CN106609146A - Method for adjusting catalytic cracking thermal balance of Fischer-Tropsch synthetic oil - Google Patents
Method for adjusting catalytic cracking thermal balance of Fischer-Tropsch synthetic oil Download PDFInfo
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Abstract
The invention relates to the field of catalytic cracking of Fischer-Tropsch synthetic oil and discloses a method for adjusting catalytic cracking thermal balance of Fischer-Tropsch synthetic oil. The method comprises that (1) Fischer-Tropsch synthetic oil undergoes a cracking reaction in the presence of a hot regenerated catalyst to produce a first reactant flow, (2) poor quality oil undergoes a cracking reaction in the presence of a fresh catalyst in a second reactor to produce a second reactant flow, and (3) the first reactant flow and the second reactant flow are injected into a settler and are separated, the separated catalyst to be regenerated is subjected to steam stripping, then is fed into a regenerator and is subjected to charring regeneration, and the obtained hot regenerated catalyst is returned to the first reactor and then is recycled. The method for adjusting catalytic cracking thermal balance of Fischer-Tropsch synthetic oil can satisfy heat balance of a catalytic cracking apparatus.
Description
Technical field
The present invention relates to the method for transformation of Fischer-Tropsch synthesis oil in the absence of hydrogen, in particular it relates to
It is a kind of to adjust 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 it is fast
Speed increases, and the research about petroleum-based products substitute increasingly heats up.Wherein, F-T synthesizes oil tech
There is independently opening for its maturation in the companies such as research existing more than 80 years, Sasol, Shell, Exxon/Mobil
The F- T synthesis technology sent out.
Fischer-Tropsch synthesis oil and natural oil have larger difference on hydro carbons composition, are one kind mainly by straight chain
Alkane and alkene constitute material, be substantially free of aromatic hydrocarbons.Each fraction of Fischer-Tropsch synthetic needs Jing
Corresponding processing modification is crossed, can just obtain meeting the fluid product using specification.At present, for Fischer-Tropsch is closed
Into diesel oil and the more heavy distillat of oil, can adopt be hydrocracked/long chain hydrocarbons therein are cut off by isomerization process
Or be isomerized to the positive structure of the good short chain of cryogenic property or isoparaffin, obtain high-quality jet fuel and
Diesel oil blending component；The preferable lube base of hydroisomerizing DEWAXING TECHNIQUE synthesising property can also be adopted
Oil.The gasoline fraction Determination of Alkane Content of Fischer-Tropsch synthesis oil is higher, and octane number is low, is not suitable for reconciling as gasoline
Component, can produce ethylene as the raw material of steam cracking device after hydrofinishing.As fully visible,
The secondary operations of Fischer-Tropsch synthesis oil are directed to greatly the higher high temperature pyrolysis of expensive hydrogenation process or energy consumption
Process.
Can be seen that from document report in recent years and F- T synthesis are processed using catalytic cracking (FCC) technology
Oily raw material, which shows the performance of outstanding production low-carbon alkene or production gasoline.The operation of FCC apparatus
It is needed to be in thermal balance.In order to solve thermal balance process operation this problem, U.S. Patent application
US684756 discloses a kind of method that Fischer Tropsch waxes are converted in fluidized catalytic cracker.This is special
Profit is pointed out to need extra heat to provide thermally equilibrated FCC operations in regeneration step, for example, can lead to
Cross thermal balance is reached using the synthesis gas that for example cleans and tail gas these potential fuel.Chinese patent application
CN103210059A discloses a kind of heat balance operation catalytic cracking Fischer-Tropsch of employing catalytic cracking system and closes
Into the method for oil.The method using high rare earth oxide large pore zeolite Cracking catalyst be adapted to split
Operate riser reactor to combine under the conditions of change, do not use extra thermal source or the heavy charge i.e. can be with
Heat balance operation.
The content of the invention
The purpose of the present invention is to propose to a kind of adjust the thermally equilibrated method of Fischer Tropsch synthetic oil in catalytic cracking mode, to solve
Certainly during catalyzed cracking processing Fischer-Tropsch synthesis oil shortage of heat problem.
The present inventor passes through to study discovery, during catalyzed cracking processing Fischer-Tropsch synthesis oil, is
Heat balance operation is reached, can be by making enough coke laydowns during the cracking reaction of heat absorption
On a catalyst, thus there are the enough combustion heat quilts when in a regenerator by coke from catalyst burn off
Catalyst absorbs to provide the heat demand of catalytic cracking reaction.However, due to the hydro carbons of Fischer-Tropsch synthesis oil
Composition is mainly alkane, is practically free of aromatic hydrocarbons, and thus coking yield is very in cracking process for these raw materials
It is low.For this purpose, the present inventor intends by poor oil green coke on fresh catalyst, to solve Fischer-Tropsch
The problem of artificial oil shortage of heat in catalytic cracking process, so as to complete the present invention.
The invention provides a kind of adjust the thermally equilibrated method of Fischer Tropsch synthetic oil in catalytic cracking mode, the method bag
Include：(1) regenerated catalyst by Fischer-Tropsch synthesis oil with heat carries out cracking reaction in first reactor, obtains
To the first reaction stream；(2) poor oil and fresh catalyst are carried out into cracking reaction in second reactor,
Obtain the second reaction stream；(3) by first reaction stream and second reaction stream injection sedimentation
Device is separated, and the reclaimable catalyst isolated enters regenerator coke burning regeneration Jing after stripping, and will obtain
Heat regenerated catalyst return first reactor recycle.
In the methods described that the present invention is provided, there is cracking reaction with fresh catalyst in poor oil, generate
Most of coke, is hung burnt catalyst and is mixed in settler with the reclaimable catalyst from first reactor
And settle, coke burns releasing heat in regenerator, can supplement Fischer-Tropsch synthesis oil reaction-regeneration system
Heat needed for system；In gasoline fraction obtained by poor oil cracking, arene content is high simultaneously, can improve expense
The low problem of arene content in support artificial oil cracking gasoline.
And, it is generally the case that catalytic cracking unit has different degrees of urging during stable operation
Agent is run and is damaged, generally 0.5-1.5 kilogram catalyst/ton oil.And to keep Catalyst Balance Activity, need
Quantitative draws off equilibrium catalyst, and this requires that catalytic cracking unit needs fresh dose quantitative of addition.Ability
It is well known that the activity of fresh catalyst is very high, hydrothermal stability is poor for domain staff, is not suitable for straight
Connect to contact with raw oil and carry out catalytic cracking reaction.The operation of catalytic cracking unit is usually to add fresh dose
Enter in regenerator.And in the present invention, fresh catalyst is urged with poor oil in being continuously added to reactor
Change cracking reaction, during on the one hand can adhering to substantial amounts of coke to make up Fischer Tropsch synthetic oil in catalytic cracking mode
The defect that raw trial of strength is not enough, in another aspect fresh catalyst continuous adding device, is conducive to the steady of device
The stability of qualitative and product slates.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Description of the drawings
Accompanying drawing is, for providing a further understanding of the present invention, and to constitute the part of description, with
Detailed description below is used for explaining the present invention together, but is not construed as limiting the invention.
In accompanying drawing：
The flow process of the thermally equilibrated method of the regulation Fischer Tropsch synthetic oil in catalytic cracking mode that Fig. 1 is provided for the present invention
Schematic diagram.
Description of reference numerals
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 regeneratoies
16 pipelines (row's regenerated flue gas)
17 regenerative agent feed-lines
Specific embodiment
Hereinafter the specific embodiment of the present invention is described in detail.It should be appreciated that this place is retouched
The specific embodiment stated is merely to illustrate and explains the present invention, is not limited to the present invention.
The thermally equilibrated method of the regulation Fischer Tropsch synthetic oil in catalytic cracking mode that the present invention is provided includes：
(1) regenerated catalyst by Fischer-Tropsch synthesis oil with heat carries out cracking reaction in first reactor,
Obtain the first reaction stream；
(2) poor oil and fresh catalyst are carried out into cracking reaction in second reactor, obtains second
Reaction stream；
(3) first reaction stream and second reaction stream injection settler are separated,
The reclaimable catalyst isolated enters regenerator coke burning regeneration Jing after stripping, and the regeneration of the heat for obtaining is urged
Agent returns first reactor and recycles.
In the methods described that the present invention is provided, the independent reactor of Fischer-Tropsch synthesis oil and each leisure of poor oil
Middle generation cracking reaction, but both reaction stream share settler carry out it is settlement separate.
In the present invention, catalyst is fresh catalyst, equilibrium catalyst, regenerated catalyst and to be generated urges
The general designation of agent.The catalyst can be the conventional Cracking catalyst in this area.In a kind of embodiment
In, the active component of the catalyst can selected from Y the or HY type zeolites with or without rare earth, containing or
Ultrastable without rare earth, ZSM-5 series zeolites, the silica-rich zeolite with five-membered ring structure
With one or more in β zeolites.
In the present invention, the fresh catalyst is that, without aging catalyst, its micro-activity can be
80-95%.
In the present invention, the regenerated catalyst is device equilibrium catalyst, and its micro-activity can be
50-75%.
In the present invention, the first reactor can be riser reactor, downer reactor, carry
Riser and fluid bed compound reactor, down pipe and fluid bed compound reactor or fluidized-bed reactor.
Wherein, riser, down pipe and fluid bed are isodiametric riser, down pipe and fluid bed, or
The riser of various variable diameters, down pipe and fluid bed.
The cracking reaction condition of the first reactor can include：Temperature is 450-650 DEG C, preferably
480-600℃；The oil gas time of staying is 0.5-40 seconds, preferably 1-20 seconds；Catalyst and raw oil
Weight ratio is 4-40：1, preferably 8-30：1.
In the present invention, the second reactor can be riser reactor or downer reactor.Its
In, riser and down pipe are isodiametric riser and down pipe, or the riser of various variable diameters
And down pipe.
The cracking reaction condition of the second reactor can include：Temperature is 450-650 DEG C, preferably
480-600℃；The oil gas time of staying is 0.5-40 seconds, preferably 1-20 seconds；Catalyst and raw oil
Weight ratio is 1-40：1, preferably 4-20：1.
In the present invention, the Fischer-Tropsch synthesis oil can be 23 selected from Fischer-Tropsch synthetic mid-boiling point scope
DEG C to one or more in the part fraction or full fraction of the end point of distillation mixture.
In the present invention, the poor oil can be the slurry oil of catalytic cracking process production, coking, hot tearing
The heavy end that change, viscosity breaking technology are generated, straight run reduced pressure distillate, and the one kind in straight asphalt
Or it is various.
In the present invention, the consumption of the poor oil can account for the 5-30 of the consumption of the Fischer-Tropsch synthesis oil
Weight %, preferably 10-25 weight %.
Method provided by the present invention is described further below in conjunction with Fig. 1.
The flow process of the thermally equilibrated method of the regulation Fischer Tropsch synthetic oil in catalytic cracking mode that Fig. 1 is provided for the present invention
Schematic diagram.The shape and size of equipment and pipeline are not limited by the accompanying figures, but determine as the case may be.
As shown in figure 1, the regenerated catalyst Jing regenerative agent feed-line 17 of heat is anti-into the first riser
The bottom of device 2 is answered, after mixing with the Fischer-Tropsch synthesis oil and vapor of injection pipeline 1, cracking reaction occurs.
The outlet of first riser reactors of mixture Jing 2 of reaction oil gas and catalyst enters fluidized-bed reactor
3.It is anti-for adjusting the thermally equilibrated poor oil of reaction regeneration and the second riser of injection of vapor Jing pipelines 4
Answer the bottom of device 8, fresh catalyst Jing after the heating of 5 heated stove of pipeline 6, by pipeline 7 with it is inferior
Simultaneously there is cracking reaction in oil contact, separate the catalyst of reaction oil gas and carbon deposit afterwards in settler 9.
Reaction oil gas Jing pipelines 10 send into subsequent separation system.In settler after detached reaction carbon deposit catalysis
Jing fluidized-bed reactors 3 enter stripper 11 under gravity for agent, and stripped vapor Jing pipelines 12 inject,
Reaction oil gas entrained by carbon deposited catalyst are stripped totally as much as possible.The carbon deposit that stripped vapor is stripped off
The hydrocarbon product adsorbed on catalyst is entered in settler 9 by fluidized-bed reactor 3.Reclaimable catalyst
Jing reclaimable catalysts inclined tube 13 sends into regenerator 15.Oxygen-containing gas such as air or oxygen Jing pipelines 14 are the bottom of from
Regenerator 15 is injected in portion, carries out coke burning regeneration.Regenerated flue gas Jing pipelines 16 are drawn.Regenerated catalyst Jing
Regenerative agent feed-line 17 is recycled in returning the first riser reactor 2.
Embodiment
Catalyst used in embodiment is by Sinopec Group's catalyst Shandong point
Company's commercial production, product designation MMC-2, the catalyst contain ultrastable and average hole
ZSP zeolite of the footpath less than 0.7 nanometer, the property of its fresh catalyst are shown in Table 1.Equilibrium catalyst is new
Fresh catalyst 100% saturated vapor hydrothermal agings of Jing 14 hours at a temperature of 800 DEG C, the catalyst
Main physico-chemical property is shown in Table 2.
In embodiment, Fischer-Tropsch synthesis oil raw material used is Fischer Tropsch waxes, and its main physico-chemical property is shown in Table 3.
The vacuum distillate of poor oil used for outsourcing in embodiment, its property are 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 |
| Freezing point/DEG C | 76 |
| Elementary composition (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 |
| Elementary composition (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 regulation Fischer Tropsch synthetic oil in catalytic cracking mode heat that the present embodiment is used for description present invention offer is flat
The method of weighing apparatus.
Tested using the middle- scale device of the successive reaction-regenerative operation shown in Fig. 1, first reactor
For riser reactor, the internal diameter of riser reactor is 16 millimeters, is highly 6 meters；Second reaction
Device is riser reactor, and the internal diameter of riser reactor is 16 millimeters, is highly 3 meters.Medium-sized dress
Put and reaction-regeneration system temperature is maintained using electrical heating.The equilibrium catalyst reserve of middle- scale device is 8kg,
The addition speed of fresh catalyst is 0.6kg/h.Because middle- scale device catalyst stack less is not obvious, therefore again
Regenerated catalyst is set at raw inclined tube and unloads agent mouth, agent speed is unloaded for 0.6kg/h.
Temperature is the bottom that 680 DEG C or so of regenerated catalyst Jing regenerator sloped tube enters the first riser reactor
Portion, and flow up in the presence of pre-lift steam.The Fischer Tropsch waxes of preheating are acted in atomizing steam
Under riser reactor is sprayed into by feed nozzle, contact and carry out Catalytic Cracking Unit of Measure with the regenerated catalyst of heat
Should.Vacuum distillate sprays into the second riser reactor by nozzle under atomizing steam effect, and is heated to
600 DEG C of contacts fresh catalyst is simultaneously reacted.The reaction oil gas of first, second riser reactor
Settler is entered into from reactor outlet with reclaimable catalyst, reaction oil gas and catalyst are fast in the settler
Speed is separated.Reaction oil gas are further separated into gaseous product and gasoline fraction, diesel oil distillate and heavy oil fraction
Deng product liquid.The reclaimable catalyst isolated in settler is entered in stripper by action of gravity, Jing
Reclaimable catalyst Jing reclaimable catalyst pipelines after stripping enter into regenerator, in the regenerator with it is heated
Air contact regenerated.The regenerated catalyst of coke burning regeneration activity recovery again returns to the first riser
Recycle in reactor.
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, except that,
The bottom of one riser reactor is 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, except that,
The bottom of two riser reactors is 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 |
| Response time/s | 1.8 | 2.5 | 1.8 | 1.8 |
| Second riser reaction condition |
| Reaction temperature/DEG C | 480 | 480 | 480 | 480 |
| Response 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 speed/(kg/h) | 0.4 | 0.6 | 0.4 | 0.4 |
| Regeneration | CO burns completely | CO burns completely | CO burns completely | CO burns completely |
| 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 |
From table 5, the regulation Fischer Tropsch synthetic oil in catalytic cracking mode provided according to the present invention is thermally equilibrated
Method, amount of coke are suitable, disclosure satisfy that the thermal balance of catalytic cracking unit itself；Simultaneously in product gasoline
Aromatics quality score ratio be improved.
Claims (11)
1. a kind of to adjust the thermally equilibrated method of Fischer Tropsch synthetic oil in catalytic cracking mode, the method includes：
(1) regenerated catalyst by Fischer-Tropsch synthesis oil with heat carries out cracking reaction in first reactor,
Obtain the first reaction stream；
(2) poor oil and fresh catalyst are carried out into cracking reaction in second reactor, obtains second
Reaction stream；
(3) first reaction stream and second reaction stream injection settler are separated,
The reclaimable catalyst isolated enters regenerator coke burning regeneration Jing after stripping, and the regeneration of the heat for obtaining is urged
Agent returns first reactor and recycles.
2. method according to claim 1, wherein, the active component of catalyst selected from containing or not
Y or HY type zeolites containing rare earth, the ultrastable with or without rare earth, ZSM-5 series boilings
One or more in stone, the silica-rich zeolite with five-membered ring structure and β zeolites.
3. method according to claim 1 and 2, wherein, the fresh catalyst is without old
The catalyst of change, its micro-activity are 80-95%.
4. method according to claim 1 and 2, wherein, the micro- anti-work of the regenerated catalyst
Property is 50-75%.
5. method according to claim 1, wherein, the first reactor is to lift tube reaction
Device, downer reactor, riser and fluid bed compound reactor, down pipe and fluid bed compound reaction
Device or fluidized-bed reactor.
6. method according to claim 1 or 5, wherein, the cracking of the first reactor is anti-
Condition is answered to include：Temperature is 450-650 DEG C, preferably 480-600 DEG C；The oil gas time of staying is 0.5-40
Second, preferably 1-20 seconds；Catalyst is 4-40 with the weight ratio of raw oil：1, preferably 8-30：1.
7. method according to claim 1, wherein, the second reactor is to lift tube reaction
Device or downer reactor.
8. the method according to claim 1 or 7, wherein, the cracking of the second reactor is anti-
Condition is answered to include：Temperature is 450-650 DEG C, preferably 480-600 DEG C；The oil gas time of staying is 0.5-40
Second, preferably 1-20 seconds；Catalyst is 1-40 with the weight ratio of raw oil：1, preferably 4-20：1.
9. method according to claim 1, wherein, the Fischer-Tropsch synthesis oil is selected from F- T synthesis
Product mid-boiling point scope is the mixed of one or more in 23 DEG C to the end point of distillation of part fraction or full fraction
Compound.
10. method according to claim 1, wherein, the poor oil is catalytic cracking process life
The slurry oil of product, the heavy end that coking, thermal cracking, viscosity breaking technology are generated, straight run reduced pressure distillate,
And one or more in straight asphalt.
11. methods according to claim 1,9 or 10, wherein, the consumption of the poor oil is accounted for
5-30 weight % of the consumption of the Fischer-Tropsch synthesis oil, preferably 10-25 weight %.
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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 |
-
2015
- 2015-10-21 CN CN201510689292.9A patent/CN106609146B/en active Active
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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