CN102102030B - Heavy oil catalytic cracking method and device by double-area coupling and catalyst tandem - Google Patents
Heavy oil catalytic cracking method and device by double-area coupling and catalyst tandem Download PDFInfo
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Abstract
The invention provides a method and a device for realizing catalytic cracking of heavy oil by a double-area coupling and catalyst tandem process, and belongs to the technical field of petroleum processing. According to difference of reaction characteristics of heavy oil catalytic cracking materials, the heavy oil catalytic cracking materials are divided into quality catalytic materials and inferior catalytic materials according to carbon residue values; and the quality catalytic materials and the inferior catalytic materials respectively enter different reaction areas in a catalytic cracking reaction system for catalytic cracking reaction. For the quality catalytic materials, a conventional riser reactor is utilized; for the inferior catalytic materials, a turbulent bed or fast bed and transport bed combined reactor is utilized, and the catalyst tandem process is adopted, so that the two parts of materials adopt respectively optimized reaction conditions in respective independent reaction areas provided by different-structure reactors; and the catalyst and oil contact temperature difference is reduced and a large catalyst-oil ratio is achieved by arranging a catalyst cooler, the problem that the catalyst in a reaction area for the inferior materials is severe in coking, quick in deactivation and low in later activity is improved and the light oil yield and the integral liquid yield are obviously improved.
Description
Technical field
The present invention relates to a kind of raising heavy oil catalytic cracking reaction transformation efficiency, the production technique of yield of light oil and liquid yield particularly, a kind of method and device that utilizes two-region coupling and catalyzer tandem process to realize heavy oil fluid catalytic cracking is especially provided, the invention belongs 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, as atmospheric residue, vacuum residuum and diasphaltene residual oil become the important selection of oil refining enterprise to increase economic efficiency.
At present, processing for heavy raw oil, for example, except carbon residue and the low especially paraffinic base of heavy metal content (especially content of vanadium) decompression oil (Daqing Vacuum Residue) can directly enter catalytic cracking unit processing (can be referring to: " Resid Fcc Technology For Processing Daqing Vacuum Residue ", Wu Xiuzhang, Yang Baokang, " refining of petroleum and chemical industry ", 2001,32 (8): 6-10; " several key measures of swallowization vacuum residue catalytic device regeneration system transformation ", Song Yichang, Ling Yiqun, Liang Fengyin, " refining of petroleum and chemical industry ", 2002,33 (5): 20-23), the residual oil of the overwhelming majority is all that part is mixed in vacuum distillate and enters 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, and 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, and result is dry gas and coke yield rising in reaction process, object product yield and Quality Down.In order to strengthen heavy oil catalytic cracking reaction process, some Catalytic Cracking Technique of Heavy Oils novel or improvement are shown one's talent.For example, Chinese invention patent ZL 00134054.9, the drawback at reaction the second half serious inactivation, oil gas overstand in reactor for catalyzer in heavy oil fluid catalytic cracking riser reactor wherein, has proposed to adopt the catalytic cracking process technology of two-stage riser reactor.This technique replaces original single riser reactor with two-stage riser reactor, in system, form the circulation of two-way catalyzer: 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, catalyzer relay, segmentation reaction have been realized, and the operation of short reaction time and high agent-oil ratio, this patented technology can be controlled undesirable cracking reaction and heat cracking reaction crossed in reactor to a certain extent, reaches and improves the object that product distributes, improves the quality of products.But, in this technology implementation, 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 that agent-oil ratio improves, a part of heavy constituent still transforms insufficient, thereby while causing this technology for the poor raw material of working properties, the problem that coke yield is high, settling vessel coking is serious of catalytic cracking unit, the operability of suitability for industrialized production is given a discount.
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 insider has developed a series of heavy oil fluid catalytic cracking complete set technologys in succession from aspects such as outside heat removing, leg outlet sharp separation, heavy metal passivation and catalyzer pre-lifts in optimizing materials atomization, revivifier, for example the HOC technique of Kellogg (" heavy petroleum hydrocarbon utilizes the modeling effort of technology-heavy hydrocarbon gasification-cracking integrated technique ". temperature great, Xu Zhihong, Wang Shaofeng, Zhao Yuehong." process engineering journal ", 2008, 8 (4): 682-689), the RCC technique of UOP (USP 4332673), the ROCC-V technique that in Chinese patent ZL95210840.2, Luoyang Petrochemical engineering corporation proposes etc., these results of study and patented technology are mostly to react-regenerate by optimization the object that equipment and catalyzer reach strengthening heavy oil catalytic cracking reaction process, although all obtained good effect, but these technology are all that various heavy oil feedstocks are carried out to charging as one " integral body ", still 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, raw material for the place of production from different and base genus, boiling range scope can there are differences, but most such component is present in (boiling range of different material can be variant) in the cut that is less than 500 ℃.In this part cut, hydrogen richness is high, contains a large amount of saturates cuts and fragrant substance cut, 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 in heavy oil, also have another cut, contain 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 ℃ of >, 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, most industrialization Catalytic Cracking Technique of Heavy Oils is not distinguished the fractions consisting of its charging and reactivity worth thereof at present, all to make raw material enter together catalytic cracking unit with blending ingredients form, and in same reactor and control the conversion that same process condition is carried out catalytic cracking, although have continuous research in the improvement of catalyzer improvement and catalytic cracking condition, but according to the reactivity worth difference of high-quality and fcc raw material inferior, do not take respectively up to now correlation technique research and the report of optimized Measures, thus, the current catalytic cracking process for heavy oil feedstock has caused not mating between feedstock property and reaction environment, affected the transformation efficiency of heavy oil catalytic cracking reaction process.
On the other hand, the combination of riser reactor and catalyst regenerator is the basic device of realizing catalytic cracking reaction, when the inferior raw material of high carbon residue, high metal content partly enters after independent reactor, green coke amount in riser tube reaction is significantly increased, cause catalyst activity reduction amplitude also to strengthen, thereby cause material reactor subsequent reactions activity inferior very low, selectivity is very poor, has a strong impact on yield and the transformation efficiency of product.This phenomenon is in fact also comparatively remarkable for conventional riser reactor, studies have found that, so only use conventional riser reactor, the average micro-activity of catalyzer only has 40% left and right of regenerator, subsequent reactions activity in riser tube is low, poor selectivity (" drawback and the two-stage riser fluid catalytic cracking of conventional catalyst cracking riser reactor ". Yang Chaohe, mountain is red, Zhang Jianfang, Ma An.《 China University Of Petroleum Beijing journal (natural science edition) ", 2007,31 (1): 127-131).Therefore the average response that improves rear portion in inferior raw material reactor is active, and for improving inferior raw material reaction depth, the selectivity that improves object product is significant.
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 heavy oil fluid catalytic cracking method of utilizing two-region coupling and catalyzer series connection 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 inferior raw material.
The invention provides a kind of heavy oil fluid catalytic cracking method of utilizing two-region coupling and catalyzer series connection, 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, riser reactor is set as the reaction zone of high-quality fcc raw material, high-quality fcc raw material is contacted in this riser reactor with the regenerated catalyst from revivifier, and there is catalytic cracking reaction, after reacted oil gas and catalyst separating, draw reactive system, the catalyzer after separation recycles through revivifier coke burning regeneration;
At the other turbulent bed or turbulent bed or fast bed of separately arranging of revivifier, add conveying bed combined reactor as the reaction zone of fcc raw material inferior, from the regenerated catalyst of revivifier, being divided into two stocks does not add and carries fast bed bottom and the top of bed combined reactor to introduce this combined reactor from described turbulent bed or turbulent bed or fast bed, make fcc raw material inferior under lift gas effect, make progress mobile in the regenerated catalyst contact introduced of first fast bed bottom, and common rising of this raw material and regenerated catalyst contacted on fast bed top with another strand of regenerated catalyst, complete catalytic cracking reaction, after reacted oil gas and catalyst separating, draw reactive system, catalyzer after separation recycles through revivifier coke burning regeneration.
The heavy oil fluid catalytic cracking method of utilizing two-region coupling and catalyzer series connection provided by the invention, compare with the catalytic cracking technology of current industrial application, be characterised in that the difference that has response characteristic for Rfcc Feedstock, first raw material is carried out to classification by boiling range, then enter respectively in catalytic-cracking reaction system and transform in differential responses district,, two the independently reaction zones that are coupled in a catalytic-cracking reaction system, set feasible reaction conditions to the high-quality fcc raw material after classification (light stock oil) and fcc raw material inferior (heavier feedstocks is oily) respectively.
The heavy oil fluid catalytic cracking method of utilizing two-region coupling and catalyzer series connection provided by the invention, first raw material to be carried out to classification by its carbon residue, then respectively the high-quality fcc raw material after classification and fcc raw material inferior are arranged to different reaction zones, set respectively preferred reaction conditions separately.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, to conventionally as the boiling range of catalytic cracking charging, be greater than character that the heavy oil of 350 ℃ is isolated, form 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 the charging of refinery, the most representative " high-quality fcc raw material " is exactly boiling spread at the decompressed wax oil of 350～500 ℃, its 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 its 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.
It is high that high-quality fcc raw material has hydrogen richness, contain a large amount of saturated cuts and fragrant cut, under catalytic cracking reaction condition, be easy to the feature transforming, the present invention adopts conventional riser reactor as the reaction zone of this part raw material, and the reaction conditions of high-quality fcc raw material is preferably: 460～520 ℃ of temperature of reaction, agent-oil ratio 5～11 (weight ratio of catalyzer and stock oil), 2.0～3.0 seconds reaction times, 100～300 ℃ of raw material preheating temperatures.
Fcc raw material inferior has and contains a large amount of polycyclic aromatic hydrocarbonss, condensed-nuclei aromatics, heavy metal and gum asphalt, and the polynuclear hydrocarbon class wherein containing or non-hydrocarbons high adsorption capacity and the slow feature of speed of reaction, the present invention has adopted turbulent bed or fast bed to add conveying bed combined reactor as the reaction zone of this part raw material, by being set, turbulent bed or the fast bed of extension diameter section formation 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, the turbulent bed of this combined reactor or fast bed top (can be with carry bed junction near), introduce a part of regenerated catalyst again, , the mode of connecting by catalyzer improves the average activity of catalyzer.In the inventive method, the reaction conditions of fcc raw material inferior can be preferably: 150～300 ℃ of raw material preheating temperatures, 450～550 ℃ of combined reactor temperature outs; In turbulent bed or fast bed, 2.0～10.0 seconds reaction times, bed linear speed 0.5～4.5m/ second, agent-oil ratio 6～10; In carrying bed, 1.0～2.0 seconds reaction times, agent-oil ratio 8～12, oil gas linear speed 8～12m/ second, and in the reaction of carrying bed, agent-oil ratio is greater than at fast bed and reacts.In actual production, according to the concrete cut-point of good and bad two kinds of raw materials, set the reaction times that the reaction times of suggestion control fcc raw material inferior is longer than high-quality fcc raw material.
Can see, according to processing method of the present invention, stock oil of different nature can be realized and transforming under applicable separately catalytic cracking environment and energy parameter control.Particularly fast for inferior raw material reaction zone catalyst deactivation, the active low problem in rear portion, utilize combined reactor, making reaction zone anterior is turbulent bed or fast bed (controlling gas speed realizes), and by adopting the mode of catalyzer series connection, the in good time make-up catalyst of counterweight stock oil reaction system in reaction process, improved the average activity (having improved agent-oil ratio) of rear portion, reaction zone catalyzer, easily reaction depth is not enough according to unified reaction conditions (in conventional riser reactor) to be conducive to overcome inferior raw material component, and the problem of the easily excessive thermally splitting of lightweight material component, also effectively avoided prior art that stock oil is processed together simultaneously, in conventional catalytic cracking riser reactor, between inferior raw material and high quality raw material, there is pernicious absorption competition and to reacting the problem that produces retardation, significantly improve yield of light oil and liquid yield, can solve to a certain extent plant catalytic cracking stock in poor quality problem day by day.
The method according to this invention, make to enter riser reactor and/turbulent bed or fast bed add and carry the regenerated catalyst temperature of bed combined reactor to be 680～710 ℃.
From the regenerated catalyst of catalyst regeneration system, can directly be admitted to riser reactor and turbulent bed or fast bed and add and carry a bed combined reactor, the stock oil of each reaction zone is implemented to catalytic cracking.For the benefit of control the agent-oil ratio of temperature of reaction and raising reaction system, at least one regenerated catalyst water cooler is preferably set in catalytic-cracking reaction system of the present invention, and to the elder generation of the regenerated catalyst from revivifier, at least one processes design temperature in by the following method:
Regenerated catalyst is first cooled to 580-670 ℃ and enters riser reactor again;
Making to introduce turbulent bed or fast bed adds in two strands of regenerated catalysts carrying bed combined reactor at least one and is first cooled to 600-670 ℃ and enters described combined reactor again.
Turbulent bed of the present invention or fast bed add to be carried in bed combined reactor, and described turbulent bed or fast bed are arranged on the bottom of whole combined reactor by hole enlargement, and preferably it is highly 5～30% of this combined reactor total height.By controlling gas short-term training, be turbulent bed or fast bed.
According to the heavy oil fluid catalytic cracking method of utilizing two-region coupling and catalyzer series connection provided by the invention, catalytic cracking for fcc raw material inferior reaction zone, preferably from described turbulent bed or fast bed, add middle part or the agent of top injection chilling of carrying fast bed bed combined reactor, to control the temperature of reaction in this reaction zone, and described chilling agent comprises water, recycle stock, gasoline, diesel oil, sump oil or its any mixture etc., and injection rate is 1～10wt% of fcc raw material amount inferior.
The invention provides a kind of method of utilizing two-region coupling to realize heavy oil fluid catalytic cracking, from the material of high-quality fcc raw material reaction zone and catalytic cracking material from fcc raw material inferior reaction zone, can utilize respectively the separated of oil and gas separating system realization response oil gas and catalyzer; Or, make the described catalytic cracking material from two reaction zones after converging, utilize the separated of an oil-gas separation mechanism realization response oil gas and catalyzer.
Carbon residue is high and component boiling range is high (conventionally will higher than 620 ℃) is the feature of mink cell focus, the present invention's defined " high-quality fcc raw material " and " fcc raw material inferior ", refer to two cut products that heavy oil cutting is obtained, before illustrate, for high-quality fcc raw material, require to control its carbon residue and be less than 2wt% (or being not more than 2wt%); For fcc raw material inferior, determine that its carbon residue is greater than 2wt%.
The present invention further provides the device of the catalyst cracking method of implementing the coupling of above-mentioned two-region and catalyzer series connection, this device at least comprises that catalyst regenerator, settling vessel, riser reactor and turbulent bed or fast bed add conveying bed combined reactor etc., described catalyst regenerator at least arranges three catalyst transports, add and carry in bed combined reactor turbulent bed or fast bed bottom and top to be communicated with riser reactor bottom, turbulent bed or fast bed respectively, and in each catalyst transport, be all provided for controlling the guiding valve of regenerated catalyst flow; Riser reactor and turbulent bed or fast bed add carries the exit end of bed combined reactor to be all communicated with the oil-gas separator in settling vessel.
In device provided by the invention, also can comprise at least one regenerated catalyst water cooler, its set-up mode at least comprises the scheme of one of the following:
This regenerated catalyst water cooler is serially connected with in the catalyst transport between catalyst regeneration system and riser reactor, and between guiding valve and catalyst regeneration system;
This regenerated catalyst water cooler is serially connected with catalyst regeneration system and turbulent bed or fast bed and adds described at least one of carrying between bed combined reactor in catalyst transport, and between guiding valve and catalyst regeneration system.
Catalytic cracking reaction device of the present invention, a regenerated catalyst water cooler can be only set, it is communicated with by least one catalyst transport with catalyst regenerator, and by described catalyst transport (catalyst transport now also claims regenerator sloped tube or dipleg), be communicated with riser reactor bottom simultaneously, and add and carry fast bed bottom and/or the top of bed combined reactor to be communicated with turbulent bed or fast bed.
Before illustrate, the object that regenerated catalyst water cooler is set is that the regenerated catalyst from catalyst regenerator is first cooled and (for example from 680-710 ℃ is cooled to 580-670 ℃, enters riser reactor, or after being cooled to 600-670 ℃, enter turbulent bed or fast bed add carry a bed combined reactor), so, this regenerated catalyst water cooler can be as required adds and carries a bed combined reactor to arrange separately for riser reactor and turbulent bed or fast bed, also a water cooler can be only set in whole reactive system, after cooling for the high-temperature regenerated catalyst from catalyst regenerator, by each catalyst transport (also weighing leg), introduce in the reactor of two reaction zones, by the guiding valve on described transfer lime, regulate operational throughput and the temperature of catalyzer.
In catalytic cracking reaction device provided by the invention, riser reactor and turbulent bed or fast bed add carries the exit end of bed combined reactor to be communicated with an oil-gas separator respectively, or riser reactor and turbulent bed or fast bed add after carrying the exit end of bed combined reactor to be connected and are communicated in same oil-gas separator again.
The present invention by arranging the reactor of two different structures on catalytic cracking reaction device, for the catalytic cracking reaction of different properties raw material provides independently reaction zone, and differential responses district adopts the processing condition of each self-optimizing, by the classification to stock oil, for high quality raw material oil, can provide the relative catalytic cracking environment being more suitable for inferior feedstock oil, especially for fcc raw material oil inferior (real heavy oil fraction), adopt catalyzer series connection that the mode of effect is provided simultaneously, coordinate the use of catalyst cooler, be beneficial to and reduce the finish contact temperature difference, improve the regenerated catalyst internal circulating load (rising agent oil ratio) that enters each reaction zone, the initial mixing temperature of control regenerated catalyst and stock oil and agent-oil ratio are in optimum range, the optimization distributing to realize product, the inventive method is also beneficial to elimination inferior feedstock oil and makes the defect that catalyzer coking is serious, inactivation is fast, improves the average activity of reaction zone postmedian catalyzer, and then has improved yield of light oil and the whole liquid yield in heavy oil fluid catalytic cracking of processing.
The inventive method is applicable to all types of catalytic cracking catalysts.Each concrete equipment in catalytic cracking reaction device of the present invention, such as catalyst regenerator, settling vessel, oil-gas separator, riser reactor, turbulent bed or fast bed, add and carry bed combined reactor, catalyst cooler etc., 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.
Fig. 3 is technical process and the device schematic diagram of the embodiment of the present invention 3.
Fig. 4 is technical process and the device schematic diagram of the embodiment of the present invention 4.
Embodiment
The beneficial effect that describes embodiment of the present invention in detail and have below in conjunction with the drawings and specific embodiments, but can not be interpreted as can practical range to the present invention any restriction.
Embodiment 1
Flow process referring to Fig. 1, at the catalyst regenerator 4 of heavy oil catalytic cracking reaction device, (the present invention is that to take settling vessel be example with the stacked FCC unit of the coaxial setting of revivifier, the height block form catalytic cracking unit that also can adopt settling vessel in production on riser reactor top but be arranged in parallel with revivifier, the two is the conventional structure of this area) side arranges conventional riser reactor 1, a part of high-temperature regenerated catalyst in catalyst regenerator 4 is entered riser reactor 1 and is upwards flowed and (stock oil is distilled to cutting in advance with high-quality fcc raw material oil 15 under the castering action of lift gas 16 by catalyst transport 6 and the regenerated catalyst guiding valve 7 on it, carbon residue is less than the stock oil of 2wt%, following examples are identical) contact reacts, by regulating raw material preheating temperature, be 100～300 ℃ and regenerated catalyst guiding valve 7 apertures, the regenerated catalyst temperature that control enters before riser reactor 1 is 680～710 ℃, make oil gas in riser reactor 1 460～520 ℃ of temperature of reaction, agent-oil ratio 5～11, under the condition of reaction times 2.0～3.0s, complete reaction.Reacted catalyzer and oil gas are through oil and gas separating system 11 (gas-solid quick disconnector, also claim oil-gas separator, following examples are identical), settling vessel 10 and top revolve 13 separated after oil gas draw catalytic-cracking reaction system (device), and catalyzer enters stripping stage 5, carry out stripping, after through catalyzer ingress pipe 18, enter catalyst regenerator 4 and carry out coke burning regeneration.
Turbulent bed or fast bed are also set on revivifier 4 sides of heavy oil catalytically cracking equipment and add a conveying bed combined reactor 2, as shown in fig. 1, this combined reactor is using conventional riser reactor as carrying bed 22, by arranging in its bottom, extension diameter section forms turbulent bed or fast bed 21 forms a combined reactor 2, reach and extend the oil gas residence time and improve wherein stock oil and contact the effect of density with beds, the height of described turbulent bed or fast bed 21 is the 5-30% (following examples are identical) of whole combined reactor height.In the time of above-mentioned high-quality fcc raw material oil reaction, the regenerated catalyst guiding valve 9 of another part high-temperature regenerated catalyst in catalyst regenerator 4 by catalyst transport 8 and its upper setting enters the bottom of turbulent bed in this combined reactor 2 or fast bed part 21, and upwards flow and (stock oil is distilled to cutting in advance with fcc raw material oil 14 inferior under the castering action of pre-lift gas 17, carbon residue is greater than the stock oil of 2.0wt%, following examples are identical) contact reacts, by regulating the preheating temperature of stock oil 14, be 150～300 ℃ (being preferably 250～300 ℃) and regenerated catalyst guiding valve 9 apertures, control enters turbulent bed or the front regenerated catalyst temperature of fast bed 21 is 680～710 ℃.Make oil gas first pass through turbulent bed or the fast bed 21 of combined reactor 2, for example, agent-oil ratio 6～10 (agent-oil ratio is 8), reaction times 2.0～10.0s, under bed linear velocity 0.5～4.5m/s condition, react, then make oil gas and catalyzer on turbulent bed or fast bed 21 tops (fast bed and the junction of carrying bed) with another strand from catalyst regenerator 4, and the regenerated catalyst of the regenerator guiding valve 91 by catalyst transport 81 and its upper setting mixes, together enter the conveying bed part 22 of combined reactor 2, at agent-oil ratio 8～12, (be the total agent-oil ratio in combined reactor herein, identical below), oil gas linear speed 8～12m/s, under the condition of reaction times 1.0～2.0s, react.For further control combination reactor 2 temperature outs are at 450～550 ℃, chilling agent 19 is injected in middle and upper part at the fast bed 21 of combined reactor 2, this chilling agent comprises water, recycle stock, gasoline, diesel oil, sump oil etc. or its any mixture, and injection rate is 1～10wt% of fcc raw material weight inferior.Reacted catalyzer and oil gas through oil and gas separating system 12, settling vessel 10 and top revolve 13 separated after oil gas draw catalytic-cracking reaction system, and catalyzer enters stripping stage 5 strippings, after through catalyzer ingress pipe 18, enter revivifier 4 and carry out coke burning regeneration.
The flow process of meaning shown in Figure 2, catalyst regenerator 4 sides at heavy oil catalytic cracking reaction device arrange conventional riser reactor 1 and regenerated catalyst water cooler 6, a part of high-temperature regenerated catalyst in catalyst regenerator 4 enters regenerator water cooler 6 by catalyst transport 70, heat-eliminating medium passes into from entrance 61, and through exporting 62 outflows, the regenerated catalyst temperature that enters this water cooler 6 is coolingly reduced to 580～670 ℃ from 680～710 ℃, cooled catalyzer enters riser reactor 1 through regenerator sloped tube 71 and regenerated catalyst guiding valve 7, under the castering action of lift gas 16, upwards flow and high-quality fcc raw material oil 15 contact reactss, the reaction conditions of riser reactor 1 is: 100～300 ℃ of raw material preheating temperatures, entering the front regenerated catalyst temperature of riser reactor 1 is 580～670 ℃, in reactor, temperature of reaction is 460～520 ℃, agent-oil ratio 5～11, under the condition of reaction times 2.0～3.0s (second), complete reaction.Reacted catalyzer and oil gas through oil and gas separating system 11, settling vessel 10 and top revolve 13 separated after oil gas draw catalytic-cracking reaction system, and catalyzer enters stripping stage 5 strippings, after through catalyzer ingress pipe 18, enter catalyst regenerator 4 and carry out coke burning regeneration.
Turbulent bed or fast bed are set on revivifier 4 sides of heavy oil catalytically cracking equipment and add a conveying bed combined reactor 2, a part of high-temperature regenerated catalyst in catalyst regenerator 4 enters the turbulent bed of this combined reactor 2 or the bottom of fast bed part 21 by the regenerated catalyst guiding valve 9 of catalyst transport 8 and setting on it, and under the castering action of pre-lift gas 17, upwards flow and fcc raw material oil inferior 14 contact reactss, by regulating raw material preheating temperature (span of control is 150～300 ℃) and regenerated catalyst guiding valve 9 apertures, control enters turbulent bed or the front regenerated catalyst temperature of fast bed 21 is 680～710 ℃, make oil gas first pass through turbulent bed or the fast bed 21 of combined reactor 2, at agent-oil ratio 6～10, reaction times 2.0～10.0s, under bed linear velocity 0.5～4.5m/s condition, react, then make oil gas and catalyzer in turbulent bed or fast bed 21 tops (junction of turbulent bed or fast bed and conveying bed) with another strand from catalyst regenerator 4, and contact mixing by catalyst transport 81 with the regenerated catalyst of the regenerator guiding valve 91 arranging on it, together enter the conveying bed part 22 of combined reactor 2, at agent-oil ratio 8～12, oil gas linear speed 8～12m/s, under the condition of reaction times 1.0～2.0s, react, for further control combination reactor 2 temperature outs are at 450～500 ℃, at the turbulent bed of combined reactor 2 or the middle and upper part of fast bed 21, inject chilling agent 19, this chilling agent comprises water, recycle stock, gasoline, diesel oil, sump oil etc. or its any mixture, injection rate is 1～10wt% of fcc raw material weight inferior.Reacted catalyzer and oil gas through oil and gas separating system 12, settling vessel 10 and top revolve 13 separated after oil gas draw catalytic-cracking reaction system, and catalyzer enters stripping stage 5 strippings, after through catalyzer ingress pipe 18, enter catalyst regenerator 4 and implement coke burning regenerations.
A variation as the present embodiment, catalyst cooler 6 can be arranged at catalyst regenerator 4 and turbulent bed or fast bed and add between conveying bed combined reactor 2, for entering one or two strands in two strands of regenerators of turbulent bed or fast bed 21, first implement cooling the regenerator temperature out of water cooler (control 600～670 ℃), in order to improving the agent-oil ratio of fcc raw material inferior in reaction.
Embodiment 3
Flow process shown in Figure 3, catalyst regenerator 4 sides at heavy oil catalytic cracking reaction device arrange conventional riser reactor 1 and regenerated catalyst water cooler 6, a part of high temperature catalyst in catalyst regenerator 4 enters regenerator water cooler 6 by catalyst transport 70, heat-eliminating medium passes into from entrance 61, and through exporting 62 outflows, the regenerated catalyst temperature that enters this water cooler 6 is coolingly reduced to 580～670 ℃ from 680～710 ℃, cooled catalyzer enters riser reactor 1 through regenerator sloped tube 71 and regenerated catalyst guiding valve 7, under the castering action of lift gas 16, upwards flow and high-quality fcc raw material oil 15 contact reactss, the processing condition of riser reactor 1 are: 100～300 ℃ of raw material preheating temperatures, entering the front regenerated catalyst temperature of riser reactor 1 is 580～670 ℃, 460～520 ℃ of temperature of reaction, agent-oil ratio 5～11, under the condition of reaction times 2.0～3.0s, complete reaction.Reacted catalyzer and oil gas through oil and gas separating system 11, settling vessel 10 and top revolve 13 separated after oil gas draw catalytic-cracking reaction system, and catalyzer enters stripping stage 5 strippings, after through catalyzer ingress pipe 18, enter catalyst regenerator 4 and carry out coke burning regeneration.
Simultaneously, turbulent bed or fast bed are set on catalyst regenerator 4 sides of heavy oil catalytic cracking reaction device and add conveying bed combined reactor 2 and regenerated catalyst water cooler 8, a part of high temperature catalyst in catalyst regenerator 4 enters this regenerator water cooler 8 by catalyst transport 90, heat-eliminating medium passes into from entrance 81, and through exporting 82 outflows, the high-temperature regenerated catalyst that enters this water cooler 8 is cooled and is cooled to 600～670 ℃ from 680～710 ℃, then, the regenerated catalyst guiding valve 9 that wherein one cooling regenerated catalyst agent arranges through regenerator sloped tube 91 (dipleg) with on it enters the bottom of turbulent bed in combined reactor 2 or fast bed part 21, and turbulent bed or the fast bed part 21 of together with the fcc raw material oil 14 inferior that is 150～300 ℃ with preheating temperature that upwards flows, first passing through combined reactor 2 under the castering action of pre-lift gas 17, at agent-oil ratio 6～10, reaction times 2.0～10.0s, under bed linear velocity 0.5～4.5m/s condition, contact, reaction, then make oil gas and catalyzer, at turbulent bed or fast bed 21 tops and another strand, from regenerated catalyst water cooler 8 and through the cooling regenerator of regenerator sloped tube 990 and regenerated catalyst guiding valve 99, mix (temperature of this regenerated catalyst is also 600～670 ℃), together enter conveying bed 22 bottoms of combined reactor 2, at agent-oil ratio 8～12, oil gas linear speed 8～12m/s, under the condition of reaction times 1.0～2.0s, react.Further in order to control whole combined reactor 2 temperature outs (span of control is 450～500 ℃), chilling agent 19 is injected in turbulent bed or fast bed 21 middle and upper parts at combined reactor 2, this chilling agent comprises water, recycle stock, gasoline, diesel oil, sump oil etc. or their arbitrary composition, and injection rate is 1～10wt% of fcc raw material weight inferior.Reacted catalyzer and oil gas through oil and gas separating system 12, settling vessel 10 and top revolve 13 separated after oil gas draw catalytic-cracking reaction system, and catalyzer enters stripping stage 5 strippings, after through catalyzer ingress pipe 18, enter catalyst regenerator 4 and carry out coke burning regeneration.
In the present embodiment, regenerated catalyst water cooler 6 and 8 can be one,, high-temperature regenerated catalyst for example, enters water cooler by regenerated catalyst (transfer lime 70 and/or 90), after cooling, a plurality of inclined tubes (or weighing leg) 71,91 and 990 that arrange through water cooler bottom are sent into respectively bottom and the top of bottom, turbulent bed or the fast bed 21 of riser reactor 1.
As another kind, change, through the cooled regenerated catalyst of regenerated catalyst water cooler 8, can only send into bottom or the top of turbulent bed or fast bed 21, that is, also can only to one regenerated catalyst of sending in fast bed 21, carry out cooling.
Embodiment 4
Flow process shown in Figure 4, catalyst regenerator 4 sides at heavy oil catalytic cracking reaction device arrange conventional riser reactor 1 and regenerated catalyst water cooler 6, a part of high-temperature regenerated catalyst in catalyst regenerator 4 enters regenerator water cooler 6 by catalyst transport 70, heat-eliminating medium passes into from entrance 61, and through exporting 62 outflows, the regenerated catalyst temperature that enters this water cooler 6 is coolingly reduced to 580～670 ℃ from 680～710 ℃, cooled catalyzer enters riser reactor 1 through regenerator sloped tube 71 and regenerated catalyst guiding valve 7, under the castering action of lift gas 16, upwards flow and high-quality fcc raw material oil 15 contact reactss, in riser reactor 1, catalytic cracking process condition is: 100～300 ℃ of raw material preheating temperatures, entering the front regenerated catalyst temperature of riser reactor 1 is 580～670 ℃, 460～520 ℃ of temperature of reaction, agent-oil ratio 5～11, under the condition of reaction times 2.0～3.0s, complete reaction.
Simultaneously, on catalyst regenerator 4 sides of heavy oil catalytic cracking reaction device, be provided with turbulent bed or fast bed and add conveying bed combined reactor 2 and regenerated catalyst water cooler 8, a part of high temperature catalyst in catalyst regenerator 4 enters regenerator water cooler 8 by catalyst transport 90, heat-eliminating medium passes into from entrance 81, and through exporting 82 outflows, the high-temperature regenerated catalyst that enters this water cooler 8 is cooled and is cooled to 600～670 ℃ from 680～710 ℃, then, one cooling regenerator enters the bottom of turbulent bed in combined reactor 2 or fast bed part 21 through regenerator sloped tube 91 and regenerated catalyst guiding valve 9, and turbulent bed or the fast bed part 21 of together with the fcc raw material oil 14 inferior that is 150～300 ℃ with preheating temperature that upwards flows, first passing through combined reactor 2 under the castering action of pre-lift gas 17, at agent-oil ratio 6～10, reaction times 2.0～10.0s, under bed linear velocity 2～6m/s condition, contact, reaction, then make oil gas and catalyzer in reaction, at turbulent bed or fast bed 21 tops and another strand, from regenerated catalyst water cooler 8 and through the cooling regenerator of regenerator sloped tube 990 and regenerated catalyst guiding valve 99, mix (temperature of this regenerated catalyst is also 600～670 ℃), together enter conveying bed 22 bottoms of combined reactor 2, at agent-oil ratio 8～12, oil gas linear speed 8～12m/s, under the condition of reaction times 1.0～2.0s, react, further in order to control the temperature of reaction (span of control is 450～500 ℃) of whole combined reactor 2 outlets, chilling agent 19 is injected in turbulent bed or fast bed 21 middle and upper parts at combined reactor 2, this chilling agent comprises water, recycle stock, gasoline, diesel oil, sump oil etc. or their any mixture, injection rate is 1～10wt% of fcc raw material weight inferior.
Referring to Fig. 4, in the present embodiment, the conventional riser reactor 1 transforming for high-quality fcc raw material adds and carries bed combined reactor 2 to be connected with the exit of catalyzer at reaction oil gas with the turbulent bed for inferior raw material conversion processing or fast bed, through this connectivity part 12, from two reactor catalysts and oil gas, converge and pass through oil and gas separating system 11 and enter settling vessel 10, through separation system 11 and top revolve 13 separated after oil gas draw catalytic-cracking reaction system, and catalyzer enters stripping stage 5 strippings, after through catalyst transport, import 18 and enter catalyst regenerator 4 and carry out coke burning regeneration.
Set-up mode about regenerated catalyst water cooler is identical with the description of embodiment 3, that is, provide two required regenerated catalysts of reactor also can be cooled by same regenerator water cooler; And two strands of catalyzer sending into turbulent bed or fast bed 21 can all be cooled through supercooler, also can be only to one catalyzer wherein, carry out cooling.
In a word, gordian technique of the present invention is the difference existing for Rfcc Feedstock response characteristic, and it is divided into high-quality cut and cut inferior by boiling range, then enters respectively in catalytic cracking unit reactor assembly and transforms in differential responses district.The advantage of the inventive method is, it on catalytic cracking reaction device, is the reactor that high-quality cut and cut inferior arrange two different structures, for two portions raw material provides independently reaction zone, in reaction zone separately, adopt the reaction conditions of each self-optimizing, especially by setting up catalyst cooler, carry out the depressant oil contact temperature difference, realize high agent-oil ratio; Serious for the catalyzer coking of inferior raw material reaction zone, inactivation is fast, the active low feature in rear portion, adopts the operating method of combined reactor and catalyzer series connection, has improved the average activity of rear portion catalyzer, has significantly improved lightweight oil and liquid yield.
Example
For verifying the effect of catalytic cracking process provided by the invention, adopt the technical process shown in Fig. 3, on 1,000,000 tons/year of heavy oil catalytic cracking reaction devices of certain refinery, carry out commerical test, process of the test is shown 1-table 3 with the results are shown in.
Can see, adopt the catalytic cracking process of this invention, original heavy-oil catalytic raw material be carried out to fractionation cutting and obtained respectively high-quality fcc raw material (light oil raw material) and fcc raw material inferior (heavy oil feedstock), 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, and the optimization reaction conditions adopting is separately as shown in table 2.With conventional heavy oil fluid catalytic cracking compare (not cutting cut), employing the invention provides catalytic cracking technology can make yield of light oil improve 1.8 percentage points (gasoline+diesel oil), liquid yield improves 2.2 percentage points (liquefied gas+gasoline+diesel oil), and 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 | 1.63 |
| 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 technological condition
Note:
*total reaction time is the reaction times sum (wherein carry reaction times in bed be 1.5 second) of stock oil in turbulent bed or fast bed and conveying bed;
*total agent-oil ratio is the agent-oil ratio (wherein the agent-oil ratio in turbulent bed or fast bed is 8) in carrying bed.
Table 3 main products distributes
| Product distributes and character | Prior art scheme | The present invention program |
| H 2S | 0.5 | 0.8 |
| Fuel gas | 4.1 | 3.1 |
| Liquefied gas | 15.3 | 15.7 |
| Gasoline | 44.7 | 46.0 |
| Diesel oil | 25.3 | 25.8 |
| Clarified oil | 1.8 | 1.1 |
| Coke | 8.3 | 7.5 |
| 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 (9)
1. a heavy oil fluid catalytic cracking method of utilizing two-region coupling and catalyzer series connection, 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, riser reactor is set as the reaction zone of high-quality fcc raw material, high-quality fcc raw material is contacted in this riser reactor with the regenerated catalyst from revivifier, and there is catalytic cracking reaction, after reacted oil gas and catalyst separating, draw reactive system, the catalyzer after separation recycles through revivifier coke burning regeneration; Wherein, the reaction conditions of high-quality fcc raw material is: 460～520 ℃ of temperature of reaction, agent-oil ratio 5～11,2.0～3.0 seconds reaction times, and 100～300 ℃ of raw material preheating temperatures;
Turbulent bed or fast bed are separately set on revivifier side and add conveying bed combined reactor as the reaction zone of fcc raw material inferior, described turbulent bed or fast bed are arranged on the bottom of this whole combined reactor by hole enlargement, from the regenerated catalyst of revivifier, be divided into two stocks and from the turbulent bed of described combined reactor or fast bed bottom and top, do not introduce this combined reactor, fcc raw material inferior is made progress in mobile under lift gas effect first to be contacted with the regenerated catalyst of fast bed bottom introducing, and common rising of this raw material and regenerated catalyst contacted at turbulent bed or fast bed top with another strand of regenerated catalyst, complete catalytic cracking reaction, after reacted oil gas and catalyst separating, draw reactive system, catalyzer after separation recycles through revivifier coke burning regeneration, wherein, the reaction conditions of fcc raw material inferior is: 150～300 ℃ of raw material preheating temperatures, 450～550 ℃ of combined reactor temperature outs, in turbulent bed or fast bed, 2.0～10.0 seconds reaction times, bed linear speed 0.5～4.5m/ second, agent-oil ratio 6～10, in carrying bed, 1.0～2.0 seconds reaction times, agent-oil ratio 8～12, oil gas linear speed 8～12m/ second, and in the reaction of carrying bed, agent-oil ratio is greater than at fast bed and reacts.
2. the heavy oil fluid catalytic cracking method of utilizing two-region coupling and catalyzer series connection according to claim 1, wherein, arranges at least one regenerated catalyst water cooler, to the temperature of the regenerated catalyst from revivifier by the following method at least one processing:
Regenerated catalyst is first cooled to 580-670 ℃ and enters riser reactor again;
Making to introduce turbulent bed or fast bed adds in two strands of regenerated catalysts carrying bed combined reactor at least one and is first cooled to 600-670 ℃ and enters described combined reactor again.
3. the heavy oil fluid catalytic cracking method of utilizing two-region coupling and catalyzer series connection according to claim 1, wherein, for turbulent bed or fast bed, add a conveying bed combined reactor, the height of described turbulent bed or fast bed is 5～30% of this combined reactor total height.
4. according to the heavy oil fluid catalytic cracking method of utilizing two-region coupling and catalyzer series connection described in claim 1-3 any one, wherein, reaction zone for fcc raw material inferior, described turbulent bed or fast bed add carry bed combined reactor in middle part or the top of turbulent bed or fast bed inject chilling agent, to control the temperature of reaction in this reaction zone, described chilling agent comprises water, recycle stock, gasoline, diesel oil, sump oil or its any mixture, and injection rate is 1～10wt% of fcc raw material amount inferior.
5. according to the heavy oil fluid catalytic cracking method of utilizing two-region coupling and catalyzer series connection described in claim 1-3 any one, wherein, from the material of high-quality fcc raw material reaction zone and material from fcc raw material inferior reaction zone, utilize respectively the separated of oil-gas separation mechanism realization response oil gas and catalyzer; Or make the described material from two reaction zones after converging, utilize the separated of an oil-gas separation mechanism realization response oil gas and catalyzer.
6. one kind for implementing the claims the device that utilizes the heavy oil fluid catalytic cracking method of two-region coupling and catalyzer series connection described in 1-5 any one, this device at least comprises catalyst regenerator, settling vessel, riser reactor and turbulent bed or fast bed add carries bed combined reactor, described turbulent bed or fast bed are arranged on the bottom of combined reactor by hole enlargement, described catalyst regenerator at least arranges three catalyst transports, respectively with riser reactor bottom, turbulent bed or fast bed add turbulent bed or fast bed bottom and the top connection in transport bed reactor, and in each catalyst transport, be all provided for controlling the guiding valve of regenerated catalyst flow, riser reactor and turbulent bed or fast bed add carries the exit end of bed combined reactor to be all communicated with the oil-gas separator in settling vessel.
7. device according to claim 6, wherein, this device also comprises at least one regenerated catalyst water cooler, its set-up mode at least comprises one of the following:
This regenerated catalyst water cooler is serially connected with in the catalyst transport between catalyst regenerator and riser reactor, and between guiding valve and catalyst regenerator;
This regenerated catalyst water cooler is serially connected with catalyst regenerator and turbulent bed or fast bed and adds described at least one of carrying between bed combined reactor in catalyst transport, and between guiding valve and catalyst regenerator.
8. device according to claim 6, wherein, this device also arranges a regenerated catalyst water cooler, it is communicated with by least one catalyst transport with catalyst regenerator, and by described catalyst transport, be communicated with riser reactor bottom simultaneously, and add and carry fast bed bottom and/or the top of bed combined reactor to be communicated with turbulent bed or fast bed.
9. according to the device described in claim 6-8 any one, wherein, riser reactor and turbulent bed or fast bed add carries the exit end of bed combined reactor to be communicated with an oil-gas separator respectively, or riser reactor and turbulent bed or fast bed add after carrying the exit end of bed combined reactor to be connected and are communicated in same oil-gas separator.
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