CN102102026A - Method and device for heavy oil tandem regional catalytic cracking - Google Patents
Method and device for heavy oil tandem regional catalytic cracking Download PDFInfo
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Abstract
The invention relates to a method and a device for heavy oil tandem regional catalytic cracking. In the method and the device, catalytic cracking materials are divided into quality catalytic materials and inferior catalytic materials according to difference of reaction characteristics, and the quality catalytic materials and the inferior catalytic materials respectively enter different reaction regions of a catalytic cracking reactor system. The catalytic cracking reactor is divided into an upper reaction region and a lower reaction region to provide independent reaction spaces for the cracking reaction of the materials with different properties; moreover, the process conditions and reactor types of different reaction regions are optimized, so that the inferior materials and the quality materials are effectively prevented from generating cutthroat adsorption competition and retarding reaction in a conventional catalytic cracking riser reactor; meanwhile, the problem of the inferior materials have insufficient reaction depth in the conventional riser reactor is solved, the light oil yield and liquid yield are obviously improved, and the problem that the quality of catalytic cracking materials in refineries is increasingly poor is solved in a certain degree.
Description
Technical field
The present invention relates to a kind of method and apparatus that improves heavy oil catalytic cracking reaction efficient, relate in particular to the method and apparatus of a kind of heavy oil series connection subregion catalytic cracking, belong to the Petroleum Processing Technology field.
Background technology
Catalytic cracking process is the main means of light materialization of heavy oil, is the important production process of light-end products such as liquefied petroleum gas (LPG), gasoline, diesel oil.Traditional catalytically cracked material mainly is a vacuum distillate, owing to, utilize catalytic cracking technology processing heavy raw oil ballast oil as usual, vacuum residuum and diasphaltene residual oil to become the important selection of oil refining enterprise to increase economic efficiency to the continuous growth of lightweight oil demand and the raising of crude oil price.
At present, processing for heavy raw oil, the residual oil of the overwhelming majority all is partly to mix to enter catalytic cracking unit processing in the vacuum distillate, and the ratio of mixing is subjected to the strictness restriction of carbon residue in the residual oil, heavy metal and hydrogen richness, and this has also seriously limited the ability of utilizing the direct process residual oils of catalytic cracking unit.
In recent years, the catalytically cracked material heaviness is on the rise, and its density, carbon residue and colloid, asphalt content increase gradually, causes dry gas and coke yield rising in the reaction process, purpose product yield and downgrade.In order to solve a series of problems that the processing inferior heavy oil is brought, strengthen the heavy oil catalytic cracking reaction process, some novel heavy oil fluid catalytic cracking technology are shown one's talent.For example, ZL00134054.9 has proposed two-stage riser reactor catalysis cracking Technology at the drawback of catalyzer in the heavy oil fluid catalytic cracking riser reactor at the serious inactivation of reaction the second half, oil gas overstand in reactor.This technology replaces original single riser reactor with the two-stage riser reactor, and constitute the two-way catalyst recirculation: fresh feed enters first section riser reactor and regenerated catalyst contact reacts; Turning oil enters second section riser reactor and regenerated catalyst contact reacts, by the different operational condition of control two-stage riser, has realized catalyzer relay, segmentation reaction, short reaction time and high agent-oil ratio operation.This technology to a certain extent can controlling reactor in unwanted cracking reaction and the heat cracking reaction crossed, reach and improve the purpose that product distributes, improves the quality of products.But, this technology has been ignored the characteristic that each constitutive property difference is big in the heavy raw oil, reaction is out of step, owing to adopt the short reaction time, even in the reaction environment that agent-oil ratio improves, part heavy constituent still transform insufficient, thereby when causing the raw material of this technology working properties difference, catalytic cracking unit coke yield height, settling vessel coking are serious.
WO9955801 has proposed the non-linear feed process of a kind of petroleum hydrocarbon.This method is that distillate is injected same riser tube by different nozzles respectively with inferior heavy oil, or injects the differential responses district of the axial division of same riser tube respectively, or injects different riser tubes respectively.When but petroleum hydrocarbon of different nature injects the differential responses district of axial distribution of same riser tube respectively, the reaction severity of the petroleum hydrocarbon of injecting lift pipe lower reaction zone is higher, and the petroleum hydrocarbon of injecting lift pipe top reaction zone reaction severity is lower, thereby total reaction conversion ratio and product selectivity can be subjected to influence to a certain degree, is difficult to guarantee the implementation result of non-linear charging.The general boiling range of inferior heavy oil described in this patent wherein contains the cut that some is easy to process element all greater than 500 ℃ in addition, as: 500-620 ℃, this method is not distinguished.
Sinopec Research Institute of Petro-Chemical Engineering has also developed a kind of catalytic cracking novel process VRFCC that processes grand celebration vacuum residuum, this technology is used the visbreaking atomization technique of high viscosity feedstock, special-purpose catalyst and antiskid fall riser reactor to improve the preventing from heavy metal pollution ability of heavy oil conversion performance and catalyzer, can solve cracking problem (the Processing and Engineering Technology ofthe Whole Daqing Vacuum Residue FCC (VRFCC) of the fcc raw material of similar grand celebration vacuum residuum (this vacuum residuum carbon residue and heavy metal content are relatively low) character; Li Zhiqiang, Wang Yamin.EngineeringScience.2003,1 (2): 53-60).
In addition, in order to adapt to heavy oil feedstock boiling point height, carbon residue height and the high characteristics of heavy metal content, both at home and abroad in optimizing materials atomizing, the revivifier aspect developings such as outside heat removing, riser tube outlet sharp separation, heavy metal passivation and the pre-lifting of catalyzer a series of heavy oil fluid catalytic cracking complete set technologys, for example (heavy petroleum hydrocarbon utilizes the modeling effort of technology-heavy hydrocarbon gasification-cracking integrated technique to the HOC technology of Kellogg; Wen Hao, Xu Zhihong, Wang Shaofeng, Zhao Yuehong; The process engineering journal, 2008,8 (4): 682-689), RCC technology (US4332673) of UOP, the ROCC-V technology (ZL95210840.2) of Luoyang Petrochemical engineering corporation etc., these patented technologies mostly are by optimizing reaction-regeneration equipment and catalyzer to strengthen the heavy oil catalytic cracking reaction process, though all obtained effect preferably, but these technology all are that various heavy oil feedstocks are come charging as one " integral body ", do not take into full account that there is bigger difference in the different components cracking performance in the heavy oil feedstock of wide boiling range.
For heavy oil catalytic cracking process, the chemical constitution of raw material is the deciding factor of its reactivity worth.And the chemical constitution of heavy oil fluid catalytic cracking raw material changes with its flow process range, a kind ofly contain the cut that a large amount of catalytic cracking unit are easy to process element, belong to for the different places of production and base, the boiling range scope there are differences, but most being present in less than in 500 ℃ the cut.This part cut hydrogen richness height contains a large amount of saturated branches and fragrance divides, and carbon residue is lower than 2.0wt%, and these all are the components that is easy to transform under the catalytic cracking reaction condition, and therefore, this part cut can be called the high-quality fcc raw material.And another cut contains a large amount of polycyclic aromatic hydrocarbonss and even condensed-nuclei aromatics, heavy metal and colloid, bituminous matter, this part cut overwhelming majority is present in greater than in 500 ℃ the catalytically cracked material cut, carbon residue is far above 2.0wt%, because this part cut is difficult to transform under conventional heavy oil catalytic cracking reaction condition, so this part cut can be called fcc raw material inferior.For high-quality or fcc raw material inferior, boiling range scope and chemical structure and composition determined their reactivity worth to exist than big-difference than big-difference.Yet, present heavy oil fluid catalytic cracking technology is not distinguished the fractions consisting and the reactivity worth thereof of its charging, all be to be blended together to enter catalytic cracking unit, and in same reactor He under the same process condition, transform, do not take optimized Measures respectively according to the reactivity worth difference of high-quality and fcc raw material inferior, this has just caused not matching between feedstock property and the reaction environment, has influenced the transformation efficiency of heavy oil catalytic cracking reaction process.
For heavy oil catalytic cracking reaction, there are very big difference in various hydro carbons, non-hydrocarbons compound in the absorption and the cracking ability of catalyst surface in the raw material, be in particular in non-hydrocarbons compound, condensed-nuclei aromatics and the condensed ring naphthenic hydrocarbon high adsorption capacity of condensed ring and speed of reaction is low, and have the mononuclear aromatics of longer side chain and macromole isoparaffin, the naphthenic hydrocarbon adsorptive power is weak and the speed of reaction height, this just caused between the different hydrocarbons competitive adsorption and to the retardation of reaction.The condensed ring non-hydrocarbons compound that high adsorption capacity and speed of reaction are low, condensed-nuclei aromatics are in case at first occupy catalyst surface, their speed of reaction are slow, be difficult for desorption, even condensation becomes coke and covers catalyst surface, cause catalyst deactivation, this has just had a strong impact on other and has been easy to the reaction efficiency of cracking hydrocarbons.And for the high quality raw material of heavy oil catalytically cracking equipment, wherein contain a large amount of components that under the catalytic cracking reaction condition, is easy to transform, if this part raw material and together charging reaction of the inferior raw material that contains a large amount of non-hydrocarbons compounds, condensed-nuclei aromatics, pernicious absorption competition and the retardation to reacting certainly will take place in same reaction zone, and the reaction that the result can influence whole raw material transforms.
On the other hand, condensed ring non-hydrocarbons compound, condensed-nuclei aromatics and gum asphalt speed of reaction a large amount of in the inferior raw material are low, need the long reaction times just can reach the ideal depth of conversion.The reaction times of conventional riser reactor is controlled at about 3s, high-quality fcc raw material part for easy conversion, this reaction times is suitable, but for fcc raw material part inferior, this reaction times is nowhere near, cause a large amount of non-conversions heavy constituent completely to be adsorbed on and be brought into stripping stage on the spent agent, easy condensation was got off after these heavy constituent parts were come out to enter settling vessel by stripping, cause the settling vessel coking, another part is brought in the revivifier as coke burns (" to some New understanding of heavy oil catalytic cracking reaction course---the proposition of " the novel multi-region control heavy oil fluid catalytic cracking technology MZCC of association " "; Gao Jinsen, Xu Chunming, Lu Chunxi, filoplume; Oil Refining Technologies and engineering, 2006,36 (12): 1-6; ), also seriously reduced the yield of light oil and the liquid yield of heavy oil catalytic cracking process.
Summary of the invention
Technical problem underlying solved by the invention is, at present plant catalytic cracking stock inferiorization problem day by day, provide a kind of to heavy oil the connect method and the device of subregion catalytic cracking, the difference that has response characteristic at the heavy oil fluid catalytic cracking raw material, carry out classification by boiling range, in reaction zone separately, set different catalytic cracking reaction conditions respectively then, significantly improve yield of light oil and liquid yield, especially improved the transformation efficiency of fcc raw material inferior.
The present invention at first provides the method for a kind of heavy oil series connection subregion catalytic cracking, and this method comprises:
Heavy oil feedstock is divided into high-quality fcc raw material and fcc raw material inferior, and wherein, the carbon residue of described high-quality fcc raw material is less than 2.0wt%, and the carbon residue of described fcc raw material inferior is greater than 2.0wt%.
(for example turbulent bed or fast bed add the combined reactor of carrying bed on the revivifier side combined reactor to be set, perhaps vertical sleeve tubular type hole enlargement riser tube adds the combined reactor of carrying bed), reaction zone is formed at the top of this combined reactor, and its underpart is provided with a hole enlargement structure and forms down reaction zone;
Make one catalyzer (regenerated catalyst) from revivifier under the effect of lift gas, enter, contact at reaction zone down with fcc raw material inferior by the bottom of reaction zone down, and the generation catalytic cracking reaction, reacted oil gas and catalyzer enter reaction zone;
Make from another strand catalyzer (regenerated catalyst) of revivifier bottom and enter by last reaction zone, and under castering action from oil gas that descends reaction zone and catalyzer, contact at last reaction zone with the high-quality fcc raw material, finish catalytic cracking reaction, draw reactive system after reacted oil gas and the catalyst separating, the catalyzer after the separation recycles through the revivifier coke burning regeneration.
The method of above-mentioned heavy oil series connection subregion provided by the invention catalytic cracking, compare with the catalytic cracking technology of present industrial application, mainly be difference according to the response characteristic of catalytically cracked material existence, earlier raw material is carried out classification by its carbon residue, catalytically cracked material is divided into high-quality fcc raw material and fcc raw material inferior, make then in its differential responses district that enters the catalytic cracking unit reactor assembly respectively and transform, being about to a complete catalytic-cracking reaction system is divided into, following two reaction zones, for the cracking reaction of different properties raw material provides independently conversion zone, and be optimum processing condition and reactor pattern of its coupling according to the reactivity worth of different material.
The present invention's defined " high-quality fcc raw material " and " fcc raw material inferior ", be meant that refinery passes through distillation or solvent extraction method, with the character of usually separating greater than 350 ℃ heavy oil and obtaining as the boiling range of catalytic cracking charging, form distinct two portions,, carbon residue lower for boiling range is less than the part of 2.0wt%, as " high-quality fcc raw material ",, carbon residue higher for the boiling range scope is greater than the part of 2.0wt%, as " fcc raw material inferior ".
In the refinery, the most representative " high-quality fcc raw material " is exactly boiling spread at 350-500 ℃ decompressed wax oil, carbon residue is much smaller than 2.0wt%, is 0.12wt% as the decompressed wax oil carbon residue of Daqing crude oil, and the carbon residue of the decompressed wax oil of LIAOHE CRUDE is 0.75wt%; The most representative " fcc raw material inferior " is exactly boiling spread greater than 500 ℃ vacuum residuum, and carbon residue is far above 2.0wt%, is 9.0wt% as the carbon residue of Daqing crude oil vacuum residuum, and the carbon residue of the vacuum residuum of LIAOHE CRUDE is 17.5wt%.
Really, in different atmospheric and vacuum distillation unit, along with the difference of operational condition, decompressed wax oil is extracted also difference of the degree of depth, and the cut point of decompressed wax oil and vacuum residuum will change between 500-600 ℃.If the carbon residue of control decompressed wax oil is below 2.0wt%, everything cutpoint is high more, and the amount of high-quality fcc raw material will be big more, helps improving the yield of light oil and the liquid yield of heavy oil catalytic cracking process more.This heavy oil classification subregion catalyst cracking method provided by the invention just carries out the fractionated intension with the difference of heavy oil feedstock according to response characteristic by its carbon residue.The present invention is by cutting provides high-quality and fcc raw material inferior to the raw material oil fraction, the foundation of dividing is the carbon residue of cut, theoretically, carbon residue just should be seldom in the situation of 2.0wt%, this moment, the division result of cut can determine as the case may be, but take all factors into consideration from industrial production, carbon residue is that the cut of 2.0wt% belongs to the high-quality fcc raw material.
Fcc raw material inferior contains a large amount of polycyclic aromatic hydrocarbonss, condensed-nuclei aromatics, heavy metal and gum asphalt, polynuclear hydrocarbon class that wherein contains or non-hydrocarbons compound high adsorption capacity and the slow characteristics of speed of reaction, the bottom of the riser reactor of routine can be provided with a hole enlargement structure and form down reaction zone (formation combined reactor), with reaction zone as this part raw material, by being set, the hole enlargement structure can reach the effect that prolongs the oil gas residence time, and being beneficial to increases beds density to improve the contact probability of oil gas and catalyzer, fast at fcc raw material reaction zone catalyst deactivation inferior in addition, the active low characteristics in rear portion, the bottom of reaction zone (going up the joint portion of reaction zone and following reaction zone in other words) introduces a part of catalyzer (or regenerated catalyst) on this combined reactor again, that is, improve the average activity of catalyzer by the placed in-line mode of catalyzer.In aforesaid method provided by the invention, preferably, the reaction conditions of following reaction zone is: the preheating temperature of fcc raw material inferior is controlled to be 150-300 ℃, agent-oil ratio (being fcc raw material inferior and the catalyzer that is entered by following reaction zone bottom) is controlled to be 5-7, reaction times is 2.0-10.0s, temperature of reaction is 450-550 ℃, and the bed linear velocity is 0.5-4.5m/s.
High-quality fcc raw material hydrogen richness height, contain a large amount of saturated cuts and fragrant cut, have the advantages that under the catalytic cracking reaction condition, to be easy to transform, the present invention adopts the top of conventional combined reactor to form one and goes up the reaction zone that reaction zone is used as this part raw material, preferably, the reaction conditions of last reaction zone is: the preheating temperature of high-quality fcc raw material is controlled to be 100-300 ℃, the high-quality fcc raw material is controlled to be 5-7 with the agent-oil ratio of the regenerated catalyst that is entered by last reaction zone bottom, reaction times is 2.0-3.0s, and reactor outlet temperature (being the outlet of the last reaction zone of combined reactor) is 480-520 ℃.
The present invention is to provide a kind of series connection catalytic cracking reaction method, here the agent-oil ratio of Xian Dinging is the high-quality fcc raw material and the agent-oil ratio of the regenerated catalyst that is entered by last reaction zone bottom, in the real reaction, part catalyzer also can enter reaction zone by following reaction zone, this part catalyzer also can participate in reaction, therefore, the agent oil of real reaction process increases many than above-mentioned agent-oil ratio.For the reaction times too, reaction times of fcc raw material inferior for example, what limit above is the reaction times of fcc raw material inferior in following reaction zone, and in the real reaction process, catalytic cracking reaction also can take place in fcc raw material inferior in last reaction zone, therefore, Shi Ji reaction times is than the reaction times of the top fcc raw material inferior that limits in following reaction zone.
In aforesaid method provided by the invention, preferably, the temperature of the temperature of the catalyzer (regenerated catalyst) that enters bottom following reaction zone and/or the catalyzer (regenerated catalyst) that enters bottom last reaction zone is 680-710 ℃.
In aforesaid method provided by the invention, preferably, for described combined reactor, the hole enlargement structure that its underpart is provided with can account for the 5-30% of whole combined reactor total height.
In aforesaid method provided by the invention, preferably, reaction zone for fcc raw material inferior, can be in the middle part or the agent of top injection chilling of reaction zone down, to control the temperature of reaction in this reaction zone, this chilling agent comprises water, recycle stock, gasoline, diesel oil, sump oil or its mixture, and injection rate is the 1-10wt% of fcc raw material amount inferior.
In aforesaid method provided by the invention, preferably, finished oil gas and catalyzer after the reaction of last reaction zone and can utilize separating of gas-oil separation mechanism realization response oil gas and catalyzer.
In aforesaid method, the hole enlargement structure of combined reactor bottom is as the reaction zone of fcc raw material inferior, its size is bigger than the diameter of existing riser reactor, can be for fcc raw material inferior and catalyzer provide bigger attaching space and more touch opportunity, help in the measured response time and reaction conditions such as low agent-oil ratio under realize the catalytic cracking of fcc raw material inferior is handled.
The present invention also provides a kind of device that is used to implement the method for above-mentioned heavy oil series connection subregion catalytic cracking, and this device comprises catalyst regenerator and combined reactor at least, wherein:
Described combined reactor is that turbulent bed or fast bed add the combined reactor of carrying bed, and its top is for carrying bed, and the bottom is turbulent bed or fast bed (can be that the hole enlargement structure that hole enlargement obtains is carried out in the bottom of riser reactor);
Described catalyst regenerator is provided with two catalyst transports at least, is communicated with the described bottom of bottom, described turbulent bed or the fast bed of bed of carrying respectively, and all is provided for the guiding valve of control catalyst (regenerated catalyst) flow in each catalyst transport; The exit end of combined reactor is communicated with oil-gas separator in the catalyst regenerator.
The present invention also provides the another kind of device that is used to implement the method for above-mentioned heavy oil series connection subregion catalytic cracking, and this device comprises catalyst regenerator and combined reactor, wherein:
Described combined reactor is that vertical sleeve tubular type hole enlargement riser tube adds the combined reactor of carrying bed, and its top is for carrying bed, and the bottom is vertical sleeve tubular type hole enlargement riser tube (being the hole enlargement structure);
Described catalyst regenerator is provided with two catalyst transports at least, be communicated with, and all be provided for the guiding valve of control catalyst (regenerated catalyst) flow in each catalyst transport with the described bottom of bed, the bottom of described vertical sleeve tubular type hole enlargement riser tube of carrying respectively; The exit end of combined reactor is communicated with oil-gas separator in the catalyst regenerator.
In said apparatus provided by the invention, preferably, pipe and outer tube in above-mentioned vertical sleeve tubular type hole enlargement riser tube has, should form interior territory, area under control in the interior pipe, form annular region between interior pipe and the outer tube, and described interior territory, area under control is 1 with the cross-sectional area ratio of annular region: 0.1-10; More preferably, territory, interior area under control is 1 with the cross-sectional area ratio of annular region: 0.5-4.
By the method for above-mentioned heavy oil series connection subregion provided by the invention catalytic cracking and the device of implementing this method, can avoid effectively pernicious absorption competition taking place and reaction being produced retardation between interior inferior raw material of conventional catalytic cracking riser reactor and high quality raw material, the part inferior that overcomes raw material simultaneously is in the insufficient problem of the conventional riser reactor internal reaction degree of depth, significantly improve lightweight oil and liquid yield, solve plant catalytic cracking stock inferiorization problem day by day to a certain extent.
The inventive method is suitable for all types of catalytic cracking catalysts.Each concrete equipment in the catalytic cracking reaction device of the present invention, for example catalyst regenerator, riser reactor, turbulent bed or fast bed add combined reactor, the vertical sleeve tubular type hole enlargement riser tube of carrying bed and add the combined reactor of carrying bed etc., be the common equipment in refining of petroleum field, carry out appropriate reconstruction and assemble and to come into operation according to processing requirement of the present invention, be beneficial to industrializing implementation.
Description of drawings
Fig. 1 is the technical process and the device synoptic diagram of the embodiment of the invention 1;
Fig. 2 is the technical process and the device synoptic diagram of the embodiment of the invention 2.
Embodiment
Understand for technical characterictic of the present invention, purpose and beneficial effect being had more clearly, technical scheme of the present invention is carried out following detailed description, but but can not be interpreted as qualification practical range of the present invention referring now to Figure of description.
Referring to technical process shown in Figure 1 and device synoptic diagram, the catalyst regenerator 4 other combined reactors 1 that are provided with at the heavy oil catalytic cracking reaction device, this combined reactor 1 adds the combined reactor of conveying bed for turbulent bed or fast bed, its top is for carrying bed, reaction zone 21 in the formation, the bottom is the turbulent bed or the fast bed of hole enlargement, forms reaction zone 22 down, and the height of described turbulent bed or fast bed is the 5-30% of whole combined reactor height;
A part of high temperature catalyst (high-temperature regenerated catalyst) in the catalyst regenerator 4 enters the following reaction zone 22 of combined reactor 1 by catalyst transport 8 and regenerated catalyst guiding valve 9, and under the castering action of lift gas 16, upwards flow and fcc raw material 14 inferior (distills cutting in advance to stock oil, the boiling range scope is higher than 580 ℃ classification stock oil, and following examples are identical) contact mixes, reaction; By the preheating temperature (span of control is 180-300 ℃) and regenerated catalyst guiding valve 7 apertures of regulating fcc raw material 14 inferior, the temperature that control enters the catalyzer (regenerated catalyst) of reactive system is 680-710 ℃, making down the agent-oil ratio in the reaction zone is 5-7, reaction times is 2.0-10.0s, the bed linear velocity is 2-6m/s, and temperature of reaction is 450-550 ℃.For control reaction temperature, in reaction zone (being fast bed) 22 middle and upper parts injection chilling agent 19 down, this chilling agent 19 comprises water, recycle stock, gasoline, diesel oil, sump oil or its mixture, and injection rate is the 1-10wt% of fcc raw material amount inferior; Reacted finish together enters the bottom of reaction zone 21.
Another strand high temperature catalyst (high-temperature regenerated catalyst) in the catalyst regenerator 4 enters the bottom of reaction zone 21 by catalyst transport 6 and regenerated catalyst guiding valve 7, under from the castering action of oil gas that descends reaction zone 22 and catalyst mixture, upwards flow, and (stock oil is distilled cutting in advance with high-quality fcc raw material 15, the vertex of boiling range scope is less than 580 ℃, and carbon residue is less than the stock oil of 1.5wt%, following examples are identical) the contact mixing, reaction; By regulating high quality raw material preheating temperatures (span of control is 100-300 ℃) and regenerated catalyst guiding valve 7 apertures, it is 680-710 ℃ that control enters the preceding regenerated catalyst temperature of combined reactor, making the agent-oil ratio (high-quality fcc raw material/live catalyst) in the reaction zone 21 is 5-7, reaction times is 2.0-3.0s, the controlling reactor temperature out is 480-520 ℃, reacted catalyzer and oil gas are through oil and gas separating system 11, settling vessel 10 and top are revolved 13 and are separated back oil gas and draw catalytic-cracking reaction system, and catalyzer enters stripping stage 5 strippings, after enter revivifier 4 through catalyst transport 18 and carry out coke burning regeneration.
Embodiment 2
Referring to technical process shown in Figure 2 and device synoptic diagram, the catalyst regenerator 4 other combined reactors 1 that are provided with at the heavy oil catalytic cracking reaction device, this combined reactor 1 adds the combined reactor of carrying bed for vertical sleeve tubular type hole enlargement riser tube, its top is for carrying bed, reaction zone 21 in the formation, the bottom is a vertical sleeve tubular type hole enlargement riser tube, form reaction zone 22 down, the interior pipe of this vertical sleeve tubular type hole enlargement riser tube and outer tube are divided into inside and outside two isolated areas with it, and the ratio of interior pipe cross-sectional area and annular space (annular region promptly between pipe and the outer tube) cross-sectional area is 1: 0.1-10, and the height of this vertical sleeve tubular type hole enlargement riser tube is the 5-30% of whole combined reactor height;
A part of high temperature catalyst (high-temperature regenerated catalyst) in the catalyst regenerator 4 enters by catalyst transport 8 and regenerated catalyst guiding valve 9 in the interior pipe of following reaction zone 22 of combined reactor 1, and upwards flows under the castering action of lift gas 16 and contact mixing with fcc raw material 14 inferior, react; The preheating temperature (span of control is 180-300 ℃) by regulating fcc raw material inferior and the aperture of regenerated catalyst guiding valve 7, the temperature that control enters the catalyzer (regenerated catalyst) of reactive system is 680-710 ℃, making down the agent-oil ratio in the reaction zone 22 is 5-7, reaction times is 2.0-10.0s, the bed linear velocity is 2-6m/s, and temperature of reaction is 450-550 ℃; For control reaction temperature, in the middle and upper part injection chilling agent 19 of the interior pipe of reaction zone 22 down, this chilling agent comprises water, recycle stock, gasoline, diesel oil, sump oil or its mixture, and injection rate is the 1-10wt% of fcc raw material amount inferior; Reacted finish enters the bottom of reaction zone 21 through a tapered pipeline;
Enter down the bottom of annular region between the interior pipe of reaction zone and the outer tube by catalyst transport 6 and regenerated catalyst guiding valve 7 from another strand high temperature catalyst (high-temperature regenerated catalyst) of catalyst regenerator 4, by water vapour 12 by a circle distributor within it portion carry out fluidisation and promote, and the top of following reaction zone 22 with from pipe in the reaction zone 22 down in finish behind the initial reaction converge, together enter the bottom of reaction zone 21 through a tapered pipeline, and contact mixing with high-quality fcc raw material 15, reaction; By the preheating temperature (span of control is 100-300 ℃) of adjusting high-quality fcc raw material and the aperture of regenerated catalyst guiding valve 7, the temperature that control enters the catalyzer (regenerated catalyst) in the transfer lime 6 is 680-710 ℃, making the agent-oil ratio (live catalyst/high-quality fcc raw material) in the reaction zone is 5-7, reaction times is 2.0-3.0s, the controlling reactor temperature out is 480-520 ℃, reacted catalyzer and oil gas are through oil and gas separating system 11, settling vessel 10 and top are revolved 13 and are separated back oil gas and draw catalytic-cracking reaction system, and catalyzer enters stripping stage 5 strippings, after enter revivifier 4 through catalyst transport 18 and carry out coke burning regeneration.
Catalyst cracking method provided by the present invention is to carry out catalytic cracking reaction at raw material of different nature to need different energy and catalytic environment with device, catalytically cracked material is divided into high-quality fcc raw material and fcc raw material inferior according to the difference section of response characteristic, makes then in its differential responses district that enters the catalytic cracking unit reactor assembly respectively to transform.The invention has the advantages that, by catalyst cracker being divided into two reaction zones up and down, the cracking reaction that can be embodied as the different properties raw material provides independently reaction compartment, and by optimizing the processing condition and the reactor pattern in differential responses district, thereby effectively avoid pernicious absorption competition taking place and reaction being produced retardation between interior inferior raw material of conventional catalytic cracking riser reactor and high quality raw material, also overcome simultaneously raw material part inferior in the insufficient problem of the conventional riser reactor internal reaction degree of depth, significantly improve lightweight oil and liquid yield, solve plant catalytic cracking stock inferiorization problem day by day to a certain extent.
Example
For verifying the effect of catalyst cracking method provided by the invention, device and the technical process of adopting embodiment 1 to provide are carried out commerical test on 1,000,000 tons of/year heavy oil catalytically cracking equipments of certain refinery, and test-results is listed in table 1.
After adopting this invention, original fcc raw material is carried out the fractionation cutting obtain high-quality fcc raw material and fcc raw material inferior (its character sees Table 1) respectively, the catalytic cracking reaction zone that high-quality fcc raw material and fcc raw material inferior are entered respectively separately reacts, the optimization reaction conditions of Cai Yonging is as shown in table 2 separately, compare with conventional heavy oil fluid catalytic cracking, adopt the technical scheme of this embodiment can make yield of light oil (in gasoline+diesel oil) improve 1.0 percentage points, liquid yield has improved 1.4 percentage points (in liquefied gas+gasoline+diesel oil), and dry gas and coke yield obviously reduce.Detailed product distributes can see Table 3.
Table 1 heavy oil feedstock character
| Project | Raw material before the fractionation | Fcc raw material inferior | The high-quality fcc raw material |
| Density (20 ℃) kg/m 3 | 0.9206 | 0.9962 | 0.8954 |
| Carbon residue, wt% | 5.79 | 17.14 | 2.00 |
| Ultimate analysis | |||
| Carbon content, wt% | 87.18 | 88.18 | 86.85 |
| Hydrogen richness, wt% | 12.02 | 10.32 | 12.58 |
| Sulphur content, wt% | 0.38 | 0.42 | 0.37 |
| Nitrogen content, wt% | 0.36 | 0.61 | 0.27 |
| Hydrocarbon group composition analysis | |||
| Stable hydrocarbon, wt% | 60.26 | 36.30 | 68.24 |
| Aromatic hydrocarbons, wt% | 24.69 | 38.48 | 20.09 |
| Colloid, wt% | 13.12 | 20.32 | 10.72 |
| Bituminous matter, wt% | 1.94 | 4.90 | 0.95 |
| Ni content, wt% | 10.6 | 29.3 | 4.3 |
| V content, wt% | 7.4 | 16.4 | 4.4 |
Table 2 main technique condition
Annotate: total reaction time is the reaction times sum of stock oil in turbulent bed or fast bed and conveying bed;
Total agent-oil ratio is the agent-oil ratio in carrying bed.
Table 3 main products distributes
| Product distributes and character | The prior art scheme | Process program of the present invention |
| H 2S | 0.5 | 0.7 |
| Fuel gas | 4.1 | 3.5 |
| Liquefied gas | 15.3 | 15.7 |
| Gasoline | 44.7 | 45.5 |
| Diesel oil | 25.3 | 25.5 |
| Clarified oil | 1.8 | 1.3 |
| Coke | 8.3 | 7.8 |
| Add up to | 100.0 | 100.0 |
Need to prove at last, above embodiment only is used to illustrate technical scheme of the present invention and is unrestricted, although the present invention is had been described in detail with reference to preferred embodiment, those of ordinary skill in the art is to be understood that, can make amendment or be equal to replacement technical scheme of the present invention, and not break away from the spirit and scope of technical solution of the present invention.
Claims (10)
1. the method for heavy oil series connection subregion catalytic cracking, this method comprises:
Heavy oil feedstock is divided into high-quality fcc raw material and fcc raw material inferior, and wherein, the carbon residue of described high-quality fcc raw material is less than 2.0wt%, and the carbon residue of described fcc raw material inferior is greater than 2.0wt%;
On the revivifier side combined reactor is set, reaction zone is formed at the top of this combined reactor, and its underpart is provided with a hole enlargement structure and forms down reaction zone;
Make one catalyzer from revivifier under the effect of lift gas, enter, contact at reaction zone down with fcc raw material inferior by the bottom of reaction zone down, and the generation catalytic cracking reaction, reacted oil gas and catalyzer enter reaction zone;
Make from another strand catalyzer of revivifier bottom and enter by last reaction zone, and under castering action from oil gas that descends reaction zone and catalyzer, contact at last reaction zone with the high-quality fcc raw material, finish catalytic cracking reaction, draw reactive system after reacted oil gas and the catalyst separating, the catalyzer after the separation recycles through the revivifier coke burning regeneration.
2. the method for claim 1, wherein, the reaction conditions of following reaction zone is: the preheating temperature of fcc raw material inferior is 150-300 ℃, fcc raw material inferior is 5-7 with the agent-oil ratio of the regenerated catalyst that is entered by following reaction zone bottom, reaction times is 2.0-10.0s, temperature of reaction is 450-550 ℃, and the bed linear velocity is 0.5-4.5m/s;
The reaction conditions of last reaction zone is: the preheating temperature of high-quality fcc raw material is 100-300 ℃, the high-quality fcc raw material is 5-7 with the agent-oil ratio of the regenerated catalyst that is entered by last reaction zone bottom, reaction times is 2.0-3.0s, and the reactor outlet temperature is 480-520 ℃.
3. method as claimed in claim 2, wherein, the temperature of the temperature of the catalyzer that enters bottom following reaction zone and/or the catalyzer that enters bottom last reaction zone is 680-710 ℃.
4. method as claimed in claim 2, wherein, for described combined reactor, the hole enlargement structure that its underpart is provided with accounts for the 5-30% of whole combined reactor total height.
5. as each described method of claim 1-4, wherein, reaction zone for fcc raw material inferior, the chilling agent is injected on middle part or top at described reaction zone down, to control the temperature of reaction in this reaction zone, described chilling agent comprises water, recycle stock, gasoline, diesel oil, sump oil or its mixture, and injection rate is the 1-10wt% of fcc raw material amount inferior.
6. as each described method of claim 1-4, wherein, finish oil gas and catalyzer after the reaction of reaction zone and utilize separating of gas-oil separation mechanism realization response oil gas and catalyzer.
7. device that is used to implement the method for each described heavy oil series connection subregion catalytic cracking of claim 1-6, this device comprises catalyst regenerator and combined reactor at least, wherein:
Described combined reactor is that turbulent bed or fast bed add the combined reactor of carrying bed, and its top is for carrying bed, and the bottom is turbulent bed or fast bed;
Described catalyst regenerator is provided with two catalyst transports at least, is communicated with the described bottom of bottom, described turbulent bed or the fast bed of bed of carrying respectively, and all is provided for the guiding valve of control catalyst flow in each catalyst transport; The exit end of combined reactor is communicated with oil-gas separator in the catalyst regenerator.
8. device that is used to implement the method for each described heavy oil series connection subregion catalytic cracking of claim 1-6, this device comprises catalyst regenerator and combined reactor, wherein:
Described combined reactor is that vertical sleeve tubular type hole enlargement riser tube adds the combined reactor of carrying bed, and its top is for carrying bed, and the bottom is a vertical sleeve tubular type hole enlargement riser tube;
Described catalyst regenerator is provided with two catalyst transports at least, is communicated with, and all is provided for the guiding valve of control catalyst flow in each catalyst transport with the described bottom of bed, the bottom of described vertical sleeve tubular type hole enlargement riser tube of carrying respectively; The exit end of combined reactor is communicated with oil-gas separator in the catalyst regenerator.
9. device as claimed in claim 8, wherein, pipe and outer tube in described vertical sleeve tubular type hole enlargement riser tube has, should form interior territory, area under control in the interior pipe, form annular region between interior pipe and the outer tube, and described interior territory, area under control is 1 with the cross-sectional area ratio of annular region: 0.1-10.
10. device as claimed in claim 9, wherein, described interior territory, area under control is 1 with the cross-sectional area ratio of annular region: 0.5-4.
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| CN103509596A (en) * | 2013-09-29 | 2014-01-15 | 中国石油大学(北京) | Method for processing inferior heavy oil |
| CN105419868A (en) * | 2015-11-27 | 2016-03-23 | 中国石油大学(北京) | Heavy oil fluid catalytic cracking method and device |
| CN110272760A (en) * | 2018-05-29 | 2019-09-24 | 石宝珍 | A kind of petroleum hydrocarbon multi-stage fluidized catalytic reaction method and reactor |
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| CN1462792A (en) * | 2002-05-31 | 2003-12-24 | 中国石油化工股份有限公司 | Method for eatalyzing and transfering petroleum hydrocarbon compounds by using reactor with dual reacting regions |
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| 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 |
| CN2506644Y (en) * | 2001-09-27 | 2002-08-21 | 中国石油化工股份有限公司 | Double-pathway feeding sleeve type catalyzing-cracking reactor |
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| CN105419868A (en) * | 2015-11-27 | 2016-03-23 | 中国石油大学(北京) | Heavy oil fluid catalytic cracking method and device |
| CN110272760A (en) * | 2018-05-29 | 2019-09-24 | 石宝珍 | A kind of petroleum hydrocarbon multi-stage fluidized catalytic reaction method and reactor |
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| CN102102026B (en) | 2014-04-02 |
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