CN106609146B - A kind of adjusting thermally equilibrated method of Fischer Tropsch synthetic oil in catalytic cracking mode - Google Patents
A kind of adjusting thermally equilibrated method of Fischer Tropsch synthetic oil in catalytic cracking mode Download PDFInfo
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Abstract
The present invention relates to Fischer Tropsch synthetic oil in catalytic cracking mode fields, specifically disclose a kind of adjusting thermally equilibrated method of Fischer Tropsch synthetic oil in catalytic cracking mode, and this method includes：(1) Fischer-Tropsch synthesis oil and the regenerated catalyst of heat in first reactor are subjected to cracking reaction, obtain the first reaction stream；(2) poor oil and fresh catalyst in second reactor are subjected to cracking reaction, obtain the second reaction stream；(3) first reaction stream and second reaction stream injection settler are detached, the reclaimable catalyst isolated enters regenerator coke burning regeneration after stripping, and the obtained regenerated catalyst of heat is returned first reactor and is recycled.According to the adjusting thermally equilibrated method of Fischer Tropsch synthetic oil in catalytic cracking mode provided by the invention, the thermal balance of catalytic cracking unit itself disclosure satisfy that.
Description
Technical field
The present invention relates to the method for transformation of Fischer-Tropsch synthesis oil in the absence of hydrogen, and in particular, to a kind of adjusting
The thermally equilibrated method of Fischer Tropsch synthetic oil in catalytic cracking mode.
Background technology
Oil is a kind of non-renewable resources, with current petroleum reserves increasingly reduce and consumption increases sharply,
Research in relation to petroleum-based products substitute increasingly heats up.Wherein, the research that F-T synthesizes oil tech had for more than 80 years, Sasol,
The F- T synthesis technology for the independent development that the companies such as Shell, Exxon/Mobil have it ripe.
Fischer-Tropsch synthesis oil and natural oil have larger difference on hydro carbons composition, be it is a kind of mainly by the alkane of straight chain and
The substance that alkene is formed, is substantially free of aromatic hydrocarbons.Each fraction of Fischer-Tropsch synthetic needs to modify by corresponding processing, ability
It obtains meeting the fluid product using specification.At present, for the diesel oil of Fischer-Tropsch synthesis oil and more heavy distillat, it may be used plus hydrogen is split
The positive structure of the good short chain of cryogenic property or isoparaffin are cut off or be isomerized to long chain hydrocarbons therein by change/isomerization process, obtains
To the jet fuel of high quality and diesel oil blending component；It can also preferably be lubricated using hydroisomerizing DEWAXING TECHNIQUE synthesising property
Oil base oil.The gasoline fraction Determination of Alkane Content of Fischer-Tropsch synthesis oil is higher, and octane number is low, is not suitable for as gasoline blend component, warp
Ethylene can be produced after crossing hydrofinishing as the raw material of steam cracking device.To sum up, the secondary of Fischer-Tropsch synthesis oil adds
Work is directed to greatly the hydrogenation process of costliness or the high temperature pyrolysis process that energy consumption is higher.
It can be seen that from document report in recent years and Fischer-Tropsch synthesis oil raw material, table processed using catalytic cracking (FCC) technology
Reveal outstanding production low-carbon alkene or produce the performance of gasoline.The operation of FCC apparatus needs it to be in thermal balance.In order to solve
Thermal balance process operates this problem, and U.S. Patent application US684756 discloses one kind and converted in fluidized catalytic cracker
The method of Fischer Tropsch waxes.The patent is pointed out to need additional heat in regeneration step to provide thermally equilibrated FCC operations, example
Reach thermal balance such as by for example clean synthesis gas and tail gas these potential fuel are used.Chinese patent application
CN103210059A discloses a kind of method of the heat balance operation catalytic cracking Fischer-Tropsch synthesis oil using catalytic cracking system.It should
Method is using the large pore zeolite Cracking catalyst of high rare earth oxide with operating riser reactor under suitable cracking conditions
Combine, it can heat balance operation without using additional heat source or heavy charge.
Invention content
The purpose of the present invention is to propose to a kind of adjusting thermally equilibrated method of Fischer Tropsch synthetic oil in catalytic cracking mode, to solve be catalyzed
During cracking processing Fischer-Tropsch synthesis oil the problem of shortage of heat.
The present inventor is by the study found that during catalyzed cracking processing Fischer-Tropsch synthesis oil, in order to reach heat
Balancing run, can by making enough coke laydowns during the cracking reaction of heat absorption on a catalyst, thus when
In regenerator by coke from catalyst burn off when there are enough combustions heat to be absorbed by catalyst to provide catalytic cracking reaction
Heat demand.However, the hydro carbons composition due to Fischer-Tropsch synthesis oil is mainly alkane, aromatic hydrocarbons is practically free of, thus these raw materials
Coking yield is very low in cracking process.For this purpose, the present inventor intends through poor oil green coke on fresh catalyst, with
Solve the problems, such as Fischer-Tropsch synthesis oil shortage of heat in catalytic cracking process, so as to complete the present invention.
The present invention provides a kind of adjusting thermally equilibrated method of Fischer Tropsch synthetic oil in catalytic cracking mode, this method includes：(1) will take
Support synthetic oil and the regenerated catalyst of heat carry out cracking reaction in first reactor, obtain the first reaction stream；It (2) will be inferior
Oil carries out cracking reaction with fresh catalyst in second reactor, obtains the second reaction stream；(3) by first reactant
Stream and second reaction stream injection settler are detached, and the reclaimable catalyst isolated enters regenerator after stripping and burns
Coke regeneration, and the obtained regenerated catalyst of heat is returned into first reactor and is recycled.
In the method provided by the invention, with fresh catalyst cracking reaction occurs for poor oil, generates most of burnt
Charcoal hangs burnt catalyst and mixes and settle in settler with the reclaimable catalyst from first reactor, and coke is in regenerator
Releasing heat is inside burnt, the heat needed for Fischer-Tropsch synthesis oil reaction-regeneration system can be supplemented；Obtained by poor oil cracking simultaneously
Arene content is high in gasoline fraction, can improve the problem of arene content is low in Fischer-Tropsch synthesis oil cracking gasoline.
And, it is generally the case that catalytic cracking unit has different degrees of catalyst stack less during stable operation,
Generally 0.5-1.5 kilograms catalyst/ton oil.And to keep Catalyst Balance Activity, what need to be quantified draws off equilibrium catalyst, this
Fresh dose of addition for requiring catalytic cracking unit that need to quantify.This field staff is it is well known that the activity of fresh catalyst
Very high, hydrothermal stability is poor, is not suitable for directly contacting progress catalytic cracking reaction with feedstock oil.The operation of catalytic cracking unit
Usually fresh dose is added in regenerator.And in the present invention, fresh catalyst is continuously added in reactor and fry dried food ingredients inferior
On the one hand raw catalytic cracking reaction can adhere to a large amount of coke and be haggled not with making up life during Fischer Tropsch synthetic oil in catalytic cracking mode
The defects of sufficient, in another aspect fresh catalyst continuous adding device, is conducive to the stability of device and the stabilization of product distribution
Property.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Description of the drawings
Attached drawing is to be used to provide further understanding of the present invention, and a part for constitution instruction, with following tool
Body embodiment is used to explain the present invention, but be not construed as limiting the invention together.In the accompanying drawings：
Fig. 1 is the flow diagram for adjusting the thermally equilibrated method of Fischer Tropsch synthetic oil in catalytic cracking mode provided by the invention.
Reference sign
1 pipeline (injection Fischer-Tropsch synthesis oil and vapor)
2 first riser reactors
3 fluidized-bed reactors
4 pipelines (injection poor oil and vapor)
5 pipelines (injection fresh catalyst)
6 heating furnaces
7 pipelines (fresh catalyst of injection heating)
8 second riser reactors
9 settlers
10 pipelines (logical reaction oil gas)
11 strippers
12 pipelines (injection stripped vapor)
13 reclaimable catalyst inclined tubes
14 pipelines (injection oxygen-containing gas)
15 regenerators
16 pipelines (row's regenerated flue gas)
17 regenerative agent feed-lines
Specific embodiment
The specific embodiment of the present invention is described in detail below.It is it should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The adjusting thermally equilibrated method of Fischer Tropsch synthetic oil in catalytic cracking mode provided by the invention includes：
(1) Fischer-Tropsch synthesis oil and the regenerated catalyst of heat in first reactor are subjected to cracking reaction, it is anti-obtains first
Answer logistics；
(2) poor oil and fresh catalyst in second reactor are subjected to cracking reaction, obtain the second reaction stream；
(3) first reaction stream and second reaction stream injection settler are detached, that isolates treats
Raw catalyst enters regenerator coke burning regeneration after stripping, and the obtained regenerated catalyst of heat is returned first reactor cycle
It uses.
In the method provided by the invention, split in Fischer-Tropsch synthesis oil and the independent reactor of each leisure of poor oil
Change reaction, but the reaction stream of the two shares settler and carries out sedimentation separation.
In the present invention, catalyst is the system of fresh catalyst, equilibrium catalyst, regenerated catalyst and reclaimable catalyst
Claim.The catalyst can be the Cracking catalyst of this field routine.In one embodiment, the activearm of the catalyst
Point can be selected from Y the or HY types zeolite with or without rare earth, the ultrastable with or without rare earth, ZSM-5 series zeolites,
It is one or more in silica-rich zeolite and β zeolites with five-membered ring structure.
In the present invention, the fresh catalyst is the catalyst without aging, and micro-activity can be 80-95%.
In the present invention, the regenerated catalyst is device equilibrium catalyst, and micro-activity can be 50-75%.
In the present invention, the first reactor can be riser reactor, downer reactor, riser and fluidisation
Bed compound reactor, down pipe and fluid bed compound reactor or fluidized-bed reactor.Wherein, riser, down pipe and stream
Change the riser, down pipe and fluid bed that bed is isodiametric riser, down pipe and fluid bed or various variable diameters.
The cracking reaction condition of the first reactor can include：Temperature is 450-650 DEG C, preferably 480-600 DEG C；
The oil gas residence time is 0.5-40 seconds, preferably 1-20 seconds；The weight ratio of catalyst and feedstock oil is 4-40：1, preferably 8-
30：1.
In the present invention, the second reactor can be riser reactor or downer reactor.Wherein, riser
It is the riser and down pipe of isodiametric riser and down pipe or various variable diameters with down pipe.
The cracking reaction condition of the second reactor can include：Temperature is 450-650 DEG C, preferably 480-600 DEG C；
The oil gas residence time is 0.5-40 seconds, preferably 1-20 seconds；The weight ratio of catalyst and feedstock oil is 1-40：1, preferably 4-
20：1.
In the present invention, the Fischer-Tropsch synthesis oil can be selected from ranging from 23 DEG C of Fischer-Tropsch synthetic mid-boiling point to the end point of distillation
Part fraction or full fraction in one or more mixtures.
In the present invention, the poor oil can be the slurry oil of catalytic cracking process production, and coking, thermal cracking, visbreaking are split
Change the heavy end of Process Production, it is one or more in straight run reduced pressure distillate and straight asphalt.
In the present invention, the dosage of the poor oil can account for the 5-30 weight % of the dosage of the Fischer-Tropsch synthesis oil, excellent
It is selected as 10-25 weight %.
Method provided by the present invention is described further below in conjunction with Fig. 1.
Fig. 1 is the flow diagram for adjusting the thermally equilibrated method of Fischer Tropsch synthetic oil in catalytic cracking mode provided by the invention.
Equipment and the shape and size of pipeline are not limited by the accompanying figures, but are determined as the case may be.
As shown in Figure 1, the regenerated catalyst of heat enters the bottom of the first riser reactor 2 through regenerative agent feed-line 17
After being mixed with the Fischer-Tropsch synthesis oil and vapor for injecting pipeline 1, cracking reaction occurs for portion.The mixing of reaction oil gas and catalyst
Outlet of the object through the first riser reactor 2 enters fluidized-bed reactor 3.For adjust the thermally equilibrated poor oil of reaction regeneration and
Vapor injects the bottom of the second riser reactor 8 through pipeline 4, and fresh catalyst leads to after the heating of 5 heated stove 6 of pipeline
It crosses pipeline 7 to contact with poor oil and cracking reaction occurs, later the catalyst of separation reaction oil gas and carbon deposit in settler 9.
Reaction oil gas is sent into subsequent separation system through pipeline 10.The catalyst of carbon deposit is under the effect of gravity after the reaction detached in settler
Enter stripper 11 through fluidized-bed reactor 3, stripped vapor is injected through pipeline 12, by the reaction oil gas entrained by carbon deposited catalyst
Stripping is clean as much as possible.The hydrocarbon product adsorbed on the carbon deposited catalyst that stripped vapor is stripped off passes through fluidized-bed reactor 3
Into in settler 9.Reclaimable catalyst is sent into regenerator 15 through reclaimable catalyst inclined tube 13.Oxygen-containing gas such as air or oxygen passes through
Pipeline 14 injects regenerator 15 from bottom, carries out coke burning regeneration.Regenerated flue gas is drawn through pipeline 16.Regenerated catalyst is through regenerative agent
Feed-line 17 returns to be recycled in the first riser reactor 2.
Embodiment
Catalyst used in embodiment is by the industry of catalyst asphalt in Shenli Refinery of Sinopec Group
Production, product designation MMC-2, the catalyst contain the ZSP zeolites of ultrastable and average pore size less than 0.7 nanometer,
The property of fresh catalyst is shown in Table 1.Equilibrium catalyst for fresh catalyst at a temperature of 800 DEG C through 100% saturated vapor water
Heat ageing 14 hours, the main physico-chemical property of the catalyst are shown in Table 2.
Fischer-Tropsch synthesis oil raw material used in embodiment is Fischer Tropsch waxes, and main physico-chemical property is shown in Table 3.In embodiment
Poor oil used is the vacuum distillate of outsourcing, and property is shown in Table 4.
Table 1
| Catalyst | Fresh dose |
| Zeolite content/weight % | |
| Y | 16 |
| ZSP | 12 |
| Specific surface/(m2/g) | 203 |
| Micro-activity, % | 89 |
Table 2
| Catalyst | Equilibrium catalyst |
| Zeolite content/weight % | |
| Y | 16 |
| ZSP | 12 |
| Physical property | |
| Specific surface/(m2/g) | 143 |
| Pore volume/(cm3/g) | 0.186 |
| Apparent density/(g/cm3) | 0.85 |
| Screening/weight % | |
| 0-20μm | 0.8 |
| 0-40μm | 10.4 |
| 0-80μm | 70.8 |
| 0-110μm | 88.5 |
| 0-149μm | 97.8 |
| >149μm | 2.2 |
| Micro-activity, % | 64 |
Table 3
| Project | F-T waxes |
| Density (20 DEG C)/gcm-3 | 0.806 |
| Solidification point/DEG C | 76 |
| Element forms (ω)/% | |
| C | 85.18 |
| H | 14.47 |
| O | 0.35 |
| S/μg·g-1 | 1.6 |
| N/μg·g-1 | 5 |
| Boiling range/DEG C | |
| Initial boiling point | 268 |
| 10% | 391 |
| 30% | 465 |
| 50% | 521 |
| 70% | 584 |
| 90% | 652 |
Table 4
| Project | Vacuum distillate |
| Density (20 DEG C)/(gcm-3) | 1.038 |
| Carbon residue/% | 4.13 |
| Element forms (ω)/% | |
| C | 89.1 |
| H | 9.3 |
| Boiling range/DEG C | |
| Initial boiling point | 304 |
| 10% | 351 |
| 50% | 473 |
| Four components/% | |
| Saturated hydrocarbons | 34.05 |
| Aromatic hydrocarbons | 59.88 |
| Colloid | 5.31 |
| Asphalitine | 0.76 |
Embodiment 1-2
The present embodiment is for the specification adjusting thermally equilibrated method of Fischer Tropsch synthetic oil in catalytic cracking mode provided by the invention.
It is tested using the middle- scale device of successive reaction-regenerative operation shown in FIG. 1, first reactor is anti-for riser
Device is answered, the internal diameter of riser reactor is 16 millimeters, is highly 6 meters；Second reactor is riser reactor, promotes tube reaction
The internal diameter of device is 16 millimeters, is highly 3 meters.Middle- scale device maintains reaction-regeneration system temperature using electrical heating.Middle- scale device
Equilibrium catalyst reserve is 8kg, and the addition rate of fresh catalyst is 0.6kg/h.Because middle- scale device catalyst stack less is unknown
It is aobvious, therefore regenerated catalyst is set to unload agent mouth at regenerator sloped tube, agent rate is unloaded as 0.6kg/h.
Temperature be 680 DEG C or so regenerated catalyst through regenerator sloped tube enter the first riser reactor bottom, and
It is flowed up under the action of pre-lift steam.The Fischer Tropsch waxes of preheating are sprayed by feed nozzle under atomizing steam effect and are promoted
Pipe reactor contacts with the regenerated catalyst of heat and carries out catalytic cracking reaction.Vacuum distillate is under atomizing steam effect by spraying
Mouth sprays into the second riser reactor, with being heated to 600 DEG C of contacts fresh catalyst and being reacted.First, second is promoted
The reaction oil gas and reclaimable catalyst of pipe reactor enter settler from reactor outlet, reaction oil gas and are urged in settler
Agent quick separating.Reaction oil gas is further separated into the liquid such as gaseous product and gasoline fraction, diesel oil distillate and heavy oil fraction
Product.The reclaimable catalyst isolated in settler is entered by gravity in stripper, the reclaimable catalyst after stripping
Regenerator is entered through reclaimable catalyst pipeline, contacts and is regenerated with heated air in regenerator.Coke burning regeneration is extensive
Active regenerated catalyst is again returned in the first riser reactor and is recycled.
Prevailing operating conditions and result are listed in table 5.
Comparative example 1
Fischer Tropsch synthetic oil in catalytic cracking mode reaction is carried out according to the method for embodiment 1, the difference is that anti-in the first riser
The bottom of device is answered to be not injected into Fischer-Tropsch synthesis oil.
Prevailing operating conditions and result are listed in table 5.
Comparative example 2
Fischer Tropsch synthetic oil in catalytic cracking mode reaction is carried out according to the method for embodiment 1, the difference is that anti-in the second riser
The bottom of device is answered to be not injected into vacuum distillate.
Prevailing operating conditions and result are listed in table 5.
Table 5
| Project | Embodiment 1 | Embodiment 2 | Comparative example 1 | Comparative example 2 |
| Fischer Tropsch waxes treating capacity/(kg/h) | 1 | 1 | 0 | 1 |
| Vacuum distillate treating capacity/(kg/h) | 0.10 | 0.25 | 0.10 | 0 |
| First riser reaction condition | ||||
| Reaction temperature/DEG C | 500 | 580 | 500 | 500 |
| Reaction time/s | 1.8 | 2.5 | 1.8 | 1.8 |
| Second riser reaction condition |
| Reaction temperature/DEG C | 480 | 480 | 480 | 480 |
| Reaction time/s | 2.1 | 1.8 | 2.1 | 2.1 |
| Fresh dose of charge velocity/(kg/h) | 0.4 | 0.6 | 0.4 | 0.4 |
| Regenerative agent draws off rate/(kg/h) | 0.4 | 0.6 | 0.4 | 0.4 |
| Regeneration | CO completely burneds | CO completely burneds | CO completely burneds | CO completely burneds |
| Regeneration temperature/DEG C | 680 | 680 | 680 | 680 |
| Product yield/(kg/h) | ||||
| Dry gas | 0.014 | 0.025 | 0.005 | 0.009 |
| Liquefied gas | 0.529 | 0.684 | 0.026 | 0.503 |
| Gasoline | 0.471 | 0.402 | 0.023 | 0.448 |
| Diesel oil | 0.040 | 0.046 | 0.007 | 0.033 |
| Heavy oil | 0.002 | 0.004 | 0.002 | 0 |
| Coke | 0.044 | 0.089 | 0.037 | 0.007 |
| Aromatic Hydrocarbon in Gasoline mass fraction/% | 26.3 | 54.6 | 67.2 | 24.2 |
By table 5 as it can be seen that according to the adjusting thermally equilibrated method of Fischer Tropsch synthetic oil in catalytic cracking mode provided by the invention, coke
It is suitable to measure, and disclosure satisfy that the thermal balance of catalytic cracking unit itself；The aromatics quality score ratio in product gasoline obtains simultaneously
It improves.
Claims (13)
1. a kind of adjusting thermally equilibrated method of Fischer Tropsch synthetic oil in catalytic cracking mode, this method include：
(1) Fischer-Tropsch synthesis oil and the regenerated catalyst of heat in first reactor are subjected to cracking reaction, obtain the first reactant
Stream；
(2) poor oil and fresh catalyst in second reactor are subjected to cracking reaction, obtain the second reaction stream；
(3) first reaction stream and second reaction stream injection settler are detached, that isolates to be generated urges
Agent enters regenerator coke burning regeneration after stripping, and the obtained regenerated catalyst of heat return first reactor cycle is made
With；
Wherein, the second reactor is riser reactor.
2. according to the method described in claim 1, wherein, the active component of catalyst is selected from Y the or HY types with or without rare earth
Zeolite, ZSM-5 series zeolites, has the silica-rich zeolite of five-membered ring structure and β zeolites at the ultrastable with or without rare earth
In it is one or more.
3. method according to claim 1 or 2, wherein, the fresh catalyst is the catalyst without aging, micro- anti-
Activity is 80-95%.
4. method according to claim 1 or 2, wherein, the micro-activity of the regenerated catalyst is 50-75%.
5. according to the method described in claim 1, wherein, the first reactor is riser reactor, downer reactor,
Riser and fluid bed compound reactor, down pipe and fluid bed compound reactor or fluidized-bed reactor.
6. method according to claim 1 or 5, wherein, the cracking reaction condition of the first reactor includes：Temperature is
450-650℃；The oil gas residence time is 0.5-40 seconds；The weight ratio of catalyst and feedstock oil is 4-40：1.
7. according to the method described in claim 6, wherein, the cracking reaction condition of the first reactor includes：Temperature is
480-600℃；The oil gas residence time is 1-20 seconds；The weight ratio of catalyst and feedstock oil is 8-30：1.
8. according to the method described in claim 1, wherein, the cracking reaction condition of the second reactor includes：Temperature is
450-650℃；The oil gas residence time is 0.5-40 seconds；The weight ratio of catalyst and feedstock oil is 1-40：1.
9. according to the method described in claim 8, wherein, the cracking reaction condition of the second reactor includes：Temperature is
480-600℃；The oil gas residence time is 1-20 seconds；The weight ratio of catalyst and feedstock oil is 4-20：1.
10. according to the method described in claim 1, wherein, the Fischer-Tropsch synthesis oil is selected from Fischer-Tropsch synthetic mid-boiling point range
For one or more mixtures in 23 DEG C to the end point of distillation of part fractions or full fraction.
11. according to the method described in claim 1, wherein, the poor oil is the slurry oil of catalytic cracking process production, coking,
Thermal cracking, the heavy end of viscosity breaking technology generation, it is one or more in straight run reduced pressure distillate and straight asphalt.
12. according to the method described in claim 1,10 or 11, wherein, the dosage of the poor oil accounts for the Fischer-Tropsch synthesis oil
The 5-30 weight % of dosage.
13. according to the method for claim 12, wherein, the dosage of the poor oil accounts for the dosage of the Fischer-Tropsch synthesis oil
10-25 weight %.
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| CN1382528A (en) * | 2001-04-28 | 2002-12-04 | 中国石油化工股份有限公司 | Cyclic polluting and ageing process for catalyst |
| CN101743292A (en) * | 2006-07-13 | 2010-06-16 | 沙特阿拉伯石油公司 | Ancillary cracking of heavy oils in conjuction with FCC unit operations |
| CN102533322A (en) * | 2010-12-30 | 2012-07-04 | 中国石油化工股份有限公司 | Method for producing propylene by using Fischer Tropsch synthetic oil in catalytic cracking mode |
| CN102925210A (en) * | 2011-08-12 | 2013-02-13 | 中国石油天然气股份有限公司 | Catalytic cracking method and device with low oil agent contact temperature difference |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1382528A (en) * | 2001-04-28 | 2002-12-04 | 中国石油化工股份有限公司 | Cyclic polluting and ageing process for catalyst |
| CN101743292A (en) * | 2006-07-13 | 2010-06-16 | 沙特阿拉伯石油公司 | Ancillary cracking of heavy oils in conjuction with FCC unit operations |
| CN102533322A (en) * | 2010-12-30 | 2012-07-04 | 中国石油化工股份有限公司 | Method for producing propylene by using Fischer Tropsch synthetic oil in catalytic cracking mode |
| CN102925210A (en) * | 2011-08-12 | 2013-02-13 | 中国石油天然气股份有限公司 | Catalytic cracking method and device with low oil agent contact temperature difference |
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