CN102102026B - 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 efficiency, relate in particular to a kind of method and apparatus of heavy oil tandem regional catalytic cracking, belong to 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 the light-end products such as liquefied petroleum gas (LPG), gasoline, diesel oil.Traditional catalytically cracked material is mainly vacuum distillate, due to the continuous growth of lightweight oil demand and the raising of crude oil price, utilize catalytic cracking technology processing heavy raw oil to increase economic efficiency, to become the important selection of oil refining enterprise as atmospheric residue, vacuum residuum and diasphaltene residual oil.
At present, processing for heavy raw oil, the residual oil of the overwhelming majority is all that part is mixed and in vacuum distillate, entered catalytic cracking unit processing, and the ratio of mixing is subject to the strict restriction of carbon residue in residual oil, heavy metal and hydrogen richness, this has also seriously limited the ability of utilizing the direct process residual oils of catalytic cracking unit.
In recent years, 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 reaction process, object product yield and Quality Down.The series of problems bringing in order to solve processing inferior heavy oil, strengthening heavy oil catalytic cracking reaction process, some novel Catalytic Cracking Technique of Heavy Oils are shown one's talent.For example, ZL00134054.9 is the drawback at the serious inactivation of reaction the second half, oil gas overstand in reactor for catalyzer in heavy oil fluid catalytic cracking riser reactor, has proposed two-stage riser reactor catalysis cracking Technology.This technique replaces original single riser reactor with two-stage riser reactor, forms two-way catalyst recirculation: fresh feed enters first paragraph riser reactor and regenerated catalyst contact reacts; Turning oil enters second segment riser reactor and regenerated catalyst contact reacts, by controlling the different operational condition of two-stage riser, has realized catalyzer relay, segmentation reaction, short reaction time and high agent-oil ratio operation.This technology can be controlled unwanted cracking reaction and the heat cracking reaction crossed in reactor to a certain extent, reaches and improves the object that product distributes, improves the quality of products.But, this technology has been ignored the characteristic that in heavy raw oil, each constitutive property difference is large, reaction is out of step, owing to adopting the short reaction time, even in the reaction environment improving at agent-oil ratio, part heavy constituent still transforms insufficient, thereby while causing the poor raw material of this technology working properties, catalytic cracking unit coke yield is high, settling vessel coking is serious.
WO9955801 has proposed the non-linear feed process of a kind of petroleum hydrocarbon.The method is that distillate and inferior heavy oil are injected to same riser tube by different nozzles respectively, or injects respectively the differential responses district of the axial division of same riser tube, or injects respectively different riser tubes.When but petroleum hydrocarbon of different nature injects respectively the differential responses district of axial distribution of same riser tube, the reaction severity of the petroleum hydrocarbon of injecting lift pipe lower reaction zone is higher, and the petroleum hydrocarbon of reaction zone, injecting lift pipe top reaction severity is lower, thereby total reaction conversion ratio and product selectivity can be subject to impact to a certain extent, be difficult to guarantee the implementation result of non-linear charging.The general boiling range of inferior heavy oil described in this patent is all greater than 500 ℃ in addition, wherein containing some, is easy to the cut of process element, as: 500-620 ℃, the method is not distinguished.
Sinopec Research Institute of Petro-Chemical Engineering has also developed a kind of catalytic cracking novel process VRFCC that processes Daqing Vacuum Residue, the visbreaking atomization technique of this utilization 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 Daqing Vacuum Residue (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 the feature that heavy oil feedstock boiling point is high, carbon residue is high and heavy metal content is high, both at home and abroad from the aspect developing such as outside heat removing, leg outlet sharp separation, heavy metal passivation and catalyzer pre-lift in optimizing materials atomization, revivifier 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 technique of Kellogg; Wen Hao, Xu Zhihong, Wang Shaofeng, Zhao Yuehong; Process engineering journal, 2008,8 (4): 682-689), the RCC technique (US4332673) of UOP is, the ROCC-V technique (ZL95210840.2) of Luoyang Petrochemical engineering corporation etc., these patented technologies are mostly to react-regenerate equipment and catalyzer with strengthening heavy oil catalytic cracking reaction process by optimization, although all obtained good effect, but these technology are all that various heavy oil feedstocks are carried out to charging as one " integral body ", do not take into full account the larger difference of 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 Rfcc Feedstock 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, for the different places of production and base, belong to, boiling range scope there are differences, but most being present in the cut that is less than 500 ℃.This part cut hydrogen richness is high, contains a large amount of saturated minute and fragrance minute, and carbon residue is lower than 2.0wt%, and these are all the components that is easy to conversion under catalytic cracking reaction condition, and therefore, this part cut can be called 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 the catalytically cracked material cut that is greater than 500 ℃, 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, the larger difference of boiling range scope and chemical structure and composition has determined that their reactivity worth exist larger difference.Yet, current Catalytic Cracking Technique of Heavy Oil is not distinguished the fractions consisting of its charging and reactivity worth thereof, all to be blended together to enter catalytic cracking unit, and transform in same reactor He under same process condition, according to the reactivity worth difference of high-quality and fcc raw material inferior, do not take respectively optimized Measures, this has just caused not mating between feedstock property and reaction environment, has affected the transformation efficiency of heavy oil catalytic cracking reaction process.
For heavy oil catalytic cracking reaction, in raw material there is very large difference in absorption and the cracking ability of catalyst surface in various hydro carbons, non-hydrocarbons, be in particular in non-hydrocarbons, condensed-nuclei aromatics and the condensed ring naphthenic hydrocarbon high adsorption capacity of condensed ring and speed of reaction is low, and with compared with a little less than the mononuclear aromatics of long side chain and macromole isoparaffin, naphthenic hydrocarbon adsorptive power and speed of reaction is high, this has just caused competitive adsorption and the retardation to reaction between different hydrocarbons.Once high adsorption capacity and first low condensed ring non-hydrocarbons, the condensed-nuclei aromatics of speed of reaction 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 is easy to conversion under catalytic cracking reaction condition, if this part raw material and the inferior raw material that contains a large amount of non-hydrocarbons, condensed-nuclei aromatics together charging react, pernicious absorption competition and the retardation to reaction certainly will occur in same reaction zone, and the reaction that result can affect whole raw material transforms.
On the other hand, condensed ring non-hydrocarbons, condensed-nuclei aromatics and gum asphalt speed of reaction a large amount of in inferior raw material are low, and reaction times that need to be longer just can reach desirable depth of conversion.The reaction times of conventional riser reactor is controlled at 3s left and right, 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-transformed heavy constituents to be thoroughly adsorbed on and on spent agent, be brought into stripping stage, after these heavy constituent parts are out entered settling vessel by stripping, easy condensation is got off, cause settling vessel coking, another part is brought in revivifier and burns as coke (" the some of heavy oil catalytic cracking reaction course are familiar with again---the proposition of " the control Catalytic Cracking Technique of Heavy Oil MZCC of Novel multi association " ", Gao Jinsen, Xu Chunming, Lu Chunxi, filoplume, oil Refining Technologies and engineering, 2006,36 (12): 1-6, ), also seriously reduced 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, for current plant catalytic cracking stock in poor quality problem day by day, a kind of method and device that heavy oil is carried out to tandem regional catalytic cracking is provided, for Rfcc Feedstock, there is the difference of response characteristic, by boiling range, carry out classification, then, in reaction zone separately, set respectively different catalytic cracking reaction conditions, significantly improve yield of light oil and liquid yield, especially improved the transformation efficiency of fcc raw material inferior.
First the present invention provides a kind of method of heavy oil tandem regional catalytic cracking, and the 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 revivifier side, combined reactor to be set, or 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 arranges a hole enlargement structure and forms lower reaction zone;
Make one catalyzer (regenerated catalyst) from revivifier under the effect of lift gas, bottom by lower reaction zone enters, contact in lower reaction zone with fcc raw material inferior, and catalytic cracking reaction occurs, reacted oil gas and catalyzer enter reaction zone;
The bottom by upper reaction zone from another strand of catalyzer (regenerated catalyst) of revivifier is entered, and under the castering action of the oil gas from lower reaction zone and catalyzer, contact in upper reaction zone with high-quality fcc raw material, complete catalytic cracking reaction, after reacted oil gas and catalyst separating, draw reactive system, the catalyzer after separation recycles through revivifier coke burning regeneration.
The method of above-mentioned heavy oil tandem regional catalytic cracking provided by the invention, compare with the catalytic cracking technology of current industrial application, mainly according to the difference of the response characteristic of catalytically cracked material existence, first raw material is carried out to classification by its carbon residue, catalytically cracked material is divided into high-quality fcc raw material and fcc raw material inferior, then make to transform in its differential responses district that enters respectively catalytic cracking unit reactor assembly, being about to a complete catalytic-cracking reaction system is divided into, lower two reaction zones, for the cracking reaction of different properties raw material provides independently conversion zone, and for it, mate optimum processing condition and type of reactor according to the reactivity worth of different material.
The present invention's defined " high-quality fcc raw material " and " fcc raw material inferior ", refer to that refinery passes through distillation or solvent extraction method, boiling range usually used as catalytic cracking charging is greater than to character that the heavy oil of 350 ℃ is isolated, forms distinct two portions, the part lower for boiling range, carbon residue is less than 2.0wt%, as " high-quality fcc raw material ", the part higher for boiling range scope, carbon residue is greater than 2.0wt%, as " fcc raw material inferior ".
In refinery, the most representative " high-quality fcc raw material " is exactly boiling spread at the decompressed wax oil of 350-500 ℃, carbon residue is much smaller than 2.0wt%, and if the decompressed wax oil carbon residue of Daqing crude oil is 0.12wt%, the carbon residue of the decompressed wax oil of LIAOHE CRUDE is 0.75wt%; The most representative " fcc raw material inferior " is exactly the vacuum residuum that boiling spread is greater than 500 ℃, and carbon residue is far above 2.0wt%, and if the carbon residue of Daqing crude oil vacuum residuum is 9.0wt%, 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 control the carbon residue of decompressed wax oil below 2.0wt%, everything cutpoint is higher, and the amount of high-quality fcc raw material will be larger, is more conducive to improve yield of light oil and the liquid yield of heavy oil catalytic cracking process.This just heavy oil provided by the invention Grading And Zoning catalyst cracking method by heavy oil feedstock according to the difference of response characteristic, by its carbon residue, carry out the intension of classification.The present invention is by raw material oil fraction, cutting provides high-quality and fcc raw material inferior, divide according to the carbon residue that is cut, theoretically, carbon residue just should be seldom in the situation of 2.0wt%, now the division result of cut can determine as the case may be, but from industrial production, consider, the cut that carbon residue is 2.0wt% belongs to 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, the polynuclear hydrocarbon class wherein containing or non-hydrocarbons high adsorption capacity and the slow feature of speed of reaction, the bottom of conventional riser reactor can be arranged to a hole enlargement structure and form lower reaction zone (formation combined reactor), the reaction zone of usining as this part raw material, by being set, hole enlargement structure can reach the effect that extends the oil gas residence time, and be beneficial to and increase beds density to improve the contact probability of oil gas and catalyzer, in addition fast for fcc raw material inferior reaction zone catalyst deactivation, the active low feature in rear portion, in the bottom (going up the joint portion of Yu Xia reaction zone, reaction zone in other words) of the upper reaction zone of this combined reactor, introduce a part of catalyzer (or regenerated catalyst) again, , the mode of connecting by catalyzer improves the average activity of catalyzer.In aforesaid method provided by the invention, preferably, the reaction conditions of lower reaction zone is: the preheating temperature of fcc raw material inferior is controlled as 150-300 ℃, agent-oil ratio (being fcc raw material inferior and the catalyzer being entered by bottom, lower reaction zone) is controlled as 5-7, reaction times is 2.0-10.0s, temperature of reaction is 450-550 ℃, and bed linear velocity is 0.5-4.5m/s.
High-quality fcc raw material hydrogen richness is high, contain a large amount of saturated cuts and fragrant cut, the feature with the conversion of being easy under catalytic cracking reaction condition, the present invention adopts the top of conventional combined reactor to form the reaction zone that a upper reaction zone is used as this part raw material, preferably, the reaction conditions of upper reaction zone is: the preheating temperature of high-quality fcc raw material is controlled as 100-300 ℃, it is 5-7 that high-quality fcc raw material is controlled with the agent-oil ratio of the regenerated catalyst being entered by bottom, upper reaction zone, reaction times is 2.0-3.0s, reactor outlet temperature (being the outlet of the upper reaction zone of combined reactor) is 480-520 ℃.
The present invention is to provide a kind of series connection Catalytic Cracking Unit of Measure induction method, here the agent-oil ratio limiting is high-quality fcc raw material and the agent-oil ratio of the regenerated catalyst being entered by bottom, upper reaction zone, in real reaction, part catalyzer also can enter upper reaction zone by lower 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 lower reaction zone, and in real reaction process, in upper reaction zone, also can there is catalytic cracking reaction in fcc raw material inferior, therefore, the actual reaction times than the fcc raw material inferior that limited above the reaction times in lower reaction zone.
In aforesaid method provided by the invention, preferably, the temperature of the temperature of the catalyzer (regenerated catalyst) being entered by bottom, lower reaction zone and/or the catalyzer (regenerated catalyst) that entered by bottom, upper reaction zone is 680-710 ℃.
In aforesaid method provided by the invention, preferably, for described combined reactor, the hole enlargement structure that its underpart arranges 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 inject chilling agent on middle part or the top of lower reaction zone, 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, completed oil gas after the reaction of upper reaction zone and catalyzer and can utilize the separated of oil-gas 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 larger than the diameter of existing riser reactor, can be for fcc raw material inferior and catalyzer provide larger attaching space and more touch opportunity, be conducive within the measured response time and the reaction conditions such as lower agent-oil ratio under realize the catalytic cracking of fcc raw material inferior processed.
The present invention also provides that a kind of this device at least comprises catalyst regenerator and combined reactor for implementing the device of the method for above-mentioned heavy oil tandem regional catalytic cracking, 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 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 at least arranges two catalyst transports, be communicated with the described bottom of bottom, described turbulent bed or the fast bed of bed of carrying respectively, and in each catalyst transport, be all provided for controlling the guiding valve of catalyzer (regenerated catalyst) flow; The exit end of combined reactor is communicated with the oil-gas separator in catalyst regenerator.
The present invention also provides another kind for implementing the device of the method for above-mentioned heavy oil tandem regional 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 bottom is vertical sleeve tubular type hole enlargement riser tube (being hole enlargement structure);
Described catalyst regenerator at least arranges two catalyst transports, be communicated with, and in each catalyst transport, be all provided for controlling the guiding valve of catalyzer (regenerated catalyst) flow 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 the oil-gas separator in catalyst regenerator.
In said apparatus provided by the invention, preferably, above-mentioned vertical sleeve tubular type hole enlargement riser tube has inner and outer tubes, in this inner tube, form inner tube region, between inner tube and outer tube, form annular region, and described inner tube region is 1 with the cross-sectional area ratio of annular region: 0.1-10; More preferably, inner tube region is 1 with the cross-sectional area ratio of annular region: 0.5-4.
By the method for above-mentioned heavy oil tandem regional catalytic cracking provided by the invention and the device of implementing the method, can effectively avoid between inferior raw material and high quality raw material, pernicious absorption competition occurring in conventional catalytic cracking riser reactor and to react generation retardation, overcome the problem of part inferior reaction depth deficiency in conventional riser reactor of raw material simultaneously, significantly improve lightweight oil and liquid yield, solve to a certain extent plant catalytic cracking stock in poor quality problem day by day.
The inventive method is suitable for all types of catalytic cracking catalysts.Each concrete equipment in catalytic cracking reaction device of the present invention, such as catalyst regenerator, riser reactor, turbulent bed or fast bed, add the combined reactor etc. of carrying combined reactor, the vertical sleeve tubular type hole enlargement riser tube of bed to add to carry bed, be the common equipment in refining of petroleum field, according to processing requirement of the present invention, carry out appropriate reconstruction and assemble coming into operation, be beneficial to industrializing implementation.
Accompanying drawing explanation
Fig. 1 is technical process and the device schematic diagram of the embodiment of the present invention 1;
Fig. 2 is technical process and the device schematic diagram of the embodiment of the present invention 2.
Embodiment
For technical characterictic of the present invention, object and beneficial effect being had more clearly, understand, referring now to Figure of description, technical scheme of the present invention is carried out to following detailed description, but can not be interpreted as restriction that can practical range of the present invention.
Technical process shown in Figure 1 and device schematic diagram, the other combined reactor 1 that arranges of catalyst regenerator 4 at heavy oil catalytic cracking reaction device, this combined reactor 1 is that turbulent bed or fast bed add the combined reactor of carrying bed, its top is for carrying bed, in formation, reaction zone 21, bottom is turbulent bed or the fast bed of hole enlargement, forms lower reaction zone 22, 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 catalyst regenerator 4 enters the lower reaction zone 22 of combined reactor 1 by catalyst transport 8 and regenerated catalyst guiding valve 9, and upwards flow and (stock oil is distilled to cutting in advance with fcc raw material 14 inferior under the castering action of lift gas 16, boiling range scope is higher than the classification stock oil of 580 ℃, and following examples are identical) contact mixes, reaction; By regulating preheating temperature (span of control is 180-300 ℃) and regenerated catalyst guiding valve 7 apertures of fcc raw material 14 inferior, the temperature that control enters the catalyzer (regenerated catalyst) of reactive system is 680-710 ℃, making the agent-oil ratio in lower reaction zone is 5-7, reaction times is 2.0-10.0s, bed linear velocity is 2-6m/s, and temperature of reaction is 450-550 ℃.In order to control temperature of reaction, in lower reaction zone, chilling agent 19 is injected in (being fast bed) 22 middle and upper parts, and 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 of high temperature catalyst (high-temperature regenerated catalyst) in catalyst regenerator 4 enters the bottom of upper reaction zone 21 by catalyst transport 6 and regenerated catalyst guiding valve 7, under the castering action of the oil gas from lower reaction zone 22 and catalyst mixture, upwards flow, and (stock oil is distilled to 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) 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 front regenerated catalyst temperature of combined reactor, making the agent-oil ratio (high-quality fcc raw material/live catalyst) in reaction zone 21 is 5-7, reaction times is 2.0-3.0s, controlling reactor outlet temperature is 480-520 ℃, reacted catalyzer and oil gas are through oil and gas separating system 11, settling vessel 10 revolves 13 separated rear oil gas with top draws catalytic-cracking reaction system, and catalyzer enters stripping stage 5 strippings, after through catalyst transport 18, enter revivifier 4 and carry out coke burning regeneration.
Embodiment 2
Technical process shown in Figure 2 and device schematic diagram, the other combined reactor 1 that arranges of catalyst regenerator 4 at heavy oil catalytic cracking reaction device, this combined reactor 1 is that vertical sleeve tubular type hole enlargement riser tube adds the combined reactor of carrying bed, its top is for carrying bed, in formation, reaction zone 21, bottom is vertical sleeve tubular type hole enlargement riser tube, form lower reaction zone 22, the inner tube of this vertical sleeve tubular type hole enlargement riser tube and outer tube are divided into inside and outside two isolated areas, and the ratio of inner tube cross-sectional area and annular space (being the annular region between inner tube and outer tube) cross-sectional area is 1: 0.1-10, 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 catalyst regenerator 4 enters by catalyst transport 8 and regenerated catalyst guiding valve 9 in the inner tube of lower reaction zone 22 of combined reactor 1, and under the castering action of lift gas 16, upwards flows and contact mixing with fcc raw material 14 inferior, react; By regulating the preheating temperature (span of control is 180-300 ℃) of 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 the agent-oil ratio in lower reaction zone 22 is 5-7, reaction times is 2.0-10.0s, bed linear velocity is 2-6m/s, and temperature of reaction is 450-550 ℃; In order to control temperature of reaction, in the middle and upper part of the inner tube of lower reaction zone 22, inject chilling agent 19, this chilling agent comprises water, recycle stock, gasoline, diesel oil, sump oil or its mixture, injection rate is the 1-10wt% of fcc raw material amount inferior; Reacted finish enters the bottom of upper reaction zone 21 through a tapered pipeline;
From another strand of high temperature catalyst (high-temperature regenerated catalyst) of catalyst regenerator 4, by catalyst transport 6 and regenerated catalyst guiding valve 7, enter the bottom of annular region between the inner tube of lower reaction zone and outer tube, by water vapour 12 by a circle distributor within it portion carry out fluidisation lifting, and the top of lower reaction zone 22 with from lower reaction zone 22 inner tubes in finish after initial reaction converge, through a tapered pipeline, together enter the bottom of upper reaction zone 21, and contact mixing with high-quality fcc raw material 15, reaction, by regulating the preheating temperature (span of control is 100-300 ℃) of high-quality fcc raw material and the aperture of regenerated catalyst guiding valve 7, the temperature that control enters the catalyzer (regenerated catalyst) in transfer lime 6 is 680-710 ℃, making the agent-oil ratio (live catalyst/high-quality fcc raw material) in reaction zone is 5-7, reaction times is 2.0-3.0s, controlling reactor outlet temperature is 480-520 ℃, reacted catalyzer and oil gas are through oil and gas separating system 11, settling vessel 10 revolves 13 separated rear oil gas with top draws catalytic-cracking reaction system, and catalyzer enters stripping stage 5 strippings, after through catalyst transport 18, enter revivifier 4 and carry out coke burning regeneration.
Catalyst cracking method provided by the present invention and device are to carry out Catalytic Cracking Unit of Measure in requisition for different energy and catalytic environment for raw material of different nature, catalytically cracked material is divided into high-quality fcc raw material and fcc raw material inferior according to the difference section of response characteristic, then makes to transform in its differential responses district that enters respectively catalytic cracking unit reactor assembly.The invention has the advantages that, by catalyst cracker being divided into upper and lower two reaction zones, the cracking reaction that can be embodied as different properties raw material provides independently reaction compartment, and by optimizing processing condition and the type of reactor in differential responses district, thereby effectively avoid between inferior raw material and high quality raw material, pernicious absorption competition occurring in conventional catalytic cracking riser reactor and to react generation retardation, also overcome the problem of raw material part inferior reaction depth deficiency in conventional riser reactor simultaneously, significantly improve lightweight oil and liquid yield, solve to a certain extent plant catalytic cracking stock in poor quality problem day by day.
Example
For verifying the effect of catalyst cracking method provided by the invention, the device and the technical process that adopt embodiment 1 to provide are carried out commerical test on 1,000,000 tons/year of heavy oil catalytically cracking equipments of certain refinery, and test-results is listed in table 1.
Adopt after this invention, original fcc raw material is carried out to fractionation cutting and obtain respectively high-quality fcc raw material and fcc raw material inferior (its character is in Table 1), react the catalytic cracking reaction zone that high-quality fcc raw material and fcc raw material inferior are entered respectively separately, the optimization reaction conditions adopting is separately as shown in table 2, with conventional heavy oil fluid catalytic cracking, compare, 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), dry gas and coke yield obviously reduce.Detailed product distributes can be in Table 3.
Table 1 heavy oil feedstock character
| Project | Raw material before fractionation | Fcc raw material inferior | 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 |
[0055]table 2 technological condition
Note: 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 | 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 |
Finally it should be noted that, above embodiment is only unrestricted for technical scheme of the present invention is described, 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 modify or be equal to replacement technical scheme of the present invention, and not depart from the spirit and scope of technical solution of the present invention.
Claims (4)
1. a method for heavy oil tandem regional catalytic cracking, the 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 revivifier side, combined reactor is set, reaction zone is formed at the top of this combined reactor, and its underpart arranges a hole enlargement structure and forms lower reaction zone; For described combined reactor, the hole enlargement structure that its underpart arranges accounts for the 5-30% of whole combined reactor total height;
Make one catalyzer from revivifier under the effect of lift gas, by the bottom of lower reaction zone, entered, contact, and catalytic cracking reaction occurs with fcc raw material inferior in lower reaction zone, reacted oil gas and catalyzer enter reaction zone; Wherein, the reaction conditions of lower 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 being entered by bottom, lower reaction zone, reaction times is 2.0-10.0s, temperature of reaction is 450-550 ℃, and bed linear velocity is 0.5-4.5m/s;
The bottom by upper reaction zone from another strand of catalyzer of revivifier is entered, and under the castering action of the oil gas from lower reaction zone and catalyzer, contact in upper reaction zone with high-quality fcc raw material, complete catalytic cracking reaction, after reacted oil gas and catalyst separating, draw reactive system, the catalyzer after separation recycles through revivifier coke burning regeneration; The reaction conditions of upper reaction zone is: the preheating temperature of high-quality fcc raw material is 100-300 ℃, high-quality fcc raw material is 5-7 with the agent-oil ratio of the regenerated catalyst being entered by bottom, upper reaction zone, reaction times is 2.0-3.0s, and reactor outlet temperature is 480-520 ℃.
2. the temperature of the temperature of the catalyzer the method for claim 1, wherein being entered by bottom, lower reaction zone and/or the catalyzer that entered by bottom, upper reaction zone is 680-710 ℃.
3. method as claimed in claim 1 or 2, wherein, reaction zone for fcc raw material inferior, chilling agent is injected on middle part or top in described lower reaction zone, 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.
4. method as claimed in claim 1 or 2, wherein, completes oil gas after the reaction of reaction zone and catalyzer and utilizes the separated of oil-gas separation mechanism realization response oil gas and catalyzer.
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| CN105419868B (en) * | 2015-11-27 | 2017-07-11 | 中国石油大学(北京) | RFCC method and apparatus |
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