CN105368493A - Catalytic conversion method for producing high-octane gasoline - Google Patents
Catalytic conversion method for producing high-octane gasoline Download PDFInfo
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Abstract
The invention relates to a catalytic conversion method for producing high-octane gasoline. The method comprises the steps that preheated raw oil and a first catalytic conversion catalyst are subjected to a catalytic conversion reaction in an initial reaction region of a riser reactor, and an oil mixture produced in the initial reaction region is made to enter a main reaction region of the riser reactor and continues to be subjected to a catalytic conversion reaction with a second catalytic conversion catalyst injected in a supplemented mode, wherein the reaction temperature of the main reaction region is higher than that of the initial reaction region, the temperature of the second catalytic conversion catalyst is higher than that of the first catalytic conversion catalyst, and the reaction time of the initial reaction region is shorter than that of the main reaction region. According to the catalytic conversion method for producing high-octane gasoline, the gasoline product with the high RON can be obtained, and the obtained gasoline product is better in quality, and has the obviously low olefin content and high isomerization alkane and arene content.
Description
Technical field
The present invention relates to a kind of catalysis conversion method of hydrocarbon ils, particularly, relate to a kind of catalysis conversion method producing stop bracket gasoline.
Background technology
In recent years, along with automobile pollution increases fast, environmental regulation is increasingly strict, and market demand petroleum chemical enterprise provides sufficient high-quality gasoline, and current quality of gasoline escalation process, inevitably cause the loss of octane number of gasoline.Catalytic cracking (FCC) is the main secondary processing process of producing gasoline, and Chinese commodity gasoline more than 80% is from fluid catalytic cracking (FCC) gasoline.But catalytically cracked gasoline is due to the restriction of technique own, RON octane value is generally lower than 93, and olefin(e) centent is higher in gasoline composition, volume content is generally more than 35%, aromaticity content is lower, general volume content is 10-25% (GB17930-2011 regulation olefin(e) centent is no more than 30%, and aromaticity content is no more than 40%).Reduce content of olefin in gasoline and improve between gasoline octane rating and there is certain contradiction, need to do more deep work.Improve gasoline octane rating, especially improve gasoline octane rating bucket, become the most important thing of catalytic cracking worker work.
US3784463A discloses a kind of method utilizing catalytic cracking process to improve gasoline octane rating.The method adopts the riser reactor of more than two or two, and wherein a riser tube is specifically designed to the low-quality gasoline of processing, makes it at a higher temperature catalytic cracking reaction occur.The method at high temperature carries out upgrading to gasoline, and some olefin is cracking again, causes gasoline waste larger.
The method of quantity flexibility disclosed in CN1069054A, adopts two independently riser tube and two corresponding settling vessels, uses same catalyzer, light petroleum hydrocarbon and heavy petroleum hydrocarbon are reacted under different reaction conditionss.In first riser reactor, the thermocatalyst that light hydrocarbons and revivifier come 600-700 DEG C, agent-oil ratio 10-40, residence time 2-20 second, coke on regenerated catalyst 0.1-0.4 % by weight condition under react, with yield-increasing gas alkene, improve gasoline octane rating, remove the impurity such as sulphur nitrogen, improve gasoline stability, reducing atmosphere is provided, passivation is carried out to the heavy metal contaminants on catalyzer, for the cracking reaction carrying out heavy hydrocarbon in catalyst recirculation to second riser tube provides favourable condition.Heavy hydrocarbon reacts under Conventional riser catalytic cracking reaction condition.
CN1160746A discloses a kind of catalysis conversion method improving gasoline octane number.The method is by the upstream injecting lift pipe reactor of Conventional catalytic cracking feed(raw material)inlet by low octane value gasoline, contact with the high temperature catalyst from revivifier, temperature of reaction be 600-730 DEG C, agent-oil ratio is 6-180, weight hourly space velocity is reacted under being the condition of 1-180h-1.
Although the method for directly carrying out high temperature upgrading to catalytic gasoline in riser tube of above-mentioned employing contributes to improving institute and produces gasoline octane rating, increase rate is limited, and the waste of gasoline comparatively greatly, the yield reduction of gasoline.
CN1237477A discloses a kind of riser reactor, and this reactor is vertically followed successively by the outlet area of pre lift zone coaxial each other, the first reactor, expanding second reaction zone, undergauge from bottom to up, has a level pipe at outlet area end.It is different with the processing condition of second reaction zone that this reactor both can optionally control the first reaction zone, and stock oil of different nature can be made again to carry out segmentation cracking, obtains required object product.Producing Trimethylmethane and being rich in the catalysis conversion method of isoparaffin gasoline based on above-mentioned new texture riser reactor is disclosed in CN1232069A, the method be by preheating after stock oil introduce the reducing reactor that comprises two reaction zones, contact with the cracking catalyst of heat, first reaction zone temperature 530 DEG C-620 DEG C, reaction times 0.5-2.0 second; Second reaction zone temperature 460-530 DEG C, reaction times 2-30 second, after reaction product isolated, reclaimable catalyst enters revivifier through stripping and burns Posterior circle and use.Trimethylmethane content 20-40 % by weight in the liquefied gas adopting the method to produce, isoparaffin content 30-45 % by weight in gasoline family's composition, olefin(e) centent is reduced to less than 30 % by weight, and its research octane number (RON) is 90-93, motor-method octane number is 80-84, improves limited to gasoline octane rating.
US4268700A discloses a kind of method utilizing polymerization of low-carbon olefin to produce stop bracket gasoline.The oligomerisation of C3 and C4 component, the oligomerization of propene wherein in C3 component, in C4 component 80% iso-butylene and generate polymkeric substance in gasoline boiling range less than the n-butene oligomerisation of 40%.The gasoline fraction that unreacted C4 alkylating hydrocarbons generates can produce stop bracket gasoline with the polymkeric substance blending of C3, C4 component.But still contain comparatively polyene hydrocarbon in this kind of method product, and containing more diolefine, gasoline stability is poor.
In sum, carrying out high temperature upgrading to catalytic gasoline, to put forward the waste of high-octane method to gasoline larger, reduce the yield of gasoline, double-reaction area is produced the method being rich in isoparaffin gasoline and is improved limited to gasoline octane rating, and the quality of gasoline that the method for polymerization of low-carbon olefin is produced is difficult to meet the requirements, the olefin(e) centent of gasoline is high.
Summary of the invention
The gasoline octane rating that the object of the invention is existing for the method in order to overcome existing raising gasoline octane rating improves limited, or the yield of gasoline can be reduced while improving gasoline octane rating, and the more high defect of olefin(e) centent in gasoline, a kind of catalysis conversion method of production stop bracket gasoline is newly provided.
The invention provides a kind of catalysis conversion method producing stop bracket gasoline, the method comprises: the stock oil after preheating and the first catalytic converting catalyst are carried out catalytic conversion reaction in the initial reaction district of riser reactor, and make the oil agent mixture produced by described initial reaction district enter the main reaction region of riser reactor, catalytic conversion reaction is proceeded with the second catalytic converting catalyst of supplementary injection, wherein, the temperature of reaction of described main reaction region is higher than the temperature of reaction in described initial reaction district, the temperature of described second catalytic converting catalyst is higher than the temperature of described first catalytic converting catalyst, and the reaction times in described initial reaction district is less than the reaction times of described main reaction region.
The catalysis conversion method of described production stop bracket gasoline provided by the invention is implemented in riser reactor, by reducing the reaction severity in the initial reaction district of riser reactor, control cracking level, and promote the aromatization of the alkene in the crackate in initial reaction district in main reaction region by high temperature, high agent-oil ratio and long residence time, reduce heat cracking reaction ratio, thus reduce olefin(e) centent in dry gas yied and gasoline, and gasoline octane rating is improved while increase gasoline production, improve product selectivity.
In addition, described method provided by the invention is simple to operate, the basis of the catalytic cracking unit of routine is carried out simple transformation and just can operate.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and forms a part for specification sheets, is used from explanation the present invention, but is not construed as limiting the invention with embodiment one below.In the accompanying drawings:
Fig. 1 is the schematic flow sheet of the catalysis conversion method of production stop bracket gasoline according to one embodiment of the present invention.
Description of reference numerals
1-riser reactor; 2-revivifier; 3-settling vessel;
4-stripping stage; 5-catalyzer heat collector;
6-(riser reactor 1 exit end) cyclonic separator;
7-(being communicated with pneumatic outlet and the main oil gas piping 20 of cyclonic separator 6) collection chamber;
8-reclaimable catalyst inclined tube pipeline;
9-(being connected with bottom main reaction region) regenerated catalyst inclined tube pipeline 1;
10-(being communicated with catalyst outlet and the catalyzer heat collector 5 of described revivifier 2) pipeline;
11-(being communicated with the initial reaction district of catalyzer heat collector 5 and riser reactor 1) pipeline;
14-is the pipeline that pre-lift medium carried by riser reactor 1;
15-is the pipeline of riser reactor 1 transferring raw material;
16-is the pipeline of riser reactor 1 delivery of mist steam transferring raw material;
The initial reaction district of 17-riser reactor;
The main reaction region of 18-riser reactor;
19-is the pipeline of stripping stage 4 delivery of mist steam;
20-main oil gas piping;
21-(revivifier 2 main air entrance) pipeline;
22-air distributor;
23-revivifier cyclonic separator;
24-(being communicated with cyclonic separator 24 pneumatic outlet) flue.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The all scopes disclosed herein all comprise end points and can independently combine.The end points of scope presently disclosed and any value are all not limited to this accurate scope or value, and these scopes or value should be understood to the value comprised close to these scopes or value.
The catalysis conversion method of described production stop bracket gasoline provided by the invention comprises: the stock oil after preheating and the first catalytic converting catalyst are carried out catalytic conversion reaction in the initial reaction district of riser reactor, and make the oil agent mixture produced by described initial reaction district enter the main reaction region of riser reactor, catalytic conversion reaction is proceeded with the second catalytic converting catalyst of supplementary injection, wherein, the temperature of reaction of described main reaction region is higher than the temperature of reaction in described initial reaction district, the temperature of described second catalytic converting catalyst is higher than the temperature of described first catalytic converting catalyst, and the reaction times in described initial reaction district is less than the reaction times of described main reaction region.
In described method provided by the invention, preferably, the temperature of reaction of described main reaction region than the temperature of reaction height 5-100 DEG C in described initial reaction district, more preferably 10-80 DEG C, preferred 30-60 DEG C further.
In described method provided by the invention, in described initial reaction district, can also water vapour be injected, and the amount of water vapour injected and the weight ratio of stock oil can be 0.01-2:1, be preferably 0.05-1:1.Described water vapour can inject with the form of atomizing steam.
In described method provided by the invention, preferably, reaction times in described initial reaction district than the reaction times of described main reaction region short 0.5-5 second, more preferably 0.6-4 second, further preferred 0.7-3.8 second.
In described method provided by the invention, the reaction conditions in described initial reaction district can comprise: temperature of reaction is 400-600 DEG C, is preferably 450-550 DEG C; Agent-oil ratio (i.e. the weight ratio of catalyzer and stock oil) is 1-50: 1, is preferably 1-30: 1; Reaction times is 0.1-1.9 second, is preferably 0.2-1.5 second.
In described method provided by the invention, the reaction conditions of described main reaction region can comprise: temperature of reaction is 450-700 DEG C, is preferably 500-600 DEG C; Reaction pressure is 130-450kPa, is preferably 200-400kPa; Agent weight of oil, than for 5-50: 1, is preferably 10-40: 1; Reaction times is 1-8 second, is preferably 1.5-6 second.The agent weight of oil of described main reaction region is than the weight ratio of the total amount and stock oil that refer to the first catalytic converting catalyst and the second catalytic converting catalyst.
In the present invention, the temperature of reaction of riser reactor refers to the temperature out of certain reaction zone of riser reactor or riser reactor; Reaction pressure refers to gauge pressure.
In described method provided by the invention, the main reaction region in the riser reactor adopted can be provided with one or more.In order to enable raw material fully react, and according to different object product qualities demands, in described riser reactor, the quantity of main reaction region can be set to 2-8, is preferably 2-3.
According to one embodiment of the present invention, as shown in Figure 1, described riser reactor comprises initial reaction district and main reaction region from bottom to top successively.In this riser reactor, described initial reaction district can distribute with described main reaction region in a conventional manner or be connected.Under preferable case, described initial reaction district is undergauge relative to described main reaction region, and described main reaction region can be 1.2-1.5:1 with the ratio of the riser diameter in described initial reaction district.The junction of described initial reaction district and described main reaction region can be truncated cone-shaped, and preferably the drift angle of the longitudinal section isosceles trapezoid of this truncated cone-shaped can be 45-75 °.In this embodiment, described first catalytic converting catalyst preferably injects in the bottom in described initial reaction district, and described second catalytic converting catalyst preferably injects in the bottom of described main reaction region.Particularly, first catalytic converting catalyst after injection it, under the effect of pre-lift medium in described initial reaction district on flowing, stock oil after preheating injects in the bottom in initial reaction district, with the first catalytic converting catalyst contact reacts, the oil agent mixture formed is advanced into main reaction region on continuing, and continues to react with the second catalytic converting catalyst of supplementary injection.
For the initial reaction district of riser reactor, its structure also can be conventional equal diameter riser reactor, and its diameter can be 0.2-5 rice, and length can be 0.5-5 rice.For the main reaction region of riser reactor, its structure can be conventional equal diameter riser reactor, and its length can be 10-50 rice.
In the present invention, the weight ratio of described pre-lift medium and stock oil can be 0.01-2:1, is preferably 0.05-1:1.Described pre-lift medium can be selected from least one in water vapour, dry gas and nitrogen.
In described method provided by the invention, the temperature of described second catalytic converting catalyst is higher than the temperature of described first catalytic converting catalyst.Under preferable case, the temperature of described second catalytic converting catalyst is than the temperature height 10-150 DEG C of described first catalytic converting catalyst, more preferably 15-100 DEG C.Further preferably, the temperature of described first catalytic converting catalyst is 450-650 DEG C, is more preferably 500-620 DEG C; The temperature of described second catalytic converting catalyst is 600-730 DEG C, is more preferably 620-700 DEG C.
In the present invention, described catalysis conversion method can also comprise: the reaction mass that the outlet by described riser reactor is discharged is carried out gas solid separation, isolated solid catalyst is carried out stripping, coke burning regeneration to obtain high-temperature regenerated catalyst, a part of high-temperature regenerated catalyst is cooled, and the circulation of the regenerated catalyst of cooling is used as described first catalytic converting catalyst, the circulation of another part high-temperature regenerated catalyst is used as described second catalytic converting catalyst simultaneously.The process of described gas solid separation can be carried out in cyclonic separator.For reaction oil gas isolated in gas solid separation process, be usually injected into subsequent separation system, be separated cuts such as obtaining dry gas, liquefied gas, gasoline and diesel oil.
The process of described regeneration can be implemented according to the catalyst regeneration process of this area routine, such as, described renovation process can comprise: introduce oxygen-containing gas (as air) from the bottom of revivifier, after oxygen-containing gas introduces revivifier, reclaimable catalyst contacts coke burning regeneration with oxygen, the flue gas generated after catalyzer coke burning regeneration is in revivifier top gas solid separation, and flue gas can enter subsequent power recovery system.The regeneration condition of described reclaimable catalyst can be the operational condition of this area routine, such as, can comprise: temperature is 550-750 DEG C, is preferably 600-730 DEG C, more preferably 650-700 DEG C; Gas superficial linear speed is 0.5-3 meter per second, is preferably 0.8-2.5 meter per second, is more preferably 1-2 meter per second; Reclaimable catalyst mean residence time is 0.6-3 minute, is preferably 0.8-2.5 minute, is more preferably 1-2 minute.
Can be high-temperature regenerated catalyst is mixed with low temperature reclaimable catalyst cool by the mode that high-temperature regenerated catalyst cools, also high-temperature regenerated catalyst can be cooled to temperature required by water cooler.
In described method provided by the invention, at a feed entrance point, whole stock oil can be introduced in reactor, also at least two different feed entrance points, stock oil can be introduced in reactor according to identical or different ratio.But no matter be one or plural feed entrance point, all feed entrance points of preferred feedstock oil are all positioned at the initial reaction district of described riser reactor, are more preferably positioned at the bottom in described initial reaction district.
In described method provided by the invention, before described stock oil is contacted with the first catalytic converting catalyst, described stock oil is carried out preheating, such as by fuel oil preheating to the initial reaction district introducing riser reactor after 150-400 DEG C again, be preferably preheated to 250-360 DEG C.
In described method provided by the invention, described stock oil can be the catalytically cracked material of this area routine, can be such as petroleum hydrocarbon and/or other mineral oil, wherein, described petroleum hydrocarbon can be selected from least one in vacuum gas oil, atmospheric gas oil, coker gas oil, deasphalted oil, vacuum residuum and long residuum.
In described method provided by the invention, described catalytic converting catalyst can be that the routine of this area is selected, and for the present invention, described catalytic converting catalyst is preferably solid acid catalyst.Described solid acid catalyst contains active ingredient and carrier.At least one that described active ingredient can be selected from containing or not contain in Y or the HY type zeolite of rare earth, the zeolite with MFI structure, faujusite and pure aluminium silicate, is preferably selected from containing or does not contain ultrastable Y－type zeolite, at least one had in the zeolite of MFI structure and the faujusite of rare earth ion exchanged of rare earth.Described carrier can be selected from least one in inorganic oxide (as synthetic) and natural clay.
In the present invention, in described catalytic converting catalyst, each component accounts for total catalyst weight respectively: zeolite 1-50 % by weight, inorganic oxide 5-99 % by weight, clay 0-70 % by weight.Its mesolite, as active ingredient, is selected from mesopore zeolite and/or optional large pore zeolite, and mesopore zeolite accounts for the 0-100 % by weight of zeolite gross weight, preferred 0-50 % by weight, more preferably 0-20 % by weight, large pore zeolite accounts for the 0-100 % by weight of zeolite gross weight, preferred 20-80 % by weight.Mesopore zeolite is selected from ZSM series zeolite and/or ZRP zeolite, also modification can be carried out to transition metals such as the non-metallic elements such as above-mentioned mesopore zeolite phosphorus and/or iron, cobalt, nickel, about the more detailed description of ZRP is see US5,232,675, ZSM series zeolite is selected from least one among the zeolite of ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38, ZSM-48 and other similar structures, about the more detailed description of ZSM-5 is see US3,702,886.At least one in this group zeolite that large pore zeolite is selected from the super steady Y obtained by Rare Earth Y (REY), rare earth hydrogen Y (REHY), different methods, high silicon Y is formed.
In the present invention, described inorganic oxide, as caking agent, is preferably selected from silicon-dioxide (SiO2) and/or aluminium sesquioxide (Al
2o
3).
In the present invention, described clay, as matrix (i.e. carrier), is preferably selected from kaolin and/or halloysite.
According to a kind of embodiment of the present invention, the catalysis conversion method of described production stop bracket gasoline comprises the steps:
From revivifier high-temperature regenerated catalyst through overcooling laggard enter the bottom of riser reactor, the initial reaction district of riser reactor is upwards flowed under the effect of pre-lift medium, stock oil after preheating is entered in initial reaction district by riser reactor bottom, contacts, to react and up with regenerated catalyst, the oil agent mixture formed enters the main reaction region of riser reactor, the high-temperature regenerated catalyst from revivifier (without cooling) supplementing injection with the bottom in main reaction region proceeds to react, the rear logistics of reaction enters in the cyclonic separator in settling vessel carries out gas solid separation, isolated solid catalyst through stripping to obtain reclaimable catalyst, and this reclaimable catalyst is injected revivifier coke burning regeneration, then a part of high-temperature regenerated catalyst is carried out cooling and with the bottom of Posterior circle injecting lift pipe reactor, by the main reaction region of another part high-temperature regenerated catalyst direct circulation injecting lift pipe reactor, isolated reaction oil gas is delivered to subsequent product separation system and is isolated the cuts such as dry gas, liquefied gas, gasoline and diesel oil.
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
Fig. 1 is the schematic flow sheet of the catalysis conversion method of described production stop bracket gasoline provided by the invention.
The technical process of method provided by the invention is illustrated: as shown in Figure 1 referring to Fig. 1, pre-lift medium enters by bottom riser reactor 1 through pipeline 14, from pipeline 11 and through catalyzer heat collector 5 lower the temperature after regenerated catalyst enter bottom riser reactor 1, along riser tube upwards accelerated motion under the castering action of pre-lift medium, the stock oil of preheating is through the initial reaction district 17 of pipeline 15 injecting lift pipe 1 bottom together with the atomizing steam from pipeline 16, mix with the existing logistics of riser reactor, cracking reaction is there is in stock oil on the catalyzer of heat, and upwards accelerated motion, enter the main reaction region 18 of riser reactor.The reaction product oil gas generated and the reclaimable catalyst of inactivation enter the cyclonic separator 6 in settling vessel 3, and realize being separated of reclaimable catalyst and reaction product oil gas, reaction product oil gas enters collection chamber 7, and catalyst fines returns settling vessel 3 by dipleg.In settling vessel 3, reclaimable catalyst flows to stripping stage 4, contacts with the steam from pipeline 19.The reaction product oil gas that stripping goes out from reclaimable catalyst enters collection chamber 7 after cyclonic separator.Reclaimable catalyst after stripping enters revivifier 2 by pipeline 8 after guiding valve to be generated regulates, air from pipeline 21 enters revivifier 2 after air distributor 22 distributes, burning-off is arranged in the coke on the dense-phase bed reclaimable catalyst bottom revivifier 2, the reclaimable catalyst of inactivation is regenerated, and flue gas enters subsequent power recovery system through the upper gas flue 24 of cyclonic separator 23.Wherein, described pre-lift medium can be dry gas, water vapour or their mixture.
The pipeline 10 of high-temperature regenerated catalyst one tunnel obtained after regeneration through being connected with revivifier 2 enters catalyzer heat collector 5, enters riser reactor 1 bottom after being regulated after lowering the temperature with the heat-obtaining media for heat exchange of pipeline 12 by the regeneration guiding valve of pipeline 11; The pipeline 9 of one tunnel through being connected with revivifier 2 enters the bottom of the main reaction region 18 of riser reactor 1 under the adjustment regenerating guiding valve.Reaction product oil gas in collection chamber 7 enters subsequent separation system through main oil gas piping 20.Wherein, described heat-obtaining medium can be at least one in raw gasline, gasoline, diesel oil, separation column first stage casing turning oil and water.
Below will the invention will be further described by embodiment, but not thereby limiting the invention.
In the following Examples and Comparative Examples, transformation efficiency obtains according to following formulae discovery:
Transformation efficiency=dry gas yield+yield of liquefied gas+yield of gasoline+coking yield
Raw material oil properties used in following examples and comparative example is as shown in table 1, the character of catalytic converting catalyst used is as shown in table 2, this catalyzer is produced by catalyzer branch office of Sinopec Group Shandong catalyst plant, and trade names are MLC-500.
Table 1
Table 2
| The catalyzer trade mark | MLC-500 |
| Molecular sieve type | ZSM-5+Y |
| Chemical quality forms, and % by weight | |
| Al 2O 3 | 55.9 |
| Na 2O | 0.29 |
| Re 2O 3 | 2.7 |
| Specific surface area, m 2/g | 153 |
| Pore volume (water droplet method), ml/g | 0.174 |
| Apparent density, ml/g | 0.70 |
| * micro-activity after burin-in process, % | 65 |
Embodiment 1
The present embodiment is for illustration of the catalysis conversion method of production stop bracket gasoline provided by the invention.
Test according to the flow process shown in Fig. 1, the middle-scale device of riser reactor is tested, fuel oil preheating to 300 DEG C through the initial reaction district of pipeline 15 injecting lift pipe reactor bottom, contacts in initial reaction district with the regenerated catalyst (560 DEG C) after the cooling promoted by water vapour, reacts.The weight ratio of catalyzer and stock oil is 10, and the residence time of stock oil in initial reaction district is 0.8 second, and temperature of reaction is 480 DEG C.Oil agent mixture is advanced into main reaction region on continuing, contact with the high-temperature regenerated catalyst (630 DEG C) from pipeline 9 bottom main reaction region and continue to react, temperature of reaction is 530 DEG C, and the reaction times is 1.6 seconds, and the weight ratio of catalyzer and stock oil is 15.Oil gas from outlet area out after after cyclonic separator is separated, enter the fractionating system at rear portion in settling vessel dilute phase.Reclaimable catalyst with charcoal enters stripping stage, reclaimable catalyst after stripping goes revivifier to regenerate, a catalyzer part after regeneration returns to the initial reaction district of riser reactor bottom after cooling heat exchange, a part is directly transported to riser tube main reaction region bottom cycle through inclined tube and uses, and operational condition and test-results are in table 3.
Comparative example 1
Adopt Conventional catalytic cracking riser reactor, fuel oil preheating to 215 DEG C injecting lift pipe reactor bottom, contacts with the high-temperature regenerated catalyst promoted by water vapour (680 DEG C), reacts.The weight ratio of reaction zone inner catalyst and stock oil is 8, and the reaction times is 2.5 seconds, and temperature of reaction is 500 DEG C.Oil gas from outlet area out after after cyclonic separator is separated, enter the fractionating system at rear portion in settling vessel dilute phase.Reclaimable catalyst with charcoal enters stripping stage, and the reclaimable catalyst after stripping goes revivifier to regenerate, and the catalyzer after regeneration returns riser reactor and recycles, and operational condition and test-results are in table 3.
Comparative example 2
Method according to embodiment 1 carries out catalytic cracking to stock oil, difference is, the catalyzer injected in the initial reaction district of riser reactor is high-temperature regenerated catalyst (650 DEG C), the temperature of reaction in the initial reaction district of riser reactor is 540 DEG C, and operational condition and test-results are in table 3.
Embodiment 2
The present embodiment is for illustration of the catalysis conversion method of production stop bracket gasoline provided by the invention.
Test according to the flow process shown in Fig. 1, the middle-scale device of riser reactor is tested, fuel oil preheating to 300 DEG C through the initial reaction district of pipeline 15 injecting lift pipe reactor bottom, contacts in initial reaction district with the regenerated catalyst (580 DEG C) after the cooling promoted by water vapour, reacts.The weight ratio of catalyzer and stock oil is 16, and the residence time of stock oil in initial reaction district is 1 second, and temperature of reaction is 510 DEG C.Oil agent mixture is advanced into main reaction region on continuing, and contact with the high-temperature regenerated catalyst (670 DEG C) from pipeline 9 bottom main reaction region and continue to react, temperature of reaction is 550 DEG C, and the reaction times is 2 seconds, and the weight ratio of catalyzer and stock oil is 20.Oil gas from outlet area out after after cyclonic separator is separated, enter the fractionating system at rear portion in settling vessel dilute phase.Reclaimable catalyst with charcoal enters stripping stage, reclaimable catalyst after stripping goes revivifier to regenerate, a catalyzer part after regeneration returns to the initial reaction district of riser reactor after cooling heat exchange, a part is directly transported to riser tube main reaction region bottom cycle through inclined tube and uses, and operational condition and test-results are in table 3.
Comparative example 3
Method according to embodiment 2 carries out catalytic cracking to stock oil, and difference is, extend the riser tube length in the initial reaction district of riser reaction zone, make the reaction times in initial reaction district be 2 seconds, operational condition and test-results are in table 3.
Embodiment 3
The present embodiment is for illustration of the catalysis conversion method of production stop bracket gasoline provided by the invention.
Test according to the flow process shown in Fig. 1, the middle-scale device of riser reactor is tested, fuel oil preheating to 300 DEG C through the initial reaction district of pipeline 15 injecting lift pipe reactor bottom, contacts in initial reaction district with the regenerated catalyst (610 DEG C) after the cooling promoted by water vapour, reacts.The weight ratio of catalyzer and stock oil is 20, and the residence time of stock oil in initial reaction district is 0.4 second, and temperature of reaction is 520 DEG C.Oil agent mixture is advanced into main reaction region on continuing, contact with the high-temperature regenerated catalyst (680 DEG C) from pipeline 9 bottom main reaction region and continue to react, temperature of reaction is 570 DEG C, and the reaction times is 2.5 seconds, and the weight ratio of catalyzer and stock oil is 23.Oil gas from outlet area out after after cyclonic separator is separated, enter the fractionating system at rear portion in settling vessel dilute phase.Reclaimable catalyst with charcoal enters stripping stage, reclaimable catalyst after stripping goes revivifier to regenerate, a catalyzer part after regeneration returns to the initial reaction district of riser reactor after cooling heat exchange, a part is directly transported to riser tube main reaction region bottom cycle through inclined tube and uses, and operational condition and test-results are in table 3.
Table 3
| Embodiment 1 | Comparative example 1 | Comparative example 2 | Embodiment 2 | Comparative example 3 | Embodiment 3 | |
| Raw material preheating temperature, DEG C | 300 | 215 | 300 | 300 | 300 | 300 |
| Temperature of reaction, DEG C | 500 | |||||
| Initial reaction district | 480 | 540 | 510 | 510 | 520 | |
| Riser tube main reaction region | 530 | 530 | 550 | 550 | 570 | |
| Reaction times, second | 2.5 | |||||
| Initial reaction district | 0.8 | 0.8 | 1.0 | 2.0 | 0.4 | |
| Riser tube main reaction region | 1.6 | 1.6 | 2.0 | 2.0 | 2.5 | |
| Agent-oil ratio | 8 | |||||
| Initial reaction district | 10 | 10 | 16 | 16 | 20 | |
| Riser tube main reaction region | 15 | 15 | 20 | 20 | 23 | |
| Catalyst temperature | 680 | |||||
| Initial reaction district | 560 | 650 | 580 | 580 | 610 | |
| Riser tube main reaction region | 630 | 630 | 670 | 670 | 680 | |
| Water vapour and raw materials quality ratio | 0.05 | 0.05 | 0.05 | 0.05 | 0.05 | 0.05 |
| Product slates, % by weight | ||||||
| Dry gas | 1.93 | 1.99 | 3.2 | 2.1 | 2.8 | 3.5 |
| Liquefied gas | 24.72 | 9.92 | 27.2 | 26.34 | 27.92 | 29.54 |
| Gasoline | 43.09 | 39.81 | 37.61. | 41.54 | 40.16 | 39.87 |
| Diesel oil | 17.10 | 16.81 | 17.4 | 16.4 | 15.9 | 15.09 |
| Heavy oil | 8.15 | 25.34 | 8.59 | 7.74 | 7.24 | 6.8 |
| Coke | 5.01 | 6.13 | 6.0 | 5.88 | 6.7 | 5.2 |
| Transformation efficiency, % by weight | 74.75 | 57.85 | 75.01 | 75.86 | 76.86 | 78.11 |
| Quality of gasoline forms, and % by weight |
| NP | 5.01 | 3.98 | 5.6 | 4.2 | 4.3 | 3.6 |
| IP | 19.0 | 11.83 | 29.14 | 13.03 | 13.28 | 10.9 |
| O | 23.61 | 56.49 | 30.19 | 27.04 | 39.16 | 29.56 |
| N | 8.2 | 6.50 | 9.4 | 7.5 | 7.0 | 5.3 |
| A | 44.18 | 21.20 | 25.67 | 48.73 | 36.26 | 50.64 |
| Gasoline RON octane value | 98 | 90.0 | 91 | 101 | 94 | 102 |
Note: in table, NP represents normal paraffin content, IP represents isoparaffin content; O represents olefin(e) centent; N representative ring Determination of Alkane Content; A represents aromaticity content.
As can be seen from the above-described embodiment, the gasoline products of higher gasoline RON octane value can not only be obtained according to the catalysis conversion method of described production stop bracket gasoline provided by the invention, and the quality of the gasoline products obtained is better, there is obviously lower alkene and higher isoparaffin and aromaticity content.Particularly, by embodiment 1 and comparative example 1 are compared and can be found out, the gasoline yield of embodiment 1 adds 3.28%, and gasoline RON octane value reaches 98, improves 8 units; In quality of gasoline composition, olefin(e) centent has dropped to 23.61% by 56.49%, and isoparaffin content increases 19.0% by 11.83%, and aromaticity content increases 44.18% by 21.20%.By embodiment 2 and comparative example 1 are compared and can be found out, the gasoline yield of embodiment 1 adds 1.73%, and gasoline RON octane value reaches 101, improves 11 units; In quality of gasoline composition, olefin(e) centent has dropped to 27.04% by 56.49%, and isoparaffin content increases 13.03% by 11.83%, and aromaticity content increases 48.73% by 21.20%.
Claims (17)
1. produce the catalysis conversion method of stop bracket gasoline for one kind, the method comprises: the stock oil after preheating and the first catalytic converting catalyst are carried out catalytic conversion reaction in the initial reaction district of riser reactor, and make the oil agent mixture produced by described initial reaction district enter the main reaction region of riser reactor, catalytic conversion reaction is proceeded with the second catalytic converting catalyst of supplementary injection, wherein, the temperature of reaction of described main reaction region is higher than the temperature of reaction in described initial reaction district, the temperature of described second catalytic converting catalyst is higher than the temperature of described first catalytic converting catalyst, and the reaction times in described initial reaction district is less than the reaction times of described main reaction region.
2. method according to claim 1, wherein, the temperature of reaction of described main reaction region is than the temperature of reaction height 5-100 DEG C in described initial reaction district.
3. method according to claim 2, wherein, the temperature of reaction of described main reaction region is than the temperature of reaction height 10-80 DEG C in described initial reaction district.
4. method according to claim 1, wherein, reaction times in described initial reaction district is than the reaction times of described main reaction region short 0.5-5 second.
5. according to the method in claim 1-4 described in any one, wherein, the reaction conditions in described initial reaction district comprises: temperature of reaction is 400-600 DEG C, and agent weight of oil is than being 1-50: 1, and the reaction times is 0.1-1.9 second.
6. method according to claim 5, wherein, the reaction conditions in described initial reaction district comprises: temperature of reaction is 450-550 DEG C, and agent weight of oil is than being 1-30: 1, and the reaction times is 0.2-1.5 second.
7. according to the method in claim 1-4 described in any one, wherein, the reaction conditions of described main reaction region comprises: temperature of reaction is 450-700 DEG C, and reaction pressure is 130-450kPa, and agent weight of oil is than being 5-50: 1, and the reaction times is 1-8 second.
8. method according to claim 7, wherein, the reaction conditions of described main reaction region comprises: temperature of reaction is 500-600 DEG C, and reaction pressure is 200-400kPa, and agent weight of oil is than being 10-40: 1, and the reaction times is 1.5-6 second.
9. method according to claim 1, wherein, in described riser reactor, described main reaction region is 1.2-1.5:1 with the ratio of the riser diameter in described initial reaction district.
10. method according to claim 1, wherein, the temperature of described second catalytic converting catalyst is than the temperature height 10-150 DEG C of described first catalytic converting catalyst.
11. methods according to claim 1 or 10, wherein, the temperature of described first catalytic converting catalyst is 450-650 DEG C, and the temperature of described second catalytic converting catalyst is 600-730 DEG C.
12. methods according to claim 11, wherein, the temperature of described first catalytic converting catalyst is 500-620 DEG C, and the temperature of described second catalytic converting catalyst is 620-700 DEG C.
13. according to the method in claim 1 and 10-12 described in any one, wherein, described method also comprises: the reaction mass that the outlet by described riser reactor is discharged is carried out gas solid separation, isolated solid catalyst is carried out stripping, coke burning regeneration to obtain high-temperature regenerated catalyst, a part of high-temperature regenerated catalyst is cooled, and the circulation of the regenerated catalyst of cooling is used as described first catalytic converting catalyst, the circulation of another part high-temperature regenerated catalyst is used as described second catalytic converting catalyst simultaneously.
14. according to the method in claim 1 and 11-13 described in any one, wherein, catalytic converting catalyst is the solid acid catalyst containing active ingredient and carrier, described active ingredient is selected from containing or not containing at least one in Y or the HY type zeolite of rare earth, the zeolite with MFI structure, faujusite and pure aluminium silicate, described carrier is selected from least one in inorganic oxide and natural clay.
15. methods according to claim 1, wherein, the temperature after described fuel oil preheating is 150-400 DEG C.
16. methods according to claim 15, wherein, the temperature after described fuel oil preheating is 250-360 DEG C.
17. according to the method in claim 1,15 and 16 described in any one, wherein, described stock oil is petroleum hydrocarbon and/or other mineral oil, and described petroleum hydrocarbon is selected from least one in vacuum gas oil, atmospheric gas oil, coker gas oil, deasphalted oil, vacuum residuum and long residuum.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108246342A (en) * | 2018-01-16 | 2018-07-06 | 西南化工研究设计院有限公司 | A kind of in-situ synthetic method of Ni-based oligomerization of propene molecular sieve catalyst |
| CN109679687A (en) * | 2017-10-19 | 2019-04-26 | 中国石油化工股份有限公司 | A kind of catalysis conversion method producing low benzene high-knock rating gasoline |
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| US3784463A (en) * | 1970-10-02 | 1974-01-08 | Texaco Inc | Catalytic cracking of naphtha and gas oil |
| CN1237477A (en) * | 1999-04-23 | 1999-12-08 | 中国石油化工集团公司 | Lift pipe reactor for fluidized catalytic conversion |
| CN103031147A (en) * | 2011-09-29 | 2013-04-10 | 中国石油化工股份有限公司 | Catalytic conversion method for processing high-nitrogen raw material |
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| US3784463A (en) * | 1970-10-02 | 1974-01-08 | Texaco Inc | Catalytic cracking of naphtha and gas oil |
| CN1237477A (en) * | 1999-04-23 | 1999-12-08 | 中国石油化工集团公司 | Lift pipe reactor for fluidized catalytic conversion |
| CN103031147A (en) * | 2011-09-29 | 2013-04-10 | 中国石油化工股份有限公司 | Catalytic conversion method for processing high-nitrogen raw material |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109679687A (en) * | 2017-10-19 | 2019-04-26 | 中国石油化工股份有限公司 | A kind of catalysis conversion method producing low benzene high-knock rating gasoline |
| CN109679687B (en) * | 2017-10-19 | 2021-06-11 | 中国石油化工股份有限公司 | Catalytic conversion method for producing low-benzene high-octane gasoline |
| CN108246342A (en) * | 2018-01-16 | 2018-07-06 | 西南化工研究设计院有限公司 | A kind of in-situ synthetic method of Ni-based oligomerization of propene molecular sieve catalyst |
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