CN105505461A - Catalytic cracking method of heavy oil and device thereof - Google Patents

Catalytic cracking method of heavy oil and device thereof Download PDF

Info

Publication number
CN105505461A
CN105505461A CN201510850129.6A CN201510850129A CN105505461A CN 105505461 A CN105505461 A CN 105505461A CN 201510850129 A CN201510850129 A CN 201510850129A CN 105505461 A CN105505461 A CN 105505461A
Authority
CN
China
Prior art keywords
oil
reaction
outlet
gas
catalytic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201510850129.6A
Other languages
Chinese (zh)
Other versions
CN105505461B (en
Inventor
高金森
王刚
王成秀
蓝兴英
徐春明
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China University of Petroleum Beijing
Original Assignee
China University of Petroleum Beijing
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by China University of Petroleum Beijing filed Critical China University of Petroleum Beijing
Priority to CN201510850129.6A priority Critical patent/CN105505461B/en
Publication of CN105505461A publication Critical patent/CN105505461A/en
Application granted granted Critical
Publication of CN105505461B publication Critical patent/CN105505461B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
    • C10G69/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one step of catalytic cracking in the absence of hydrogen
    • 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
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/70—Catalyst aspects
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/02—Gasoline
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/04—Diesel oil
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/26—Fuel gas

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

The invention provides a catalytic cracking method of heavy oil and a device thereof. A reactor adopted in the method comprises a first riser and a second riser. The method comprises the following steps: a heavy oil raw material and a catalytic cracking catalyst enter the first riser from the lower part and are contacted with each other in the first riser and go upwards to carry out a first catalytic cracking reaction; reaction oil-gas from the first riser undergoes fractionation to obtain cracking gas, gasoline, diesel oil, recycle oil and slurry; the recycle oil undergoes a catalytic hydrogenation reaction at the reaction temperature of 340-380 DEG C, at the volume space velocity of 0.5-2.0 h<-1>, at the hydrogen-to-oil volume ratio of 300-800 and at the reaction pressure of 7-12 MPa, and oil-gas generated by the catalytic hydrogenation reaction undergoes fractionation to obtain cracking gas, gasoline, diesel oil and catalytic hydrogenation heavy oil; and the catalytic hydrogenation heavy oil is introduced into the second riser to carry out a secondary catalytic cracking reaction, and the reaction oil-gas from the second riser undergoes fractionation to obtain cracking gas, gasoline and diesel oil. According to the invention, maximum yield of light oil products and high value-added chemical materials can be realized, and utilization rate of heavy oil raw material is raised.

Description

Heavy oil fluid catalytic cracking method and apparatus
Technical field
The present invention relates to a kind of heavy oil fluid catalytic cracking method and apparatus, particularly relate to a kind of method and apparatus heavy oil feedstock Grading And Zoning being carried out catalytic cracking, belong to Petroleum Processing Technology field.
Background technology
Along with making constant progress of petroleum refining industry, the catalyzed cracking processing of heavy oil requires the output increasing high value added product, reduces the low value-added product productions such as dry gas, liquefied gas and coke as far as possible simultaneously.In Future Refineries, the device that catalytic unit will be no longer direct production the finished product.The petrol and diesel oil that catalytic cracking is produced must refine Improving The Quality of Products by subsequent product, to meet up-to-date environmental requirement.Although face lot of challenges, catalytic cracking technology, still in development of constantly bringing forth new ideas, particularly takes combination process with other heavy oil upgrading techniques, and catalytic unit will be made to wave central role at Future Refineries relaying supervention.
For this reason, some new technologies continue to bring out, as from optimizing materials atomization, a series of heavy oil fluid catalytic cracking complete set technology of the aspect developing such as outside heat removing, leg outlet sharp separation, heavy metal passivation and catalyzer pre-lift in revivifier.But existing heavy oil fluid catalytic cracking complete processing is mostly that various heavy oil feedstock is carried out charging as one " entirety ", does not take into full account the difference that in the heavy oil feedstock of wide boiling range, different components cracking performance is larger.
The patents such as ZL200910242917.1, ZL200910242920.3, ZL200910242921.8, ZL200910242922.2, ZL200910242918.6, ZL200910242919.0 and patent application propose the method for multiple heavy oil Grading And Zoning catalytic cracking, catalytically cracked material is divided into high-quality fcc raw material and fcc raw material inferior according to the difference section of response characteristic, then makes to transform in its differential responses district entering catalytic cracking unit reactor assembly respectively.But after the inferior raw material part of high carbon residue, high metal content is entered independent reactor, green coke amount is large compared with conventional lift pipe reactor, catalyst activity reduction amplitude also strengthens, cause material reactor subsequent reactions activity inferior very low, selectivity is very poor, has a strong impact on yield and the transformation efficiency of product.
Large quantity research shows, due to heavy oil composition and structure very complicated, distribution range is very wide, as vacuum residuum composition just from saturated point, fragrance assigns to colloid and bituminous matter, forms textural difference very big.The heavy oil hydrocarbon of different structure and composition or the Molecular Cloning suitable optimal operating condition of non-hydrocarbons not identical yet.If adopt single oil Refining Technologies, process according to the full fractions consisting of a set of changeless operational condition to raw material, often attend to one thing and lose sight of another, be difficult to the hydrocarbon distribution optimizing and the petroleum products maximization that realize hydro carbons.Such as, research for grand celebration paraffinic base heavy oil fluid catalytic cracking shows, optimal conversion is about 70%, dry gas yied now and coke yield increasing degree increase with transformation efficiency and increase less, namely dry gas and coke yield sum are in minimum with the ratio of transformation efficiency, but it is unconverted now to there is more heavy oil.After transformation efficiency increases and reaches certain value (as more than 75%), dry gas and coke yield increase with transformation efficiency and sharply increase, and catalytic cracking selectivity sharply declines.In addition, related industries production data shows: be in the catalytic cracking product of main raw material (intermingled dregs ratio 85%) with Daqing Vacuum Residue, when transformation efficiency reaches 76%, burn productive rate and reach 11%, dry gas, slurry oil and the total recovery of burning are more than 20%, compared to coking process, the catalytic cracking technology of high conversion there is no advantage on light receipts.
To sum up, also there is space to be modified in existing heavy oil fluid catalytic cracking method, increase yield of light oil and liquid yield while how improving heavy oil feedstock transformation efficiency, reducing the low value-added product productions such as dry gas, liquefied gas and coke as far as possible becomes problem demanding prompt solution simultaneously.
Summary of the invention
The invention provides a kind of heavy oil fluid catalytic cracking method, the difference of response characteristic is there is for Rfcc Feedstock, the heavy feed stock of composition complex is generated various dissimilar petroleum products through repeatedly conversion reaction, to meet the need of market, thus produce the industrial chemicals of light-end products and high added value with realizing maximum, improve the utilization ratio of heavy oil feedstock simultaneously.
The present invention also provides a kind of heavy oil catalytically cracking equipment realizing aforesaid method.
For achieving the above object, on the one hand, the invention provides a kind of heavy oil fluid catalytic cracking method, the reactor of employing comprises the first riser tube and the second riser tube, said method comprising the steps of:
Make heavy oil feedstock and catalytic cracking catalyst enter the first riser tube from bottom, contact in the first riser tube is also jointly up, and the first catalytic cracking reaction occurs simultaneously;
By the reaction oil gas fractionation from the first riser tube, obtain reacted gas, gasoline, diesel oil, recycle stock and slurry oil;
Described recycle stock is carried out catalytic hydrogenation reaction, and reaction conditions is temperature of reaction 340-380 DEG C, volume space velocity 0.5-2.0h -1, hydrogen to oil volume ratio 300-800, reaction pressure 7-12MPa, the oil gas fractionation generated by described catalytic hydrogenation reaction, obtains reacted gas, gasoline, diesel oil and shortening heavy oil;
Described shortening heavy oil is introduced the second riser tube and carries out the second catalytic cracking reaction, by the reaction oil gas fractionation from the second riser tube, obtain reacted gas, gasoline and diesel oil.
Further, the condition of described first catalytic cracking reaction is: temperature of reaction 460-520 DEG C, agent-oil ratio 7-11, reaction times 1.5-2.5s.
Further, the condition of described second catalytic cracking reaction is: temperature of reaction 480-520 DEG C, agent-oil ratio 6-10, reaction times 2.0-3.0s, shortening heavy oil enters described second riser tube at 200-400 DEG C, and water-oil ratio is 0.03-0.30, and pressure is 130-450kPa.
Further, the catalytic hydroconversion catalyzer that described recycle stock catalytic hydrogenation reaction uses is made up of with aluminum oxide and/or amorphous silicon aluminium carrier additive, group VIII metal, group vib metal, wherein said additive be selected from F, P, Fe and Pt one or more, described group vib metal be selected from Mo and W one or both, described group VIII metal to be selected from Co and Ni one or both.
Further, described catalytic hydroconversion catalyzer is made up of the aluminum oxide of the group VIII metal of 5-15wt% additive, 5-20wt%, 15-50wt%VIB race metal and surplus and/or amorphous silicon aluminium carrier.
Further, described method also comprises and uses solvent extration to remove bituminous matter in described slurry oil to obtain deasphalted oil, and described deasphalted oil is mixed with described recycle stock and carry out catalytic hydrogenation reaction.
Further, the extraction solvent that described solvent extration uses is selected from alkane or its mixed fraction of C3-C6.
On the other hand, the present invention also provides a kind of catalytic cracking unit implementing aforesaid method, and this device at least comprises:
First riser tube and the second riser tube, arrange feed(raw material)inlet and catalyst inlet respectively bottom it, top arranges outlet;
First oil and gas separating system and the second oil and gas separating system, it arranges oil gas and catalyst mix material entrance, oil gas vent and catalyst outlet respectively;
First main fractionating tower and the second main fractionating tower, it is inlet porting respectively, and top is provided with multiple light fraction outlet, and bottom is then provided with recycle stock outlet and slurry oil outlet;
Catalytic hydroconversion device, catalytic hydroconversion device arranges catalytic hydroconversion device portal and the outlet of catalytic hydroconversion device;
Secondary separation column, described secondary separation column arranges secondary separation column entrance, the outlet of shortening heavy oil and multiple light fraction outlet;
The oil gas of the first oil and gas separating system described in the outlet of described first riser tube and catalyst mix material entrance, the catalyst outlet of described first oil and gas separating system is communicated with the catalyst inlet of described first riser tube, oil gas vent is communicated with the entrance of described first main fractionating tower, the recycle stock outlet catalytic hydroconversion device portal of described first main fractionating tower, the secondary separation column entrance of catalytic hydroconversion device outlet, the feed(raw material)inlet of the second riser tube described in the shortening heavy oil outlet of secondary separation column, the oil gas of the second oil and gas separating system described in the outlet of described second riser tube and catalyst mix material entrance, the catalyst outlet of described second oil and gas separating system is communicated with the catalyst inlet of described second riser tube, oil gas vent is communicated with the entrance of described second main fractionating tower.
Further, also comprise extraction tower, described extraction tower has extraction tower entrance, de-oiled asphalt outlet and deasphalted oil outlet, and described extraction tower entrance is communicated with the slurry oil outlet of described first main fractionating tower, catalytic hydroconversion device portal described in described deasphalted oil outlet.
Further, described catalytic hydroconversion device is fixed-bed reactor.
The enforcement of the present invention program, at least has following advantage:
1, heavy oil fluid catalytic cracking method provided by the invention, by its component reaction characteristic difficulty or ease, heavy oil feedstock is progressively transformed, simultaneously, hydro-upgrading is carried out to not easily transforming component, the different components of heavy oil is transformed in its optimal conversion interval, improves the total conversion rate of heavy oil feedstock, improve yield of light oil and the liquid yield of high added value simultaneously, reduce the generation of dry gas and coke, to meet the need of market.
2, heavy oil catalytically cracking equipment provided by the invention can be used in realizing above-mentioned catalyst cracking method, and structure is simple, and operation is convenient.
Accompanying drawing explanation
The heavy oil catalytically cracking equipment schematic diagram of Fig. 1 for providing in one embodiment of the invention;
The heavy oil catalytically cracking equipment schematic diagram of Fig. 2 for providing in another embodiment of the present invention.
Embodiment
For making the object, technical solutions and advantages of the present invention clearly, below in conjunction with accompanying drawing, the technical scheme in the embodiment of the present invention is clearly and completely described, obviously, described embodiment is the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
In heavy oil fluid catalytic cracking method provided by the invention, the reactor adopted comprises the first riser tube and the second riser tube, said method comprising the steps of: make heavy oil feedstock and catalytic cracking catalyst enter the first riser tube from bottom, contact in the first riser tube is also jointly up, and the first catalytic cracking reaction occurs simultaneously; By the reaction oil gas fractionation from the first riser tube, obtain reacted gas, gasoline, diesel oil, recycle stock and slurry oil; Described recycle stock is carried out catalytic hydrogenation reaction, and reaction conditions is temperature of reaction 340-380 DEG C, volume space velocity 0.5-2.0h -1, hydrogen to oil volume ratio 300-800, reaction pressure 7-12MPa, the oil gas fractionation generated by described catalytic hydrogenation reaction, obtains reacted gas, gasoline, diesel oil and shortening heavy oil; Described shortening heavy oil is introduced the second riser tube and carries out the second catalytic cracking reaction, by the reaction oil gas fractionation from the second riser tube, obtain reacted gas, gasoline and diesel oil.
In aforesaid method, heavy oil feedstock enters the bottom of the first riser tube, contacts carry out the first catalytic cracking reaction with catalytic cracking catalyst, and the processing condition of this first catalytic cracking reaction can be usually: temperature of reaction 460-520 DEG C, agent-oil ratio 7-11, reaction times 1.5-2.5s.Generally, heavy oil feedstock need be preheated to 100-300 DEG C and enter riser tube reaction again.
Afterwards, the reaction oil gas (i.e. the oil gas of described first catalytic cracking reaction generation) from the first riser tube enters the first oil and gas separating system together with catalytic cracking catalyst.This first oil and gas separating system comprises settling vessel, is arranged at the stripping stage be communicated with below settling vessel and with it and the revivifier be communicated with described stripping stage.Described settling vessel is provided with oil gas and catalyst mix material entrance and oil gas vent, and described revivifier is provided with catalyst outlet.
The oil gas that described first catalytic cracking reaction generates and catalytic cracking catalyst are first by settling vessel, and the efficient air solid fast separating device arranged in settling vessel is separated.Isolated catalytic cracking catalyst enters stripping stage, enters revivifier regeneration after stripping; Catalytic cracking catalyst after regeneration returns and enters reactive system bottom the first riser tube and recycle.Isolated oil gas leaves settling vessel and enters bottom the first main fractionating tower and carry out fractionation, thus obtains heavy oil fluid catalytic cracking target product reacted gas, gasoline and diesel oil, obtains recycle stock and slurry oil simultaneously.
In one embodiment of the invention, can by reacted gas, raw gasline, diesel oil and slurry oil caterpillar, and recycle stock enters catalytic hydroconversion device and carries out shortening, under the effect of hydrogen and catalyzer, there is the upgrading reactions such as many cyclophanes ring hydrogenation fractional saturation of controllability.
Compared with existing heavy-oil hydrogenation, almost do not have the metallic impurity such as nickel, vanadium in recycle stock, nitrogen content is also very low, not asphaltenes.Because recycle stock character is more excellent, reaction conditions will relax than heavy-oil hydrogenation generally.In the recycle stock that usual employing aforesaid method obtains, hydrogen richness is 8.0wt%-11.5wt%, relative density 0.88-0.99.When hydrogen richness in recycle stock is low, relative density large, fraction distribution deflection high boiling point, harsher reaction conditions can be used.Carrying out selected catalytic hydroconversion processing condition according to above-mentioned freshening oil properties is: temperature of reaction 340-380 DEG C, volume space velocity 0.5-2.0h -1, hydrogen to oil volume ratio 300-800, reaction pressure 7-12MPa.Recycle stock after shortening generally can reach hydrogen richness 12wt%-13wt%, relative density 0.80-0.87.
In another embodiment of the invention, by reacted gas, gasoline and diesel oil caterpillar.The bituminous matter using solvent extration to remove in slurry oil obtains deasphalted oil, and this process is carried out in extraction tower.The temperature of extraction tower controls between 80-250 DEG C, and pressure is between 3.5-10.0MPa, and when entering extraction tower, the mass flux ratio of extraction solvent and slurry oil is 2.0-8.0:1, isolates diasphaltene oil phase and de-oiled asphalt phase afterwards.
The de-oiled asphalt caterpillar obtained, deasphalted oil then mixes with recycle stock, enters catalytic hydroconversion device together and carries out shortening, and reaction conditions is identical with a upper embodiment, repeats no more herein.
Afterwards, the oil gas that catalytic hydrogenation reaction generates enters secondary separation column and carries out fractionation, obtains heavy oil fluid catalytic cracking target product reacted gas, gasoline and diesel oil, obtains shortening heavy oil simultaneously.Reacted gas, gasoline and diesel oil are separated and goes out device.Hydrogenation heavy oil introduces the second riser tube from secondary Fractionator Bottom, carries out the second catalytic cracking reaction.The second catalytic cracking reaction technology condition in this second riser tube is: temperature of reaction 480-520 DEG C, agent-oil ratio 6-10, reaction times 2.0-3.0s, shortening heavy oil enters described second riser tube at 200-400 DEG C, water-oil ratio is 0.03-0.30, and pressure is 130-450kPa.Then, the reaction oil gas from the second riser tube enters the second main fractionating tower and carries out fractionation, obtains reacted gas, gasoline and diesel oil.
Be applicable to each the concrete equipment in the heavy oil catalytically cracking equipment of aforesaid method, such as riser tube, revivifier, settling vessel, oil-gas separator and catalytic hydroconversion device etc. are the common equipment in refining of petroleum field, require to carry out appropriate reconstruction and assemble coming into operation according to present invention process.Concrete structure of reactor can see suitable reactor configuration relevant in Chinese patent or patent application ZL200910242917.1, ZL200910242920.3, ZL200910242921.8, ZL200910242922.2, ZL200910242918.6 and ZL200910242919.0.
Catalyst cracking method in the present invention is suitable for all types of catalytic cracking catalyst.
Wherein, heavy oil feedstock can be the mixture of one or more arbitrary proportion in oil vacuum residuum (VR), long residuum (AR), hydrogenated residue, coker gas oil, deasphalted oil, crude oil with high acid value and high metal crude oil.
The catalytic hydroconversion catalyzer that catalytic hydrogenation reaction uses can be all types of hydrotreating catalyst with much higher Polycyclic aromatic hydrocarbons saturated activity; It can be such as the loaded catalyst of aluminum oxide and/or amorphous silicon aluminium supported on carriers group vib metal and/or group VIII metal.
The catalytic hydroconversion catalyzer used in a particular embodiment can be made up of the aluminum oxide of one or more group VIII metal of 5-15wt% additive, 5-20wt%, one or more group vib metals of 15-50wt% and surplus and/or amorphous silicon aluminium carrier.Wherein additive is selected from non-metallic element and the metallic elements such as fluorine, phosphorus, iron, platinum.Group vib metal is selected from Mo or/and W, group VIII metal are selected from Co or/and Ni.Fixed-bed reactor can be selected to realize this catalytic hydroconversion process.
In above-mentioned steps, shortening heavy oil also can enter in other catalytic cracking unit, under the condition that it is suitable, carry out efficient catalytic cracking reaction.
Below in conjunction with specific embodiments and the drawings, the present invention will be described in detail.
Embodiment 1
The heavy oil fluid catalytic cracking method provided in the present embodiment uses device as shown in Figure 1.Described device at least comprises:
First riser tube 101 and the second riser tube 302, arrange feed(raw material)inlet and catalyst inlet respectively bottom it, top arranges outlet;
First oil and gas separating system and the second oil and gas separating system, it arranges oil gas and catalyst mix material entrance, oil gas vent and catalyst outlet respectively;
First main fractionating tower 106 and the second main fractionating tower 303, it is inlet porting respectively, and top is provided with multiple light fraction outlet, and bottom is then provided with recycle stock outlet and slurry oil outlet;
Catalytic hydroconversion device 201, catalytic hydroconversion device 201 arranges catalytic hydroconversion device portal and the outlet of catalytic hydroconversion device;
Secondary separation column 202, described secondary separation column 202 arranges secondary separation column entrance, the outlet of shortening heavy oil and multiple light fraction outlet;
The oil gas of the first oil and gas separating system described in the outlet of described first riser tube 101 and catalyst mix material entrance, the catalyst outlet of described first oil and gas separating system is communicated with the catalyst inlet of described first riser tube 101, oil gas vent is communicated with the entrance of described first main fractionating tower 106, the recycle stock outlet catalytic hydroconversion device portal of described first main fractionating tower 106, the secondary separation column entrance of catalytic hydroconversion device outlet, the feed(raw material)inlet of the second riser tube 302 described in the shortening heavy oil outlet of secondary separation column 202, the oil gas of the second oil and gas separating system described in the outlet of described second riser tube 302 and catalyst mix material entrance, the catalyst outlet of described second oil and gas separating system is communicated with the catalyst inlet of described second riser tube 302, oil gas vent is communicated with the entrance of described second main fractionating tower 303.
Wherein, catalytic hydroconversion device 201 can use fixed-bed reactor.The light fraction outlet of the first main fractionating tower 106, second main fractionating tower 303 and secondary separation column 202 comprises the diesel oil outlet on oil gas product exit and the top being located at tower top, and oil gas product exit is communicated with catch pot 107, this catch pot 107 is also respectively equipped with cracking gas exit and fuel dispensing outlet.
The method that the device using the present embodiment to provide carries out heavy oil fluid catalytic cracking is summarized as follows:
Heavy oil feedstock 1 and catalytic cracking catalyst enter the bottom of the first riser tube 101, and it is up along the first riser tube 101, the first catalytic cracking reaction is carried out in contact simultaneously, the processing condition (namely carrying out the condition of the first catalytic cracking reaction) of the first riser tube 101 reaction zone are: temperature of reaction 460-520 DEG C, agent-oil ratio 7-11, reaction times 1.5-2.5s, raw material preheating temperature 100-300 DEG C.The oil gas generated enters settling vessel 102 together with catalytic cracking catalyst, and realize efficient gas solid separation through efficient air solid fast separating device 103, catalytic cracking catalyst enters revivifier 105 and regenerates after stripping stage 104; The bottom cycle that regenerated catalyst 2 returns the first riser tube 101 through inclined tube uses.
Isolated oil gas 3 from settling vessel 102 top out and enter bottom the first main fractionating tower 106 and carry out fractionation.The tower top oil gas 4 fractionated out enters catch pot 107 after condensing cooling, and reacted gas 5 is drawn from separating tank 107 top, and gasoline fraction 6 is drawn from separating tank 107 bottom, and a part is trim the top of column, another part caterpillar; Diesel oil 7 by drawing after stripping tower 108 stripping, slurry oil 9 while carrying out circulation at the bottom of tower, a part of caterpillar.Reacted gas 5, gasoline 6 and diesel oil 7 send into corresponding storage tank respectively as target product of the present invention.
Separate recycle stock 8 bottom first main fractionating tower 106, enter freshening oil tank 109, the many cyclophanes ring component in heavy oil feedstock 1 by enrichment, can carry out upgrading by further shortening in this recycle stock.With reference to accompanying drawing 1, freshening oil tank 109 recycle stock 8 out enters catalytic hydroconversion device 201, under the effect of hydrogen 16 and catalytic hydroconversion catalyzer, upgrading reaction occurs.Catalytic hydroconversion processing condition are: temperature of reaction 340-380 DEG C, volume space velocity 0.5-2.0h -1, hydrogen to oil volume ratio 300-800, reaction pressure 7-12MPa.Afterwards, reaction oil gas 10 enters secondary separation column 202 middle and lower part, carries out the separation of each component.Tower top oil gas 11 enters catch pot 107 after condensing cooling, and reacted gas 5 is drawn on catch pot 107 top, and gasoline 6 is drawn in bottom; Diesel oil 7 is by drawing after stripping tower 108 stripping, and shortening heavy oil 15 is drawn at the bottom of secondary separation column 202 tower.
Reacted gas 5, gasoline 6, diesel oil 7 are separated and gone out device.The second riser tube 302 introduced by 15, shortening heavy oil, carries out the second catalytic cracking reaction.The processing condition (namely carrying out the condition of the second catalytic cracking reaction) of this second riser tube 302 are: temperature of reaction 480-520 DEG C, agent-oil ratio 6-10, reaction times 2.0-3.0s, shortening heavy oil enters described second riser tube at 200-400 DEG C, water-oil ratio is 0.03-0.30, and pressure is 130-450kPa.Then, the reaction oil gas 316 from the second riser tube 302 enters the second main fractionating tower 303 and carries out fractionation, obtains reacted gas, gasoline and diesel oil.
For verifying effect of the present invention, adopting the device shown in Fig. 1 and technical process, the heavy oil fluid catalytic cracking pilot plant in laboratory is tested.
Table 1 is depicted as the character of heavy oil feedstock 1, recycle stock 8 and shortening heavy oil 15.Adopt the method in the present embodiment, recycle stock 8 enters catalytic hydroconversion device 201 and transforms, shortening heavy oil 15 after conversion is introduced the second riser tube 302 and is carried out the second catalytic cracking reaction, then, reaction oil gas 316 from the second riser tube 302 enters the second main fractionating tower 303 and carries out fractionation, obtains reacted gas, gasoline and diesel oil.The reaction conditions optimized is as shown in table 2, compares, adopt the method in this present embodiment that yield of light oil can be made to improve with conventional heavy oil catalytic cracking process, and liquid yield improves, and dry gas and coke yield obviously reduce, the visible table 3 of detailed product slates.
Table 1
Table 2
Table 3
Product Mass content
H 2S 0.4％
Fuel gas 2.6％
Liquefied gas 12.7％
Gasoline 49.2％
Diesel oil 27.4％ 7 -->
Slurry oil 1.2％
Coke 6.5％
Add up to 100.0％
Embodiment 2
The heavy oil fluid catalytic cracking method provided in the present embodiment uses device as shown in Figure 2.With the catalytic cracking unit in embodiment 1 unlike, the device of the present embodiment also comprises: extraction tower 301, described extraction tower 301 has extraction tower entrance, de-oiled asphalt outlet and deasphalted oil outlet, described extraction tower entrance is communicated with the slurry oil outlet of described first main fractionating tower 106, the entrance of catalytic hydroconversion device 201 described in described deasphalted oil outlet.
The method difference using the device that provides of the present embodiment to carry out in the method for heavy oil fluid catalytic cracking and embodiment 1 is, after slurry oil 9 is drawn at the bottom of the first main fractionating tower 106 tower, after mixing with the extraction solvent 26 for removing slurry oil studies on asphaltene, enter extraction tower 301, carry out diasphaltene process, this extraction solvent 26 is selected from alkane or its mixed fraction of C3-C6.The temperature of extraction tower 301 controls between 80-250 DEG C, and pressure is between 3.5-10.0MPa, and when entering extraction tower 301, extraction solvent 26 is 2.0-8.0:1 with the mass flux ratio of slurry oil 9, isolates de-oiled asphalt 17 and deasphalted oil 18.
De-oiled asphalt 17 goes out device, deasphalted oil 18 enters catalytic hydroconversion device 201 after then mixing with the recycle stock 8 of drawing from freshening oil tank 109, under the effect of hydrogen 16 and catalytic hydrogenation catalyst, generation catalytic hydroconversion reacts, and processing condition are in the same manner as in Example 1.
For verifying effect of the present invention, adopting the device shown in Fig. 2 and technical process, catalytic cracking process is carried out to the heavy oil feedstock in embodiment 1.
Table 4 contrasts for solvent extration in the present embodiment removes slurry oil studies on asphaltene processing condition and slurry oil and diasphaltene oil properties.Compare with conventional heavy oil fluid catalytic cracking, adopt the method in the present embodiment can improve yield of light oil and liquid yield, dry gas and coke yield obviously reduce, and simultaneously more effectively utilize heavy oil feedstock.The visible table 5 of product slates detailed in the present embodiment.
Table 4
Table 5
Product Weight content
H 2S 0.41％
Fuel gas 2.58％
Liquefied gas 12.81％
Gasoline 49.80％
Diesel oil 27.70％
Slurry oil 0.6％
Coke 6.1％
Add up to 100.0％
Last it is noted that above each embodiment is only in order to illustrate technical scheme of the present invention, be not intended to limit; Although with reference to foregoing embodiments to invention has been detailed description, those of ordinary skill in the art is to be understood that: it still can be modified to the technical scheme described in foregoing embodiments, or carries out equivalent replacement to wherein some or all of technical characteristic; And these amendments or replacement, do not make the essence of appropriate technical solution depart from the scope of various embodiments of the present invention technical scheme.

Claims (10)

1. a heavy oil fluid catalytic cracking method, is characterized in that, the reactor of employing comprises the first riser tube and the second riser tube, said method comprising the steps of:
Make heavy oil feedstock and catalytic cracking catalyst enter the first riser tube from bottom, contact in the first riser tube is also jointly up, and the first catalytic cracking reaction occurs simultaneously;
By the reaction oil gas fractionation from the first riser tube, obtain reacted gas, gasoline, diesel oil, recycle stock and slurry oil;
Described recycle stock is carried out catalytic hydrogenation reaction, and reaction conditions is temperature of reaction 340-380 DEG C, volume space velocity 0.5-2.0h -1, hydrogen to oil volume ratio 300-800, reaction pressure 7-12MPa, the oil gas fractionation generated by described catalytic hydrogenation reaction, obtains reacted gas, gasoline, diesel oil and shortening heavy oil;
Described shortening heavy oil is introduced the second riser tube and carries out the second catalytic cracking reaction, by the reaction oil gas fractionation from the second riser tube, obtain reacted gas, gasoline and diesel oil.
2. method according to claim 1, is characterized in that, the condition of described first catalytic cracking reaction is: temperature of reaction 460-520 DEG C, agent-oil ratio 7-11, reaction times 1.5-2.5s.
3. method according to claim 1, it is characterized in that, the condition of described second catalytic cracking reaction is: temperature of reaction 480-520 DEG C, agent-oil ratio 6-10, reaction times 2.0-3.0s, shortening heavy oil enters described second riser tube at 200-400 DEG C, and water-oil ratio is 0.03-0.30, and pressure is 130-450kPa.
4. method according to claim 1, it is characterized in that, the catalytic hydroconversion catalyzer that described recycle stock catalytic hydrogenation reaction uses is made up of with aluminum oxide and/or amorphous silicon aluminium carrier additive, group VIII metal, group vib metal, wherein said additive be selected from F, P, Fe and Pt one or more, described group vib metal be selected from Mo and W one or both, described group VIII metal to be selected from Co and Ni one or both.
5. method according to claim 4, is characterized in that, described catalytic hydroconversion catalyzer is made up of the aluminum oxide of the group VIII metal of 5-15wt% additive, 5-20wt%, 15-50wt%VIB race metal and surplus and/or amorphous silicon aluminium carrier.
6. the method according to any one of claim 1-5, is characterized in that, described method also comprises and uses solvent extration to remove bituminous matter in described slurry oil to obtain deasphalted oil, and described deasphalted oil is mixed with described recycle stock and carry out catalytic hydrogenation reaction.
7. method according to claim 6, is characterized in that, the extraction solvent that described solvent extration uses is selected from alkane or its mixed fraction of C3-C6.
8. for implementing the claims a heavy oil catalytically cracking equipment for the method described in any one of 1-7, it is characterized in that, described device at least comprises:
First riser tube and the second riser tube, arrange feed(raw material)inlet and catalyst inlet respectively bottom it, top arranges outlet;
First oil and gas separating system and the second oil and gas separating system, it arranges oil gas and catalyst mix material entrance, oil gas vent and catalyst outlet respectively;
First main fractionating tower and the second main fractionating tower, it is inlet porting respectively, and top is provided with multiple light fraction outlet, and bottom is then provided with recycle stock outlet and slurry oil outlet;
Catalytic hydroconversion device, catalytic hydroconversion device arranges catalytic hydroconversion device portal and the outlet of catalytic hydroconversion device;
Secondary separation column, described secondary separation column arranges secondary separation column entrance, the outlet of shortening heavy oil and multiple light fraction outlet;
The oil gas of the first oil and gas separating system described in the outlet of described first riser tube and catalyst mix material entrance, the catalyst outlet of described first oil and gas separating system is communicated with the catalyst inlet of described first riser tube, oil gas vent is communicated with the entrance of described first main fractionating tower, the recycle stock outlet catalytic hydroconversion device portal of described first main fractionating tower, the secondary separation column entrance of catalytic hydroconversion device outlet, the feed(raw material)inlet of the second riser tube described in the shortening heavy oil outlet of secondary separation column, the oil gas of the second oil and gas separating system described in the outlet of described second riser tube and catalyst mix material entrance, the catalyst outlet of described second oil and gas separating system is communicated with the catalyst inlet of described second riser tube, oil gas vent is communicated with the entrance of described second main fractionating tower.
9. device according to claim 8, it is characterized in that, also comprise extraction tower, described extraction tower has extraction tower entrance, de-oiled asphalt outlet and deasphalted oil outlet, described extraction tower entrance is communicated with the slurry oil outlet of described first main fractionating tower, catalytic hydroconversion device portal described in described deasphalted oil outlet.
10. device according to claim 8 or claim 9, it is characterized in that, described catalytic hydroconversion device is fixed-bed reactor.
CN201510850129.6A 2015-11-27 2015-11-27 RFCC method and apparatus Expired - Fee Related CN105505461B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510850129.6A CN105505461B (en) 2015-11-27 2015-11-27 RFCC method and apparatus

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510850129.6A CN105505461B (en) 2015-11-27 2015-11-27 RFCC method and apparatus

Publications (2)

Publication Number Publication Date
CN105505461A true CN105505461A (en) 2016-04-20
CN105505461B CN105505461B (en) 2017-05-31

Family

ID=55713770

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510850129.6A Expired - Fee Related CN105505461B (en) 2015-11-27 2015-11-27 RFCC method and apparatus

Country Status (1)

Country Link
CN (1) CN105505461B (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101191081A (en) * 2006-11-30 2008-06-04 中国石油化工股份有限公司 Catalytic conversion method for hydrocarbon oil raw material
CN103627434A (en) * 2012-08-27 2014-03-12 中国石油化工股份有限公司 Hydrotreatment combined catalytic cracking method for producing propylene
CN104449840A (en) * 2014-11-05 2015-03-25 中国石油大学(北京) Method for processing low-grade heavy oil

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101191081A (en) * 2006-11-30 2008-06-04 中国石油化工股份有限公司 Catalytic conversion method for hydrocarbon oil raw material
CN103627434A (en) * 2012-08-27 2014-03-12 中国石油化工股份有限公司 Hydrotreatment combined catalytic cracking method for producing propylene
CN104449840A (en) * 2014-11-05 2015-03-25 中国石油大学(北京) Method for processing low-grade heavy oil

Also Published As

Publication number Publication date
CN105505461B (en) 2017-05-31

Similar Documents

Publication Publication Date Title
CN101531558B (en) Catalytic conversion method for preparing propylene and aromatic hydrocarbons
CN103059972B (en) Combined hydrogenation method of producing chemical materials
CN102373084B (en) Method producing light fuel oil and propylene from poor residual oil
CN100510023C (en) Production of cleaning fuel from heavy-fraction oil
CN105462610B (en) A kind of anthracene oil hydrogenation method
CN102796559A (en) Method and apparatus for producing fuel oil by hydrocracking
CN102102028B (en) Fractional and divisional catalytic cracking method and device for heavy oil
CN105505462A (en) Catalytic cracking method of heavy oil and device thereof
CN103102982A (en) Combined process for conversion of residual oil
CN103773473A (en) Two-stage hydrocracking method used for producing high-quality jet fuel
CN103305272B (en) Catalytic conversion method for reducing yield of cokes
CN105505459A (en) Catalytic cracking method of heavy oil and device thereof
CN109777501B (en) Refinery gas combined processing method
CN115895722A (en) System for preparing light aromatic hydrocarbon from heavy oil raw material
CN105419868A (en) Heavy oil fluid catalytic cracking method and device
CN106609151B (en) A kind of method for producing low-carbon alkene
CN105505460A (en) Catalytic cracking method of heavy oil and device thereof
CN105001907B (en) A kind of method and system of paraffinic base crude oil with poor quality Poly-generation
CN203845992U (en) Paraffin base inferior crude oil poly-generation system
CN105505461A (en) Catalytic cracking method of heavy oil and device thereof
CN101875856A (en) Wax oil hydrogenated treatment and catalytic cracking combined method
CN102234532B (en) Series-connected, partitioned and classified method and apparatus for catalytic cracking of heavy oil
CN105505463A (en) Catalytic cracking method of heavy oil and device thereof
CN113817504B (en) Combined process for preparing chemical products from crude oil
CN113817503B (en) Combined process for preparing chemical products from crude oil

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20170531

Termination date: 20201127