amount of h2Carbonylation rate can be accelerated during s.And metallic nickel is in catalysis
Passing through in Cracking catalyst is presented in nickel aluminate, such as wants that generating Nickel tetracarbonyl. needs first nickel aluminate to be reduced to simple substance.
When containing h in reducing atmosphere2The reduction reaction of nickel during s, can be accelerated.
Inferior heavy oil contact cracking-coke gasification integral processing method is by contact cracking and band charcoal contact agent gasification
Process is organically combined.Can be produced rich in co and h by adjusting the composition of gasification gas2Gasification product, in reducing atmosphere
Under, the sulfur on contact agent generates h2s.Therefore, the method is passed through to design suitable flow process it is possible to online demetalization, and
To metal side-product.
Content of the invention
The technical problem to be solved in the present invention is on the basis of existing technology, provides one kind in heavy oil contact cracking gasification
In integrated process, the method that removes simultaneously and reclaim on contact agent the metal of deposition.
The heavy oil lightening method of metal on a kind of contact agent of removing simultaneously, comprising:
(1) in contact Cracking Unit, heavy oil enters contact cracker, carries out contacting cracking in the presence of contact agent
Reaction, the effluent of contact cracker includes dry gas, liquefied gas, gasoline fraction, diesel oil distillate, wax oil fraction and band charcoal and connects
Tactile agent, described band charcoal contact agent enters gasification unit；
(2) in gasification unit, step (1) resulting tape charcoal contact agent enters in fluidized-bed gasifier, containing water and oxygen
Gasifying agent in the presence of, make charcoal on contact agent and gasifying agent reaction, obtain semi regeneration contact agent and be rich in co, h2Gasification
Gas, wherein, the sulfur in gasification gas is with h2Presented in s, on contact agent, the metal of deposition is contacted with reproducibility gasification gas, is lived
Change, be reduced to metal simple-substance；
(3) in carbonylation unit, the semi regeneration contact agent of step (2) gained is contacted with co, metal simple-substance carbonyl on contact agent
Glycosylation reaction obtains gaseous metal carbonyl compound, and separates with solid state contacts agent, obtains demetallated semi regeneration contact agent；
(5) in metals recovery units, in thermal decomposition reactor, gaseous metal in the admixture of gas of step (3) gained
Carbonyl compound thermally decomposes as co gas and metal solid, and by metal recovery.
Preferably, also include between step (3) and step (5): (4) in regeneration unit, under conditions of with the presence of oxygen,
On demetallated semi regeneration contact agent, residual charcoal occurs to burn completely, is regenerated contact agent and flue gas completely, and regeneration completely connects
Tactile agent return to step (1) contacts Cracking Unit；
Preferably, also include: (6) are rich in co, h in the gas obtained by sulfur recovery unit, step (5)2And h2S, described
Gas enters sulfur recovery unit removing sulfur, and the gas part after gained desulfurization returns to carbonylation reactor circulation, partly outer row
Go out device after Water gas shift/WGS device, separate and obtain hydrogen and co2.
On removing contact agent while the present invention provides, the heavy oil lightening method of metal has the beneficial effect that
The method that the present invention provides, co, the h being generated using gasification2And h2The reducing atmosphere of s, directly passes through carbonylation
The online poisonous metal removing deposition on contact agent of reaction, extends the contact agent life-span；Demetalization operating condition connects not less than heavy oil
Tactile cracking-coke gasification condition, operating cost is relatively low；Process conditions are gentle, without compromising on the active ingredient of load on contact agent,
More will not damaging contact agent framing structure；High value metals side-product can also be obtained；The heavy oil lighting side that the present invention provides
Method environmentally safe.
Brief description
Fig. 1 is the schematic flow sheet of the heavy oil lightening method of metal on removing contact agent while the present invention provides.
Wherein: 1- contact Cracking Unit；2- gasification unit；3- carbonylation unit；4- regeneration unit；5- thermal decomposition unit；
6- sulfur recovery unit；7- Water gas shift/WGS device；8～29- pipeline.
Specific embodiment
The heavy oil lightening method of metal on a kind of contact agent of removing simultaneously, comprising:
(1) in contact Cracking Unit, heavy oil enters contact cracker, carries out contacting cracking in the presence of contact agent
Reaction, the effluent of contact cracker includes dry gas, liquefied gas, gasoline fraction, diesel oil distillate, wax oil fraction and band charcoal and connects
Tactile agent, described band charcoal contact agent enters gasification unit；
(2) in gasification unit, step (1) resulting tape charcoal contact agent enters in fluidized-bed gasifier, containing water and oxygen
Gasifying agent in the presence of, make charcoal on contact agent and gasifying agent reaction, obtain semi regeneration contact agent and be rich in co, h2Gasification
Gas, wherein, the sulfur in gasification gas is with h2Presented in s, on contact agent, the metal of deposition is contacted with reproducibility gasification gas, is lived
Change, be reduced to metal simple-substance；
(3) in carbonylation unit, the semi regeneration contact agent of step (2) gained is contacted with co, metal simple-substance carbonyl on contact agent
Glycosylation reaction obtains gaseous metal carbonyl compound, and separates with solid state contacts agent, obtains demetallated semi regeneration contact agent；
(5) in metals recovery units, in thermal decomposition reactor, gaseous metal in the admixture of gas of step (3) gained
Carbonyl compound thermally decomposes as co gas and metal solid, and by metal recovery.
Preferably, also include between step (3) and step (5): (4) in regeneration unit, under conditions of with the presence of oxygen,
On demetallated semi regeneration contact agent, residual charcoal occurs to burn completely, is regenerated contact agent and flue gas completely, and regeneration completely connects
Tactile agent return to step (1) contacts Cracking Unit；
Preferably, also include: (6) are rich in co, h in the gas obtained by sulfur recovery unit, step (5)2And h2S, described
Gas enters sulfur recovery unit removing sulfur, and the gas part after gained desulfurization returns to carbonylation reactor circulation, partly outer row
Go out device after Water gas shift/WGS device, separate and obtain hydrogen and co2.
Preferably, contain so in the flue gas obtaining in step (4) regeneration unitx, described flue gas is by alkaline cleaner or sulfur
Transfer agent desulfurization is outer after reaching discharge standard to arrange.
In the method that the present invention provides, described heavy oil can be heavy crude, acid-containing raw oil, super-viscous oil, reduced crude, subtract
Pressure residual oil, decompressed wax oil, wax tailings, deasphalted oil, oil sands bitumen, hydrocracking tail oil, coal tar, shale oil, tank bottoms oil,
Coal liquefaction residue is oily or one of other secondary operations distillate or more than one mixture.Preferably heavy oil exists for carbon residue
5wt%～40wt%, tenor is in the inferior heavy oil of 1～1000 μ g/g.
The operating condition of the contact Cracking Unit in step (1) is: reaction temperature is 450～650 DEG C, and weight (hourly) space velocity (WHSV) is 1
～100h-1, contact agent is 1～30:1 with the mass ratio of heavy oil feedstock, and vapor is 0.05～1 with the mass ratio of heavy oil feedstock:
1.
Contact agent in step (1) is silica-alumina material and/or gasifying catalyst.When contact agent is silica-alumina material and gasification is urged
During agent, gasifying catalyst and silica-alumina material are mechanical mixture, or gasifying catalyst is supported on silica-alumina material.Wherein,
Described silica-alumina material is selected from the catalytic cracking catalyst containing molecular sieve and/or the catalytic cracking catalyst without molecular sieve.
Described gasifying catalyst is selected from and comprises single metal or various metals in alkali metal, alkaline-earth metal and viii race metal
One or more of the natural crystal of combination, synthetic material and derivative compound.
The band charcoal contact agent carbon content that step (1) obtains is in 0.5wt%～7.0wt%
The gasification temperature of step (2) fluidized-bed gasifier is 550～800 DEG C.Described fluidized gasification device can be selected from solid
Constant current fluidized bed reactor, riser reactor or fixed fluidized bed and dilute-phase leanphase fluidized bed combination reactor types.Preferably, described
Fluidized-bed gasifier adopts the combined fluidized bed form of bottom close phase section top dilute phase section, and operating condition is: gas residence time
0.5～60 second, preferably 1.0～10 seconds, the gasification temperature of dense bed was 550～800 DEG C, preferably 600～700 DEG C, dense bed
Linear velocity 0.05～0.6m/s, preferably 0.2～0.4m/s；Treatment with external measures hot mode is taken to make dilute phase in the dilute phase section of fluidized-bed gasifier
The temperature of section is less than 680 DEG C.
Contain oxygen and vapor in gasifying agent in step (2) it is preferable that in gasifying agent oxygen mole fraction be 5%～
30%th, more preferably 5～20%, vapor molar fraction is 70%～95%, more preferably 80～95%.
On contact agent to be generated in step (2), coke occurs the h2s in the gasification gas that gasification reaction is generated to account in gasification gas
70v%～the 99.9v% of total sulfur.
In step (2), the carbon content of semi regeneration contact agent is in 0.4～1.0wt%.
In step (3), the concentration of carbonylation co is 10v%～99v%, preferred 40v%～90v%.
In step (3) reaction temperatures for carbonylation be 100～200 DEG C, preferably 110～180 DEG C, reaction pressure be 0.05～
1.0mpa(gauge pressure)；Response time is 0.1～24 hour, preferably 0.5～15 hour.
The semi regeneration contact agent obtaining in step (2) in the method that the present invention provides can fully enter step (3) carbonyl
Change removing metal in unit it is also possible to be partially into step (3) carbonylation unit removing metal, be partially into step (4) regeneration
Direct Regeneration in unit.
The regeneration temperature of step (4) semi regeneration contact agent is 600～750 DEG C, and being passed through gas is oxygen-containing 10v%～50v%
Gas, preferred air.
In step (5) pyrolysis temperature be 200～300 DEG C, preferably 240～290 DEG C, reaction pressure be 0.03～
0.5mpa(gauge pressure), preferably 0.03～0.5mpa(gauge pressure), the response time be 0.5～15 hour, preferably 1～10 hour.
Describe the heavy oil lightening method of metal on removing contact agent while the present invention provides referring to the drawings in detail
Preferred implementation, but the present invention is not therefore subject to any restriction.
Fig. 1 is the schematic flow sheet of the heavy oil lightening method of metal on removing contact agent while the present invention provides.As
Shown in accompanying drawing 1, heavy oil feedstock passes through pipeline 8 entrance with atomizing steam and contacts Cracking Unit 1, the fresh contact supplementing through pipeline 9
Agent connects with from regenerator pipeline 18 regeneration contact agent out and/or enter from pipeline 26 carbonylation unit semi regeneration agent out
Tactile Cracking Unit 1, after heavy oil contacts generation cracking reaction in cracker with contact agent, the oil gas of generation passes through pipeline 10
Enter subsequent separation system, contact agent to be generated enters gasification unit 2 by pipeline 11.In gasification unit 2, on contact agent to be generated
Coke there is gasification reaction with the oxygen of vapor from pipeline 13 and pipeline 12, the gasification gas of generation is drawn from pipeline 14
Enter carbonylation unit 3, in carbonylation unit 3, the metal of activated reduction and carbonylation reactor on semi regeneration contact agent
Interior co and the part co reaction returning from pipeline 28, the demetalization semi regeneration of the gaseous metal carbonyls of generation and solid-state connects
Tactile agent.Gaseous metal carbonyls and unreacted gasification gas enter thermal decomposition unit 5 by pipeline 20, in thermal decomposition unit
5, there are pyrolysis in metal carbonyls, generates metal simple-substance and co, and the metal of generation periodically reclaims from pipeline 29, containing co
Gas by pipeline 21 enter sulfur recovery unit 6, reclaim sulfur after partial gasification gas by pipeline 22 enter Water gas shift/WGS
Device 7, co is occurred transformationreation to generate co with water2And h2, by co2And h2Respectively from pipeline 23,24 extraction systems after separating.
In sulfur recovery unit 6, the gasification gas of partial desulfurization returns carbonylation unit 3 by pipeline 28, from carbonylation unit 3 taking off out
Metal semi regeneration contact agent by pipeline 15 enter regeneration unit 4, demetalization semi regeneration contact agent and/or from gasification unit come
There is complete combustion reaction, the cigarette of generation with the oxygen of the air from pipeline 16 and pipeline 17 in the coke on semi regeneration contact agent
Gas is entered after flue gas desulfurization device reaches discharge standard by pipeline 19 and can directly discharge air, the contact agent after being regenerated
Regenerator is drawn by pipeline 18.
Describe the present invention below with embodiment in detail, but embodiment use model not thereby limiting the invention
Enclose.The contact agent being adopted is aluminium oxide containing 10wt%, 80wt% kaolinic be spray-dried after roasting be obtained contact agent, be designated as
mfc-1；The contact agent that after spray drying containing 90% aluminium oxide, roasting is obtained, is designated as mfc-2；Adopted divides containing laminated clay column
The numbering of the catalytic cracking catalyst of son sieve and zsm-5 molecular sieve is designated as mfc-3；The catalytic cracking catalyst being adopted is commodity
The trade mark is crc-1 catalytic cracking catalyst (being produced by Shandong catalyst branch company of sinopec catalyst head office)；Gasification catalysis
Agent preparation method is to take 6kg Kaolin, adds 18 deionized waters, stirs at 30 DEG C, and adds 3kg oxidation while stirring
The mixture of potassium and calcium oxide, wherein potassium and calcium atom ratio for 0.4, adds 0.2kg Alumina gel, roasts at 600 DEG C after spray drying
Burn 60min and obtain gasifying agent, be designated as gc-1；Through pulverizing mean diameter in 65 μm of natural dolomite, it is designated as gc-2.
In embodiment, heavy oil feedstock property is shown in Table 1.
Table 1 heavy oil property
On contact agent, nickel content analysis method uses x-ray fluorescent spectrometry.
Nickel removal rate computational methods are as follows:
Embodiment 1
The catalytic cracking catalyst of product designation crc-1 is carried out mechanical mixture, Liang Zhezhi with gasifying catalyst gc-1
Amount ratio is 9:1, and through multiple dipping pollution metallic nickel, nickel content is 20000ppm, after 800 DEG C, 17 hours hydrothermal treatment consists
Be 18.10% with carbon residue, metal be 200 μ g/g, sulfur content be that the heavy oil of 1.12wt% splits contacting Cracking Unit and come in contact
Change reaction, the process conditions of contact cracking reaction are: 500 DEG C of cracking temperature, air speed 20h-1, oil ratio 7, water-oil factor 0.2, gained
The coke content of spent agent is 2.5wt%.
Spent agent is through stripping laggard fluidized bed gasification unit.The gas linear velocity of gasification unit is 0.12m/s, gasification
680 DEG C of temperature, is passed through oxygen-containing 20%(mole), 80%(mole of water) gasifying agent, gas residence time 5 seconds, the response time is 1 little
, there is gasification reaction, metallic nickel and h on spent agent in Shi Fa2S and h2Activate, reduction reaction.Treatment with external measures hot mode is taken to make stream
Change bed dilute phase section temperature control less than 650 DEG C.Obtain after gas solid separation in gasification unit semi regeneration agent containing charcoal 0.45wt% and
Gaseous product, (co+h in gaseous product2)/co2Mol ratio be 1.50, h2S accounts for the 95.2%(volume of total sulfur in gasification gas), gas
After activating QI enters sulfur recovery unit removing sulfur, gasification gas separates through Water gas shift/WGS and obtains hydrogen and co2.
Semi regeneration agent send into carbonylation low speed circulating fluidized bed, 110 DEG C of reaction temperature, be passed through gas molar consist of containing 60%co,
5%h2、5%h2S, remaining be co2, reaction pressure 0.15mpa(gauge pressure), the response time is 1 hour, h2S be catalyst, make ni with
Co reacts, and generates gaseous state ni (co)4.Enter thermal decomposition reactor from carbonylation reactor effluent air, reaction temperature is 240
DEG C, and in 0.1mpa(gauge pressure) react 10 hours under pressure, ni (co)4It is decomposed into solid metallic ni and co gas.Demetallated
Semi regeneration agent is sent in regeneration unit, 680 DEG C of reaction temperature, the air reaction with oxygen-containing volume fraction 18%.Gas-solid in regenerator
Regenerated flue gas and regenerative agent is obtained, the sulfur in flue gas is mainly so after separatingx, flue gas is after alkaline cleaner reaches discharge standard
Outer row, the coke content of regenerative agent is 0.02wt%.
After whole flow process, contact agent nickel removal rate is about 30%.
Embodiment 2
Raw material same as Example 1 and flow process, the except for the difference that carbonylation time.Contact agent through Cracking Unit and
Gasification unit, carbonylation low speed circulating fluidized bed, 110 DEG C of reaction temperature are sent in gained semi regeneration agent, are passed through gas molar and consist of and contain
60%co、5%h2、5%h2S, remaining be co2, reaction pressure 0.15mpa(gauge pressure), the response time is 8 hours, h2S is catalyst,
So that ni is reacted with co, generate gaseous state ni (co)4.After regeneration, contact agent nickel removal rate is 70% to demetallated semi regeneration contact agent.
Embodiment 3
By contact agent mfc-1 through multiple dipping pollution metallic nickel, nickel content is 20000ppm, through 800 DEG C, 17 hours water
It is that the heavy oil that 35.0%, metal 425 μ g/g, sulfur content are 3.12wt% connects contacting Cracking Unit with carbon residue after heat treatment
Tactile cracking reaction, the process conditions of contact cracking reaction are: 520 DEG C of cracking temperature, air speed 50h-1, oil ratio 20, water-oil factor
0.5, the coke content of gained spent agent is 2.8wt%.
Spent agent is through stripping laggard fluidized bed gasification unit.The gas linear velocity of gasification unit is 0.4m/s, gasification
560 DEG C of temperature, is passed through the gasifying agent mole consisting of containing 30% oxygen, 70% water, gas residence time 50 seconds, gasification reaction occurs.
Treatment with external measures hot mode is taken to make fluid bed dilute phase section temperature control less than 560 DEG C.Obtain containing charcoal after gas solid separation in gasification unit
The semi regeneration agent of 0.50wt% and gaseous product, (co+h in gaseous product2)/co2Mol ratio be 0.8, h2S accounts for total in gasification gas
The 76.8%(volume of sulfur), gasification gas enter sulfur recovery unit removing sulfur after, gasification gas through Water gas shift/WGS separate obtain hydrogen and
co2, hydrogen and co2After separating, co2Can trap.
Carbonylation low speed circulating fluidized bed, 110 DEG C of reaction temperature are sent in gained semi regeneration agent, are passed through gas molar and consist of and contain
50%co、5%h2、5%h2S, remaining be co2, reaction pressure 0.15mpa(gauge pressure), the response time is 6 hours, h2S is catalyst,
So that ni is reacted with co, generate gaseous state ni (co)4.Enter thermal decomposition reactor, reaction temperature from carbonylation reactor effluent air
Spend for 270 DEG C, and in 0.4mpa(gauge pressure) react 2 hours under pressure, ni (co)4It is decomposed into solid metallic ni and co gas.Half
650 DEG C of reaction temperature in regeneration unit sent into by regenerative agent, carries out complete regenerative response with the gas of oxygen-containing volume fraction 15%.Again
Regenerated flue gas and regenerative agent is obtained after gas solid separation, the sulfur in flue gas is mainly so in raw devicex.
After whole flow process, contact agent nickel removal rate is 28%.
Embodiment 4
By silica-alumina material mfc-2 and silica-alumina material mfc-3 after 2:1 mixes in mass ratio, through multiple dipping pollution metallic nickel,
Nickel content be 20000ppm with containing with carbon residue be 20.0 weight %, tenor be 120 μ g/g, sulfur content be 3.12%(mass)
Heavy oil come in contact cracking reaction in contact Cracking Unit, the process conditions of contact cracking reaction are: 550 DEG C of cracking temperature,
Air speed 80h-1, oil ratio 28, water-oil factor 0.1, the coke content of gained spent agent is 2.0 weight %.
Spent agent is through stripping laggard fluidized bed gasification unit device.The gas linear velocity of the dense bed in gasifier is
0.6m/s, 700 DEG C of gasification temperature, is passed through oxygen-containing 15%(mole), 85%(mole of water) gasifying agent, gas residence time 55 seconds,
There is gasification reaction.Treatment with external measures hot mode is taken to make fluid bed dilute phase section temperature control less than 600 DEG C.In gasification unit, gas-solid divides
From after obtain semi regeneration agent and the gaseous product of carbon content 1.0 weight %, (co+h in gaseous product2)/co2Mol ratio be 45,
h2S accounts for the 99.2%(volume of total sulfur in gasification gas), after gasification gas enters sulfur recovery unit removing sulfur, gasification gas becomes through water gas
Change to separate and obtain hydrogen and co2, hydrogen and co2After separating, co2Can trap.
Carbonylation low speed circulating fluidized bed, 150 DEG C of reaction temperature are sent in gained semi regeneration agent, are passed through gas molar and consist of and contain
50%co、5%h2、5%h2S, remaining is co2, reaction pressure 0.15mpa(gauge pressure), the response time is 6 hours, h2S is catalyst,
So that ni is reacted with co, generate gaseous state ni (co)4, enter thermal decomposition reactor, reaction temperature from carbonylation reactor effluent air
Spend for 250 DEG C, and in 0.03mpa(gauge pressure) react 15 hours under pressure, ni (co)4It is decomposed into solid metallic ni and co gas.
730 DEG C of reaction temperature in regeneration unit sent into by the later half regenerative agent of demetalization, enters with the gas of oxygen-containing volume fraction 10%
The complete regenerative response of row.Regenerated flue gas and regenerative agent is obtained, the sulfur in flue gas is mainly so after gas solid separation in regeneratorx, cigarette
Gas is outer after alkaline cleaner reaches discharge standard to be arranged, and the coke content of complete regenerative agent is 0.02wt%, and returns contact cracking
Unit.Contact agent nickel removal rate is 75%.
Embodiment 5
By contact agent mfc-2 with gc-2 1:1 mechanical mixture in mass ratio uniformly, it is that 25.0%, tenor is with carbon residue
100.1 μ g/g, sulfur content are that the petroleum hydrocarbon of 3.12wt% comes in contact cracking reaction in contact Cracking Unit, contact cracking reaction
Process conditions be: 580 DEG C of cracking temperature, air speed 30h-1, oil ratio 15, water-oil factor 0.3, the coke content of gained spent agent is
4.2%.
Spent agent is through stripping laggard fluidized bed gasification unit.The gas linear velocity of gasification unit is 0.32m/s, gasification
650 DEG C of temperature, is passed through oxygen-containing 10%(mole), 90%(mole of water) gasifying agent, gas residence time 10 seconds, occur gasified reverse
Should.Treatment with external measures hot mode is taken to make fluid bed dilute phase section temperature control less than 630 DEG C.Contained after gas solid separation in gasification unit
The semi regeneration agent of charcoal 0.8% and gaseous product, (co+h in gaseous product2)/co2Mol ratio be 5, h2S accounts for total sulfur in gasification gas
85.6%(volume), gasification gas enter sulfur recovery unit removing sulfur after, gasification gas through Water gas shift/WGS separate obtain hydrogen and
co2, hydrogen and co2After separating, co2Can trap.
Carbonylation low speed circulating fluidized bed, 150 DEG C of reaction temperature are sent in gained semi regeneration agent, are passed through gas molar and consist of and contain
70%co、5%h2、5%h2S, remaining is co2, reaction pressure 0.15mpa(gauge pressure), the response time is 15 hours, h2S is catalyst,
So that ni is reacted with co, generate gaseous state ni (co)4, enter thermal decomposition reactor, reaction temperature from carbonylation reactor effluent air
Spend for 270 DEG C, and in 0.4mpa(gauge pressure) react 2 hours under pressure, ni (co)4It is decomposed into solid metallic ni and co gas.De-
650 DEG C of reaction temperature in regeneration unit, the air reaction with oxygen-containing volume fraction 15% are sent in the semi regeneration agent of metal.Regenerator
Regenerated flue gas and regenerative agent is obtained, the sulfur in flue gas is mainly so after middle gas solid separationx, flue gas reaches discharge by alkaline cleaner
Outer row after standard, returns contact Cracking Unit.Contact agent nickel removal rate is 85%.
The contact agent demetallization per carbonylation time is relevant, therefore can design cycle as needed, such as by gasified reverse
Carbonylation unit should be fully entered for later half regenerative agent, select the shorter response time, after part demetalization, enter next unit, or
Later half for gasification reaction regenerative agent part is directly entered regeneration unit by person, and another part semi regeneration agent enters carbonylation unit, choosing
Select the longer response time, after depth demetalization, enter next unit.
Claims (19)
1. a kind of heavy oil lightening method of metal on contact agent that simultaneously removes is it is characterised in that comprise the following steps:
(1) in contact Cracking Unit, heavy oil enters contact cracker, carries out contact cracking anti-in the presence of contact agent
Should, the effluent of contact cracker includes dry gas, liquefied gas, gasoline fraction, diesel oil distillate, wax oil fraction and carries charcoal to contact
Agent, described band charcoal contact agent enters gasification unit, and the band charcoal contact agent carbon content obtaining is in 0.5wt%～7.0wt%；
(2) in gasification unit, step (1) resulting tape charcoal contact agent enters in fluidized-bed gasifier, in the gas containing water and oxygen
In the presence of agent, make the charcoal on contact agent and gasifying agent reaction, obtain semi regeneration contact agent and be rich in co, h2Gasification gas, its
In, the sulfur in gasification gas is with h2Presented in s, on contact agent, the metal of deposition is contacted with reproducibility gasification gas, is activated, also
Originally it was metal simple-substance, in step (2), the carbon content of semi regeneration contact agent is in 0.4～1.0wt%；(3) in carbonylation unit, step
(2) the semi regeneration contact agent of gained is contacted with co, and on contact agent, metal simple-substance carbonylation obtains gaseous metal carbonyl compound,
And separate with solid state contacts agent, obtain demetallated semi regeneration contact agent；
(4) in regeneration unit, under conditions of with the presence of oxygen, on demetallated semi regeneration contact agent, residual charcoal occurs to fire completely
Burn, regenerated contact agent and flue gas completely, completely regeneration contact agent return to step (1) contact Cracking Unit；
(5) in metals recovery units, in thermal decomposition reactor, gaseous metal carbonyl in the admixture of gas of step (3) gained
Compound thermally decomposes as co gas and metal solid, and by metal recovery.
2. according to claim 1 method it is characterised in that also including: (6) gas obtained by sulfur recovery unit, step (5)
It is rich in co, h in body2And h2S, described gas enters sulfur recovery unit removing sulfur, and the gas part after gained desulfurization returns to carbonyl
Change reactor cycles, partly outer discharger, after Water gas shift/WGS device, separates and obtains hydrogen and co2.
3. according to claim 1 method it is characterised in that containing so in the flue gas that obtains in step (4) regeneration unitx, described
Flue gas is outer after alkaline cleaner or sulfur transfer additive desulfurization reach discharge standard to be arranged.
4. according to claim 1 method it is characterised in that described heavy oil be carbon residue in 5wt%～40wt%, tenor exists
The inferior heavy oil of 1～1000 μ g/g.
5. according to claim 1 method it is characterised in that in step (1) contact Cracking Unit operating condition be: reaction
Temperature is 450～650 DEG C, and weight (hourly) space velocity (WHSV) is 1～100h-1, contact agent is 1～30:1 with the mass ratio of heavy oil feedstock, vapor
Mass ratio with heavy oil feedstock is 0.05～1:1.
6. according to claim 1 method it is characterised in that contact agent in step (1) is silica-alumina material and/or gasification catalysis
Agent.
7. according to claim 6 method it is characterised in that described gasifying catalyst be selected from containing alkali metal, alkaline-earth metal and
One of the natural crystal of single metal or various metals combination, synthetic material and derivative compound or several in viii race metal
Kind.
8. according to claim 1 method it is characterised in that step (2) fluidized-bed gasifier gasification temperature be 550～800
℃.
9. according to claim 8 method it is characterised in that described fluidized-bed gasifier is bottom close phase section top dilute phase section
Combined fluidized bed form, operating condition is: gas residence time 0.5～60 second, and the gasification temperature of dense bed is 550～800
DEG C, the linear velocity 0.05～0.6m/s of dense bed；Treatment with external measures hot mode is taken to make dilute phase section in the dilute phase section of fluidized-bed gasifier
Temperature is less than 680 DEG C.
10. according to claim 9 method it is characterised in that step (2) fluidized-bed gasifier operating condition: when gas stops
Between 1.0～10 seconds, the gasification temperature of dense bed is 600～700 DEG C, and the linear velocity of dense bed is 0.2～0.4m/s.
11. according to claim 1 method it is characterised in that in gasifying agent in step (2) oxygen mole fraction be 5%～
30%, vapor molar fraction is 70%～95%.
12. according to claim 1 method it is characterised in that described in step (2) gasification gas in h2S accounts for total in gasification gas
70v%～the 99.9v% of sulfur.
13. according to claim 1 method it is characterised in that in step (3) carbonylation co concentration be 10～99v%.
14. according to claim 13 method it is characterised in that in step (3) carbonylation co concentration be 40～
90v%.
15. according to claim 1 method it is characterised in that in step (3) reaction temperatures for carbonylation be 100～200 DEG C, instead
Pressure is answered to be 0.05～1.0mpa；Response time is 0.1～24 hour.
16. according to claim 15 method it is characterised in that in step (3) reaction temperatures for carbonylation be 110～180 DEG C, instead
It is 0.5～15 hour between seasonable.
17. according to claim 1 method it is characterised in that step (4) semi regeneration contact agent regeneration temperature be 600～750
DEG C, it is passed through the gas that gas is oxygen-containing 10v%～50v%.
18. according to claim 1 method it is characterised in that in step (5) pyrolysis temperature be 200～300 DEG C, instead
Pressure is answered to be 0.03～0.5mpa, the response time is 0.5～15 hour.
19. according to claim 18 method it is characterised in that in step (5) pyrolysis temperature be 240～290 DEG C, instead
Pressure is answered to be 0.03～0.5mpa, the response time is 1～10 hour.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1198366A (en) * | 1997-05-06 | 1998-11-11 | 中国石油化工总公司 | Dry demetallization regeneration technology for residue and/or heavy oil catalytic cracking catalyst |
| CN102453515A (en) * | 2010-10-26 | 2012-05-16 | 中国石油化工股份有限公司 | Inferior heavy oil contact cracking-gasification-regeneration combined method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1198366A (en) * | 1997-05-06 | 1998-11-11 | 中国石油化工总公司 | Dry demetallization regeneration technology for residue and/or heavy oil catalytic cracking catalyst |
| CN102453515A (en) * | 2010-10-26 | 2012-05-16 | 中国石油化工股份有限公司 | Inferior heavy oil contact cracking-gasification-regeneration combined method |
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