CN104593040A - 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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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 the method for a kind of heavy oil lighting processing, more particularly, relate to a kind of method of the metal refining in the process of heavy oil lighting processing simultaneously on Removal of catalyst.
Background technology
By in the process of heavy oil lighting, catalytic cracking because it is economical, rationally and can production high-quality product and be subject to the attention of refining enterprise.Along with petroleum resources become heavy day by day, carbon residue, sulphur and metal content increase, and more residual oil and/or heavy oil become the raw material of secondary processing.But in residual oil and/or heavy oil, be enriched most of metal in crude oil, carry out in catalyzed cracking processing process at heavy oil, these metals mostly deposit on a catalyst, and poisoning effect is produced to catalyzer, change its character, thus affect product slates.Residual oil catalytic cracking requires that catalyzer can keep certain activity, therefore residual oil catalytic cracking ingredient requirement (Ni+V) <25 μ gg under the condition of more harmful metal pollution
-1, be generally 10 μ gg
-1left and right, nonetheless, is the activity keeping catalyzer certain, regularly need draws off the too high catalyzer of metal content, and fresh makeup catalyst, this not only adds process cost, and spent catalyst also will cause problem of environmental pollution.
US4293403 discloses a kind of wet processing spent catalyst, metal in Removal of catalyst, as the method for nickel, iron and/or vanadium, uses sulfuration, oxidation, acid elution by metal removal, but can produce scrub raffinate, secondary pollution is caused to environment, damages catalyst activity simultaneously.CN1198366A discloses the dry method demetalization regeneration techniques of a kind of residual oil and/or catalyst for heavy oil catalytic cracking, by spent catalyst reduction after sulphur activation, then contacts with CO gas and generates gaseous metal carboxide and be separated with solid catalyst.Owing to using this chemical reaction to remove metal, activating and reducing process need introduces hydrogen sulfide and hydrogen, and carbonylation processes needs to introduce CO gas, carries out demetalization regeneration after catalyzer can only being drawn off.Chinese patent CN1398792A proposes the method for synthesizing carbonyl nickel, when containing a small amount of H in CO
2carbonylation rate can be accelerated during S.And metallic nickel on catalytic cracking catalyst by being exist with the form of nickel aluminate, generate nickle carbonoxide needs first nickel aluminate to be reduced to simple substance as wanted.When containing H in reducing atmosphere
2during S, the reduction reaction of nickel can be accelerated.
Inferior heavy oil contact cracking-coke gasification integral processing method is organically combined contact cracking and band charcoal contact substance gasification.CO and H is rich in by regulating the composition of gasification gas to produce
2gasification product, under reducing atmosphere, sulphur on contact substance generates H
2s.Therefore, the method passes through the suitable flow process of design, likely online demetalization, and obtains Metallic Pairs product.
Summary of the invention
The technical problem to be solved in the present invention is on the basis of existing technology, provides a kind of in heavy oil contact cracking gasification integrated process, removes simultaneously and reclaims the method for the metal that contact substance deposits.
Remove a heavy oil lightening method for metal on contact substance simultaneously, comprising:
(1) at contact Cracking Unit, heavy oil enters contact cracking case, contact cracking reaction is carried out under the existence of contact substance, the effluent of contact cracking case comprises dry gas, liquefied gas, gasoline fraction, diesel oil distillate, wax oil cut and band charcoal contact substance, and described band charcoal contact substance enters gasification unit;
(2) in gasification unit, step (1) resulting tape charcoal contact substance enters in fluidized-bed gasifier, under the vaporized chemical containing water and oxygen exists, makes the charcoal on contact substance and vaporized chemical reaction, obtains semi regeneration contact substance and be rich in CO, H
2gasification gas, wherein, gasification gas in sulphur with H
2the form of S exists, and the metal that contact substance deposits and the reductibility gas that gasifies contacts, and is activated, is reduced to metal simple-substance;
(3) at carbonylation unit, the semi regeneration contact substance of step (2) gained contacts with CO, and on contact substance, metal simple-substance carbonylation reaction obtains gaseous metal carboxide, and is separated with solid state contacts agent, obtains demetallated semi regeneration contact substance;
(5) in metals recovery units, in thermal decomposition reactor, in the gaseous mixture of step (3) gained, gaseous metal carboxide thermolysis is CO gas and metal solid, and by metal recovery.
Preferably, also comprise between step (3) and step (5): (4) are at regeneration unit, having under oxygen existent condition, residual charcoal generation perfect combustion on demetallated semi regeneration contact substance, obtain holomorphosis contact substance and flue gas, holomorphosis contact substance returns step (1) contact Cracking Unit;
Preferably, also comprise: (6), in sulfur recovery unit, are rich in CO, H in the gas that step (5) obtains
2and H
2s, described gas enters sulfur recovery unit and removes sulphur, and the gas fraction after gained desulfurization returns to carbonylation reactor circulation, and the outer discharger of part, after water-gas shift device, is separated and obtains hydrogen and CO
2.
The beneficial effect simultaneously removing the heavy oil lightening method of metal on contact substance provided by the invention is:
Method provided by the invention, utilizes CO, H that gasification generates
2and H
2the reducing atmosphere of S, directly removes the poisonous metal that contact substance deposits online by carbonylation reaction, extend the contact substance life-span; Demetalization operational condition does not exceed heavy oil contact cracking-coke gasification condition, and process cost is lower; Processing condition are gentle, can not damage the active ingredient of load on contact substance, more can not damaging contact agent skeleton structure; High value metals byproduct can also be obtained; Heavy oil lightening method environmentally safe provided by the invention.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet simultaneously removing the heavy oil lightening method of metal on contact substance provided by the invention.
Wherein: 1-contacts Cracking Unit; 2-gasification unit; 3-carbonylation unit; 4-regeneration unit; 5-thermal decomposition unit; 6-sulfur recovery unit; 7-water-gas shift device; 8 ~ 29-pipeline.
Embodiment
Remove a heavy oil lightening method for metal on contact substance simultaneously, comprising:
(1) at contact Cracking Unit, heavy oil enters contact cracking case, contact cracking reaction is carried out under the existence of contact substance, the effluent of contact cracking case comprises dry gas, liquefied gas, gasoline fraction, diesel oil distillate, wax oil cut and band charcoal contact substance, and described band charcoal contact substance enters gasification unit;
(2) in gasification unit, step (1) resulting tape charcoal contact substance enters in fluidized-bed gasifier, under the vaporized chemical containing water and oxygen exists, makes the charcoal on contact substance and vaporized chemical reaction, obtains semi regeneration contact substance and be rich in CO, H
2gasification gas, wherein, gasification gas in sulphur with H
2the form of S exists, and the metal that contact substance deposits and the reductibility gas that gasifies contacts, and is activated, is reduced to metal simple-substance;
(3) at carbonylation unit, the semi regeneration contact substance of step (2) gained contacts with CO, and on contact substance, metal simple-substance carbonylation reaction obtains gaseous metal carboxide, and is separated with solid state contacts agent, obtains demetallated semi regeneration contact substance;
(5) in metals recovery units, in thermal decomposition reactor, in the gaseous mixture of step (3) gained, gaseous metal carboxide thermolysis is CO gas and metal solid, and by metal recovery.
Preferably, also comprise between step (3) and step (5): (4) are at regeneration unit, having under oxygen existent condition, residual charcoal generation perfect combustion on demetallated semi regeneration contact substance, obtain holomorphosis contact substance and flue gas, holomorphosis contact substance returns step (1) contact Cracking Unit;
Preferably, also comprise: (6), in sulfur recovery unit, are rich in CO, H in the gas that step (5) obtains
2and H
2s, described gas enters sulfur recovery unit and removes sulphur, and the gas fraction after gained desulfurization returns to carbonylation reactor circulation, and the outer discharger of part, after water-gas shift device, is separated and obtains hydrogen and CO
2.
Preferably, containing SO in the flue gas obtained in step (4) regeneration unit
x, outer row after described flue gas reaches emission standard by alkaline cleaner or sulfur transfer additive desulfurization.
In method provided by the invention, described heavy oil can be one or more the mixture 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.Preferred heavy oil be carbon residue at 5wt% ~ 40wt%, metal content is in the inferior heavy oil of 1 ~ 1000 μ g/g.
The operational condition of the contact Cracking Unit in step (1) is: temperature of reaction is 450 ~ 650 DEG C, and weight hourly space velocity is 1 ~ 100h
-1, the mass ratio of contact substance and heavy oil feedstock is 1 ~ 30:1, and the mass ratio of water vapour and heavy oil feedstock is 0.05 ~ 1:1.
Contact substance in step (1) is silica-alumina material and/or gasifying catalyst.When contact substance be silica-alumina material and gasifying catalyst time, gasifying catalyst and silica-alumina material are mechanically mixing, or gasifying catalyst load is on silica-alumina material.Wherein, described silica-alumina material is selected from containing the catalytic cracking catalyst of molecular sieve and/or not containing the catalytic cracking catalyst of molecular sieve.
Described gasifying catalyst is selected from one or more in natural crystal, synthetic materials and the derivative compound comprising single metal or various metals combination in basic metal, alkaline-earth metal and group VIII metal.
The band charcoal contact substance carbon content that step (1) obtains is at 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 fixed fluidized-bed reactor, riser reactor or reactor types that is fixed fluidized bed and dilute-phase leanphase fluidized bed combination.Preferably, described fluidized-bed gasifier adopts the combined fluidized bed form of Mi Xiangduan top, bottom dilute phase section, operational condition is: gas residence time 0.5 ~ 60 second, preferably 1.0 ~ 10 seconds, the gasification temperature of dense bed is 550 ~ 800 DEG C, preferably 600 ~ 700 DEG C, the linear velocity 0.05 ~ 0.6m/s of dense bed, preferably 0.2 ~ 0.4m/s; Outside heat removing mode is taked to make the temperature of dilute phase section lower than 680 DEG C in the dilute phase section of fluidized-bed gasifier.
Contain oxygen and water vapour in vaporized chemical in step (2), preferably, in vaporized chemical, oxygen mole fraction is 5% ~ 30%, more preferably 5 ~ 20%, and water vapour molar fraction is 70% ~ 95%, more preferably 80 ~ 95%.
In step (2), on contact substance to be generated, the coke generating gasification H2S reacted in the gasification gas generated accounts for the 70v% ~ 99.9v% of total sulfur in gasification gas.
In step (2), the carbon content of semi regeneration contact substance is at 0.4 ~ 1.0wt%.
In step (3), the concentration of carbonylation reaction CO is 10v% ~ 99v%, preferably 40v% ~ 90v%.
In step (3), reaction temperatures for carbonylation will is 100 ~ 200 DEG C, preferably 110 ~ 180 DEG C, and reaction pressure is 0.05 ~ 1.0MPa(gauge pressure); Reaction times is 0.1 ~ 24 hour, preferably 0.5 ~ 15 hour.
The semi regeneration contact substance obtained in step (2) in method provided by the invention all can enter in step (3) carbonylation unit and remove metal, also partly can enter step (3) carbonylation unit and remove metal, part enters Direct Regeneration in step (4) regeneration unit.
The regeneration temperature of step (4) semi regeneration contact substance is 600 ~ 750 DEG C, and passing into gas is containing the gas of oxygen 10v% ~ 50v%, preferably air.
Pyrolysis temperature is 200 ~ 300 DEG C, preferably 240 ~ 290 DEG C in step (5), and reaction pressure is 0.03 ~ 0.5MPa(gauge pressure), preferred 0.03 ~ 0.5MPa(gauge pressure), the reaction times is 0.5 ~ 15 hour, preferably 1 ~ 10 hour.
Describe the preferred implementation simultaneously removing the heavy oil lightening method of metal on contact substance provided by the invention in detail referring to accompanying drawing, but the present invention is not therefore subject to any restriction.
Fig. 1 is the schematic flow sheet simultaneously removing the heavy oil lightening method of metal on contact substance provided by the invention.As shown in Figure 1, heavy oil feedstock and atomizing steam are entered by pipeline 8 and contact Cracking Unit 1, the fresh contact substance supplemented through pipeline 9 with from revivifier pipeline 18 regeneration contact substance out and/or enter from pipeline 26 carbonylation unit semi regeneration agent out and contact Cracking Unit 1, after heavy oil contacts with contact substance and cracking reaction occurs in cracking case, the oil gas produced enters subsequent separation system by pipeline 10, and contact substance to be generated enters gasification unit 2 by pipeline 11.In gasification unit 2, coke on contact substance to be generated with react from the water vapour of pipeline 13 and the oxygen generating gasification of pipeline 12, the gasification gas generated is drawn from pipeline 14 and is entered carbonylation unit 3, in carbonylation unit 3, CO in the metal of activated reduction on semi regeneration contact substance and carbonylation reactor and reacting from the part CO that pipeline 28 returns, generates the metal carbonyls of gaseous state and solid-state demetalization semi regeneration contact substance.Metal carbonyls and the unreacted gasification gas of gaseous state enter thermal decomposition unit 5 by pipeline 20, in thermal decomposition unit 5, metal carbonyls generation pyrolysis, generate metal simple-substance and CO, the metal generated regularly reclaims from pipeline 29, gas containing CO enters sulfur recovery unit 6 by pipeline 21, and the partial gasification gas reclaimed after sulphur enters water-gas shift device 7 by pipeline 22, and CO and water generation transformationreation are generated CO
2and H
2, by CO
2and H
2respectively from pipeline 23,24 extraction system after separation.In sulfur recovery unit 6, the gasification gas of partial desulfurization returns carbonylation unit 3 by pipeline 28, regeneration unit 4 is entered by pipeline 15 from carbonylation unit 3 demetalization semi regeneration contact substance out, demetalization semi regeneration contact substance and/or from gasification unit come semi regeneration contact substance coke with react from the air of pipeline 16 and the oxygen generation perfect combustion of pipeline 17, the flue gas generated is entered after flue gas desulfurization (FGD) unit reaches emission standard directly can be discharged air by pipeline 19, obtains the contact substance after regenerating and draws revivifier by pipeline 18.
The present invention is described in detail below by embodiment, but the use range that embodiment is not thereby limiting the invention.The contact substance adopted is containing the obtained contact substance of roasting after 10wt% aluminum oxide, the kaolinic spraying dry of 80wt%, is designated as MFC-1; Containing the contact substance that roasting after the spraying dry of 90% aluminum oxide is obtained, be designated as MFC-2; The numbering containing the catalytic cracking catalyst of clay molecular sieve with layer structure and ZSM-5 molecular sieve adopted is designated as MFC-3; The catalytic cracking catalyst adopted is trade names is CRC-1 catalytic cracking catalyst (being produced by Shandong catalyzer branch office of catalyzer main office of China Petrochemical Industry); Gasifying catalyst preparation method is for getting 6kg kaolin, add 18 deionized waters, stir at 30 DEG C, and add the mixture of 3kg potassium oxide and calcium oxide while stirring, wherein potassium is 0.4 with calcium atom ratio, add 0.2kg Alumina gel, obtain vaporized chemical at 600 DEG C of roasting 60min after spraying dry, be designated as GC-1; Through pulverizing median size at the natural rhombspar of 65 μm, be designated as GC-2.
In embodiment, heavy oil feedstock character is in table 1.
Table 1 heavy oil character
On contact substance, nickel content analysis method uses x ray fluorescence spectrometry.
Nickel removal rate method of calculation are as follows:
Embodiment 1
Be that catalytic cracking catalyst and the gasifying catalyst GC-1 of CRC-1 carries out mechanically mixing by trade names, both mass ratios are 9:1, through repeatedly flooding pollution metallic nickel, nickel content is 20000ppm, be 18.10% with carbon residue after 800 DEG C, 17 hours hydrothermal treatment consists, metal is 200 μ g/g, heavy oil that sulphur content is 1.12wt% comes in contact cracking reaction contacting Cracking Unit, the processing condition of contact cracking reaction are: cracking temperature 500 DEG C, air speed 20h
-1, agent-oil ratio 7, water-oil ratio 0.2, the coke content of gained spent agent is 2.5wt%.
Spent agent through stripping laggard enter fluid bed gasification unit.The gas linear velocity of gasification unit is 0.12m/s, and gasification temperature 680 DEG C, passes into containing oxygen 20%(mole), water 80%(mole) vaporized chemical, gas residence time 5 seconds, the reaction times be 1 hour send out, generating gasification react, metallic nickel and H on spent agent
2s and H
2activate, reduction reaction.Outside heat removing mode is taked to make fluidized-bed dilute phase section temperature control lower than 650 DEG C.The semi regeneration agent containing charcoal 0.45wt% and gaseous product is obtained after gas solid separation, (CO+H in gaseous product in gasification unit
2)/CO
2mol ratio be 1.50, H
2s accounts for the 95.2%(volume of total sulfur in gasification gas), gasification gas enters after sulfur recovery unit removes sulphur, and gasification gas is separated through water-gas shift and obtains hydrogen and CO
2.
Carbonylation low speed circulating fluidized bed is sent in semi regeneration agent, and temperature of reaction 110 DEG C, passes into gas molar and consist of containing 60%CO, 5%H
2, 5%H
2s, all the other are CO
2, reaction pressure 0.15MPa(gauge pressure), the reaction times is 1 hour, H
2s is catalyzer, and Ni and CO is reacted, and generates gaseous state Ni (CO)
4.Enter thermal decomposition reactor from carbonylation reactor effluent air, temperature of reaction is 240 DEG C, and in 0.1MPa(gauge pressure) reaction 10 hours under pressure, Ni (CO)
4be decomposed into solid metal Ni and CO gas.Demetallated semi regeneration agent is sent in regeneration unit, temperature of reaction 680 DEG C, with the air reaction containing oxygen volume fraction 18%.Obtain regenerated flue gas and regenerator after gas solid separation in revivifier, the sulphur in flue gas is mainly SO
x, outer row after flue gas reaches emission standard by alkaline cleaner, the coke content of regenerator is 0.02wt%.
After whole flow process, contact substance nickel removal rate is about 30%.
Embodiment 2
The raw material identical with embodiment 1 and flow process, unlike the carbonylation reaction time.Contact substance is through Cracking Unit and gasification unit, and carbonylation low speed circulating fluidized bed is sent in the agent of gained semi regeneration, and temperature of reaction 110 DEG C, passes into gas molar and consist of containing 60%CO, 5%H
2, 5%H
2s, all the other are CO
2, reaction pressure 0.15MPa(gauge pressure), the reaction times is 8 hours, H
2s is catalyzer, and Ni and CO is reacted, and generates gaseous state Ni (CO)
4.Demetallated semi regeneration contact substance is after regeneration, and contact substance nickel removal rate is 70%.
Embodiment 3
By contact substance MFC-1 through repeatedly flooding pollution metallic nickel, nickel content is 20000ppm, be 35.0% with carbon residue after 800 DEG C, 17 hours hydrothermal treatment consists, metal 425 μ g/g, sulphur content be that the heavy oil of 3.12wt% comes in contact cracking reaction contacting Cracking Unit, the processing condition of contact cracking reaction are: cracking temperature 520 DEG C, air speed 50h
-1, agent-oil ratio 20, water-oil ratio 0.5, the coke content of gained spent agent is 2.8wt%.
Spent agent through stripping laggard enter fluid bed gasification unit.The gas linear velocity of gasification unit is 0.4m/s, gasification temperature 560 DEG C, passes into the vaporized chemical mole consisted of containing 30% oxygen, 70% water, gas residence time 50 seconds, and generating gasification is reacted.Outside heat removing mode is taked to make fluidized-bed dilute phase section temperature control lower than 560 DEG C.The semi regeneration agent containing charcoal 0.50wt% and gaseous product is obtained after gas solid separation, (CO+H in gaseous product in gasification unit
2)/CO
2mol ratio be 0.8, H
2s accounts for the 76.8%(volume of total sulfur in gasification gas), gasification gas enters after sulfur recovery unit removes sulphur, and gasification gas is separated through water-gas shift and obtains hydrogen and CO
2, hydrogen and CO
2after separation, CO
2can trap.
Carbonylation low speed circulating fluidized bed is sent in the agent of gained semi regeneration, and temperature of reaction 110 DEG C, passes into gas molar and consist of containing 50%CO, 5%H
2, 5%H
2s, all the other are CO
2, reaction pressure 0.15MPa(gauge pressure), the reaction times is 6 hours, H
2s is catalyzer, and Ni and CO is reacted, and generates gaseous state Ni (CO)
4.Enter thermal decomposition reactor from carbonylation reactor effluent air, temperature of reaction is 270 DEG C, and in 0.4MPa(gauge pressure) reaction 2 hours under pressure, Ni (CO)
4be decomposed into solid metal Ni and CO gas.Temperature of reaction 650 DEG C in regeneration unit is sent in semi regeneration agent, carries out holomorphosis reaction with the gas containing oxygen volume fraction 15%.Obtain regenerated flue gas and regenerator after gas solid separation in revivifier, the sulphur in flue gas is mainly SO
x.
After whole flow process, contact substance nickel removal rate is 28%.
Embodiment 4
After by silica-alumina material MFC-2,2:1 mixes in mass ratio with silica-alumina material MFC-3, through repeatedly flooding pollution metallic nickel, nickel content be 20000ppm with containing be 20.0 % by weight with carbon residue, metal content is 120 μ g/g, sulphur content is 3.12%(quality) heavy oil come in contact cracking reaction contact Cracking Unit, the processing condition contacting cracking reaction are: cracking temperature 550 DEG C, air speed 80h
-1, agent-oil ratio 28, water-oil ratio 0.1, the coke content of gained spent agent is 2.0 % by weight.
Spent agent through stripping laggard enter fluid bed gasification unit device.The gas linear velocity of the dense bed in gasifier is 0.6m/s, and gasification temperature 700 DEG C, passes into containing oxygen 15%(mole), water 85%(mole) vaporized chemical, gas residence time 55 seconds, generating gasification react.Outside heat removing mode is taked to make fluidized-bed dilute phase section temperature control lower than 600 DEG C.Semi regeneration agent and the gaseous product of carbon content 1.0 % by weight is obtained after gas solid separation, (CO+H in gaseous product in gasification unit
2)/CO
2mol ratio be 45, H
2s accounts for the 99.2%(volume of total sulfur in gasification gas), gasification gas enters after sulfur recovery unit removes sulphur, and gasification gas is separated through water-gas shift and obtains hydrogen and CO
2, hydrogen and CO
2after separation, CO
2can trap.
Carbonylation low speed circulating fluidized bed is sent in the agent of gained semi regeneration, and temperature of reaction 150 DEG C, passes into gas molar and consist of containing 50%CO, 5%H
2, 5%H
2s, all the other are CO
2, reaction pressure 0.15MPa(gauge pressure), the reaction times is 6 hours, H
2s is catalyzer, and Ni and CO is reacted, and generates gaseous state Ni (CO)
4, enter thermal decomposition reactor from carbonylation reactor effluent air, temperature of reaction is 250 DEG C, and in 0.03MPa(gauge pressure) and reaction 15 hours under pressure, Ni (CO)
4be decomposed into solid metal Ni and CO gas.
Temperature of reaction 730 DEG C in regeneration unit sent into by the later half regenerator of demetalization, carries out holomorphosis reaction with the gas containing oxygen volume fraction 10%.Obtain regenerated flue gas and regenerator after gas solid separation in revivifier, the sulphur in flue gas is mainly SO
x, outer row after flue gas reaches emission standard by alkaline cleaner, the coke content of holomorphosis agent is 0.02wt%, and returns contact Cracking Unit.Contact substance nickel removal rate is 75%.
Embodiment 5
By contact substance MFC-2 and GC-2,1:1 mechanically mixing is even in mass ratio, be 25.0% with carbon residue, metal content is 100.1 μ g/g, petroleum hydrocarbon that sulphur content is 3.12wt% comes in contact cracking reaction contacting Cracking Unit, the processing condition of contact cracking reaction are: cracking temperature 580 DEG C, air speed 30h
-1, agent-oil ratio 15, water-oil ratio 0.3, the coke content of gained spent agent is 4.2%.
Spent agent through stripping laggard enter fluid bed gasification unit.The gas linear velocity of gasification unit is 0.32m/s, and gasification temperature 650 DEG C, passes into containing oxygen 10%(mole), water 90%(mole) vaporized chemical, gas residence time 10 seconds, generating gasification react.Outside heat removing mode is taked to make fluidized-bed dilute phase section temperature control lower than 630 DEG C.The semi regeneration agent containing charcoal 0.8% and gaseous product is obtained after gas solid separation, (CO+H in gaseous product in gasification unit
2)/CO
2mol ratio be 5, H
2s accounts for the 85.6%(volume of total sulfur in gasification gas), gasification gas enters after sulfur recovery unit removes sulphur, and gasification gas is separated through water-gas shift and obtains hydrogen and CO
2, hydrogen and CO
2after separation, CO
2can trap.
Carbonylation low speed circulating fluidized bed is sent in the agent of gained semi regeneration, and temperature of reaction 150 DEG C, passes into gas molar and consist of containing 70%CO, 5%H
2, 5%H
2s, all the other are CO
2, reaction pressure 0.15MPa(gauge pressure), the reaction times is 15 hours, H
2s is catalyzer, and Ni and CO is reacted, and generates gaseous state Ni (CO)
4, enter thermal decomposition reactor from carbonylation reactor effluent air, temperature of reaction is 270 DEG C, and in 0.4MPa(gauge pressure) and reaction 2 hours under pressure, Ni (CO)
4be decomposed into solid metal Ni and CO gas.Temperature of reaction 650 DEG C in regeneration unit is sent in demetallated semi regeneration agent, with the air reaction containing oxygen volume fraction 15%.Obtain regenerated flue gas and regenerator after gas solid separation in revivifier, the sulphur in flue gas is mainly SO
x, outer row after flue gas reaches emission standard by alkaline cleaner, returns contact Cracking Unit.Contact substance nickel removal rate is 85%.
The contact substance demetallization per carbonylation reaction time is relevant, therefore can design cycle as required, as later half for gasification reaction regenerator is all entered carbonylation unit, select the shorter reaction times, enter next unit after part demetalization, or later half for gasification reaction regenerator part is directly entered regeneration unit, the agent of another part semi regeneration enters carbonylation unit, select the longer reaction times, after degree of depth demetalization, enter next unit.
Claims (22)
1. remove a heavy oil lightening method for metal on contact substance simultaneously, it is characterized in that, comprise the following steps:
(1) at contact Cracking Unit, heavy oil enters contact cracking case, contact cracking reaction is carried out under the existence of contact substance, the effluent of contact cracking case comprises dry gas, liquefied gas, gasoline fraction, diesel oil distillate, wax oil cut and band charcoal contact substance, and described band charcoal contact substance enters gasification unit;
(2) in gasification unit, step (1) resulting tape charcoal contact substance enters in fluidized-bed gasifier, under the vaporized chemical containing water and oxygen exists, makes the charcoal on contact substance and vaporized chemical reaction, obtains semi regeneration contact substance and be rich in CO, H
2gasification gas, wherein, gasification gas in sulphur with H
2the form of S exists, and the metal that contact substance deposits and the reductibility gas that gasifies contacts, and is activated, is reduced to metal simple-substance;
(3) at carbonylation unit, the semi regeneration contact substance of step (2) gained contacts with CO, and on contact substance, metal simple-substance carbonylation reaction obtains gaseous metal carboxide, and is separated with solid state contacts agent, obtains demetallated semi regeneration contact substance;
(5) in metals recovery units, in thermal decomposition reactor, in the gaseous mixture of step (3) gained, gaseous metal carboxide thermolysis is CO gas and metal solid, and by metal recovery.
2. according to the method for claim 1, it is characterized in that, also comprise between step (3) and step (5): (4) are at regeneration unit, having under oxygen existent condition, residual charcoal generation perfect combustion on demetallated semi regeneration contact substance, obtain holomorphosis contact substance and flue gas, holomorphosis contact substance returns step (1) contact Cracking Unit.
3. according to the method for claim 1 or 2, it is characterized in that, also comprise: (6), in sulfur recovery unit, are rich in CO, H in the gas that step (5) obtains
2and H
2s, described gas enters sulfur recovery unit and removes sulphur, and the gas fraction after gained desulfurization returns to carbonylation reactor circulation, and the outer discharger of part, after water-gas shift device, is separated and obtains hydrogen and CO
2.
4. according to the method for claim 2, it is characterized in that, containing SO in the flue gas obtained in step (4) regeneration unit
x, outer row after described flue gas reaches emission standard by alkaline cleaner or sulfur transfer additive desulfurization.
5., according to the method for claim 1 or 2, it is characterized in that, described heavy oil be carbon residue at 5wt% ~ 40wt%, metal content is in the inferior heavy oil of 1 ~ 1000 μ g/g.
6. according to the method for claim 1 or 2, it is characterized in that, the operational condition of the contact Cracking Unit in step (1) is: temperature of reaction is 450 ~ 650 DEG C, and weight hourly space velocity is 1 ~ 100h
-1, the mass ratio of contact substance and heavy oil feedstock is 1 ~ 30:1, and the mass ratio of water vapour and heavy oil feedstock is 0.05 ~ 1:1.
7. according to the method for claim 1 or 2, it is characterized in that, the contact substance in step (1) is silica-alumina material and/or gasifying catalyst.
8. according to the method for claim 7, it is characterized in that, described gasifying catalyst is selected from one or more in natural crystal, synthetic materials and the derivative compound combined containing metal single in basic metal, alkaline-earth metal and group VIII metal or various metals.
9. according to the method for claim 1 or 2, it is characterized in that, the band charcoal contact substance carbon content that step (1) obtains is at 0.5wt% ~ 7.0wt%.
10. according to the method for claim 1 or 2, it is characterized in that, the gasification temperature of step (2) fluidized-bed gasifier is 550 ~ 800 DEG C.
11. according to the method for claim 10, it is characterized in that, described fluidized-bed gasifier is the combined fluidized bed form of Mi Xiangduan top, bottom dilute phase section, operational condition is: gas residence time 0.5 ~ 60 second, the gasification temperature of dense bed is 550 ~ 800 DEG C, the linear velocity 0.05 ~ 0.6m/s of dense bed; Outside heat removing mode is taked to make the temperature of dilute phase section lower than 680 DEG C in the dilute phase section of fluidized-bed gasifier.
12. according to the method for claim 11, and it is characterized in that, step (2) fluidized-bed gasifier operational condition: gas residence time 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.
13., according to the method for claim 1 or 2, is characterized in that, in step (2), in vaporized chemical, oxygen mole fraction is 5% ~ 30%, and water vapour molar fraction is 70% ~ 95%.
14., according to the method for claim 1 or 2, is characterized in that, the H in the gasification gas described in step (2)
2s accounts for the 70v% ~ 99.9v% of total sulfur in gasification gas.
15., according to the method for claim 1 or 2, is characterized in that, in step (2), the carbon content of semi regeneration contact substance is at 0.4 ~ 1.0wt%.
16., according to the method for claim 1 or 2, is characterized in that, in step (3), the concentration of carbonylation reaction CO is 10 ~ 99v%.
17., according to the method for claim 16, is characterized in that, in step (3), the concentration of carbonylation reaction CO is 40 ~ 90v%.
18., according to the method for claim 1 or 2, is characterized in that, in step (3), reaction temperatures for carbonylation will is 100 ~ 200 DEG C, and reaction pressure is 0.05 ~ 1.0MPa; Reaction times is 0.1 ~ 24 hour.
19., according to the method for claim 18, is characterized in that, in step (3), reaction temperatures for carbonylation will is 110 ~ 180 DEG C, and the reaction times is 0.5 ~ 15 hour.
20. according to the method for claim 1 or 2, and it is characterized in that, the regeneration temperature of step (4) semi regeneration contact substance is 600 ~ 750 DEG C, and passing into gas is gas containing oxygen 10v% ~ 50v%.
21., according to the method for claim 1 or 2, is characterized in that, in step (5), pyrolysis temperature is 200 ~ 300 DEG C, and reaction pressure is 0.03 ~ 0.5MPa, and the reaction times is 0.5 ~ 15 hour.
22., according to the method for claim 21, is characterized in that, in step (5), pyrolysis temperature is 240 ~ 290 DEG C, and reaction pressure is 0.03 ~ 0.5MPa, and the reaction times is 1 ~ 10 hour.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018177294A1 (en) * | 2017-03-27 | 2018-10-04 | 储晞 | Method, apparatus, and system for producing silicon-containing product by utilizing silicon mud byproduct of cutting silicon material with diamond wire |
| CN112717999A (en) * | 2019-10-28 | 2021-04-30 | 中国石油化工股份有限公司 | Regeneration method of hydrocracking catalyst |
Citations (2)
| 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 |
-
2013
- 2013-10-30 CN CN201310526754.6A patent/CN104593040B/en active Active
Patent Citations (2)
| 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 |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018177294A1 (en) * | 2017-03-27 | 2018-10-04 | 储晞 | Method, apparatus, and system for producing silicon-containing product by utilizing silicon mud byproduct of cutting silicon material with diamond wire |
| JP2020515505A (en) * | 2017-03-27 | 2020-05-28 | シュウ, キシーCHU, Xi | Method, device and system for manufacturing silicon-containing product by using silicon sludge produced as a by-product during diamond wire cutting of silicon material |
| CN112717999A (en) * | 2019-10-28 | 2021-04-30 | 中国石油化工股份有限公司 | Regeneration method of hydrocracking catalyst |
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