CN1928023A - Lift leg catalytic cracking method and apparatus - Google Patents
Lift leg catalytic cracking method and apparatus Download PDFInfo
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- CN1928023A CN1928023A CN 200610106993 CN200610106993A CN1928023A CN 1928023 A CN1928023 A CN 1928023A CN 200610106993 CN200610106993 CN 200610106993 CN 200610106993 A CN200610106993 A CN 200610106993A CN 1928023 A CN1928023 A CN 1928023A
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Abstract
The present invention discloses riser catalytic cracking method and apparatus for petroleum refining process. Two-stage riser reactor is adopted, in which the regenerated catalyst from the second regenerator and with relatively high temperature and material oil are made to enter to its bottom for catalytic cracking reaction in the first reaction zone, while the semi-regenerated catalyst from the first regenerator and introduced via the middle catalyst inlet is first mixed with the catalyst and oil gas from the first reaction zone and then admitted to the first reaction zone for further catalytic cracking reaction. The present invention is used mainly for the catalytic cracking of heavy petroleum fractions, and can reach the aims of lowering the dry gas yield of catalytic cracker, increasing the catalytic gasoline yield, reducing the olefin content and sulfur content in the catalytic gasoline and improving the cracked product distribution and cracked gasoline quality of catalytic cracker.
Description
Technical field
The invention belongs to the cracking hydrocarbon oil field, particularly a kind of riser catalytic cracking method and apparatus.
Background technology
Catalytic cracking is the important secondary processing technology of oil heavy ends processing, occupies considerable status in petroleum refining industry.Catalytically cracked gasoline is the important source of commodity motor spirit.In riser fluid catalytic cracking, pyrolytic cracking and condensation reaction take place in oil heavy ends (comprising decompressed wax oil, wax tailings, long residuum, vacuum residuum, solvent deasphalting wet goods) under the effect of catalytic cracking catalyst, generate dry gas, liquefied gas, gasoline, diesel oil, heavy oil (comprising recycle stock and slurry oil) and coke.In order to reach certain stock oil transformation efficiency, require stock oil in riser reactor, to need certain reaction temperature, the oil gas residence time.Conventional catalytic cracking unit, riser tube temperature out be mostly more than 500 ℃, general 2～3 seconds of the oil gas residence time.Because there is landing in catalyzer in riser tube, the residence time of catalyzer in riser tube is long more than the oil gas residence time, generally at 4～10 seconds.Catalyzer constantly has coke to generate and is deposited on catalyst surface and the active centre in the process that rises along riser tube, and catalyst activity is descended gradually.Half place's activity at the riser tube height has been lost over halfly, and the activity in the riser tube exit only reaches about 1/3rd of initial activity.Therefore, in the second half section of riser reactor katalysis variation, because temperature is still higher, with respect to catalyzed reaction, to product selectivity and the corresponding raising of the disadvantageous heat cracking reaction of product property.The long and is the dry gas yied height, and yield of light oil is low, and catalytic gasoline olefin(e) centent height (reaches 45～60v%), can not satisfy the requirement of new gasoline standard to its olefin(e) centent.
Certain depth of conversion that how should keep mink cell focus does not increase dry gas yied and the olefin(e) centent that reduces catalytic gasoline again, and key is to improve the overall activity of the catalyzer of whole riser tube by every means, reduces the riser tube temperature out.The reduction of the raising of riser tube catalyst activity and riser tube temperature out means that the catalyzed reaction ratio increases, and product selectivity and the disadvantageous heat cracking reaction of product property is suppressed.
How to improve the disadvantage in traditional riser reactor second half section reaction process, one of its main points are how to improve the catalyst activity of second half section.Chinese patent CN1302843A has proposed a kind of " catalytic cracking process with two-segment lift pipe ", realizes the purpose of oil gas series connection, catalyzer relay, segmentation reaction, shortening reaction times and raising catalyzer average behaviour by the riser reactor of two-part.This technology is divided into two sections with riser tube, and first reacting section catalyst is directly from revivifier.First conversion zone finishes, and catalyzer separates by the separator that is arranged on the first conversion zone end with reaction oil gas, and isolated catalyzer turns back to revivifier regeneration, and oil gas continues to enter the reaction of second conversion zone.The catalyzer of second conversion zone is the regenerated catalyst through the external warmer heat-obtaining from revivifier.The core of this technology be second half section (i.e. second conversion zone) of reaction with active high and through the lower regenerated catalyst displacement riser tube of the temperature of external warmer heat-obtaining preceding half section (i.e. first conversion zone) owing to coking and the catalyzer of part inactivation.This whole metathetical mode, owing to can improve the catalyst activity of second conversion zone morely, its final effect is tangible.But also there is certain problem in this technology.In riser tube, though the first reacting section catalyst inactivation, inwhole inactivations also have part active (50% initial activity is arranged) still can use nearly on it.In conventional riser tube, this part activity has been finished the catalytic cracking conversion of considerable part raw material just.But adopt separation means with itself and gas-oil separation in this technology, obviously this part active resource fails to be fully used.In addition, the catalyzer of separating must be through stripping before entering revivifier, and used here stripped vapor will all enter riser tube second conversion zone, thereby can influence the reaction of second conversion zone.Therefore, the stripped vapor amount can be restricted, and certainly will have influence on Srteam Stripping effect, must some oil gas be entered revivifier by catalyst entrainment and burns as coke, causes coking yield to increase and liquid yield reduces.Another shortcoming of this technology is that the mode of this whole replacing section decaying catalysts must increase separating device in the middle of riser tube, also will consider stripping simultaneously, obviously makes technical process complicated, has increased operation easier.
The present invention improves existing catalytic cracking riser technology, introduce half regenerated catalyst of a part at the riser tube middle part from first revivifier, improve the catalyst activity of riser tube second half section, by this method, can reduce the olefin(e) centent and the sulphur content of the dry gas yied of catalytic cracking unit, the productive rate that increases catalytic gasoline, reduction catalytic gasoline.
Summary of the invention
The object of the present invention is to provide a kind of riser catalytic cracking method and apparatus, poor to solve existing riser fluid catalytic cracking riser reactor second half section katalysis, high and the high and high problem of pressure gasoline olefin(e) centent of dry gas yied that cause of thermally splitting degree.
The invention provides a kind of riser catalytic cracking method, stock oil and catalytic cracking catalyst enter riser reactor by the stock oil inlet and the riser tube bottom catalyst inlet of riser reactor bottom respectively, be in contact with one another and along the up catalytic cracking reaction that carries out of riser reactor, reaction oil gas and reclaimable catalyst are flowed out by the riser reactor top exit and enter settling vessel, reclaimable catalyst enters behind stripping in first revivifier and second revivifier regenerates, recycle, it is characterized in that: be provided with the middle part catalyst inlet at the middle part of riser reactor, introducing is 400～600 ℃ from the temperature through behind the first revivifier external warmer heat-obtaining of first revivifier, be preferably 450～550 ℃ half regenerated catalyst, the regeneration temperature of first revivifier is 500～700 ℃, be preferably 550～650 ℃, the catalyzer that enters riser reactor bottom catalyst inlet is 600～720 ℃ for the temperature from second revivifier, be preferably 620～710 ℃ holomorphosis catalyzer, the regeneration temperature of second revivifier is 600～720 ℃, be preferably 620～710 ℃, regenerated catalyst contacts the back along the up catalytic cracking reaction that carries out of first conversion zone of the riser reactor under the catalyst inlet of described middle part with stock oil, the temperature of reaction of first conversion zone is 450～580 ℃, be preferably 480～560 ℃, the oil gas residence time is 0.5～2 second, be preferably 0.6～1 second, agent-oil ratio is 4～8, be preferably 5～8, half regenerated catalyst of being introduced by described middle part catalyst inlet mixes with oil gas with the up catalyzer from first conversion zone, enter second conversion zone of the riser reactor on the catalyst inlet of middle part, continue the up catalytic cracking reaction that carries out, the temperature of reaction of second conversion zone is 430～540 ℃, be preferably 450～530 ℃, oil gas is 1～5 second when stopping, be preferably 1.5～3 seconds, total agent-oil ratio is 8～18, be preferably 8～15, the temperature of reaction of second conversion zone is hanged down 5～50 ℃ than the temperature of reaction of first conversion zone, is preferably 10～30 ℃.
Riser fluid catalytic cracking provided by the invention, comprise riser reactor, first revivifier and second revivifier, the riser reactor bottom is provided with the stock oil inlet, the bottom catalyst inlet, the top is provided with outlet, be positioned at settling vessel, it is characterized in that: the middle part of riser reactor 2 also is provided with middle part catalyst inlet 204, first revivifier 3 is provided with the first revivifier external warmer 5, be provided with two sections catalyst transports 8 between the first revivifier external warmer 5 and the middle part catalyst inlet 204, second revivifier 4 is provided with the second revivifier external warmer 6, be provided with one section catalyst transport 9 between the described riser reactor bottom catalyst inlet 203 and second revivifier 4, riser reactor under the catalyst inlet 204 of middle part constitutes first conversion zone 201, and the riser reactor on the middle part catalyst inlet 204 constitutes second conversion zone 202.
Middle part of the present invention catalyst inlet to the distance of riser reactor bottom catalyst inlet is 20～80% of a riser reactor total length, preferred 30～70%.。
Riser reactor of the present invention is divided into two conversion zones, adopts two revivifier regenerated technologies.The catalyzer of riser tube first conversion zone is the holomorphosis high temperature catalyst from second revivifier, introduce again at riser tube middle part from the partial regeneration of first revivifier through the half lower regenerated catalyst of temperature behind the first revivifier external warmer heat-obtaining, the catalyzer of riser tube second conversion zone is above-mentioned two-part catalyzer.Because the riser tube latter half has replenished the active higher catalyzer through partial regeneration, the integer catalyzer activity of riser tube is improved, compare with the riser tube of conventional catalytic cracking, agent-oil ratio is greatly improved, catalyst activity height, agent-oil ratio are big, katalysis is increased, and disadvantageous heat cracking reaction is inhibited.The overall activity of catalyzer is improved in the riser reactor of the present invention, overcome in the conventional riser reactor, top (the being the second half section) shortcoming that catalyst activity is low, consequently compare with conventional riser catalytic cracking technology, under the situation that the transformation efficiency of stock oil is improved largely, dry gas yied reduces, the catalytic gasoline gain in yield, the catalytic gasoline olefin(e) centent reduces a lot, and the catalytic gasoline sulphur content also decreases.The present invention is in order to control the heat cracking reaction of riser tube second conversion zone, and the catalyzer that requires to augment must be active higher, but temperature is unsuitable too high, adopts two revivifier regenerated methods to realize this processing requirement.Catalyzer is carried out incomplete regen-eration in first revivifier, by control main air amount with burn temperature and be controlled at the first revivifier catalyzer and burn most carbon and all hydrogen, enter interior continuation of second revivifier through first revivifier regenerated catalyzer (being called half a regenerator) part and regenerate, enter the participation reaction of riser tube middle part after the heat collector heat-obtaining cooling of another part through first revivifier.Half regenerator that enters second revivifier continues regeneration in second revivifier, burn remaining charcoal.Second revivifier is provided with an external warmer, and the temperature of controlling the regeneration temperature of second revivifier and entering the regenerated catalyst of riser tube bottom makes it meet processing requirement.Regenerator enters the riser tube bottom and participates in reaction.Owing to introduced half high regenerator of a part of activity at the riser tube middle part, improved the overall activity of riser tube, strengthened degree to the favourable catalyzed reaction of product selectivity and gasoline property, and reduced the level of response of disadvantageous thermally splitting, the long and is that the heavy oil conversion rate improves, dry gas yied reduces, and the olefin(e) centent of catalytic gasoline reduces.
Compare with existing two-part riser catalytic cracking technology (CN1302843A), the present invention need not carry out catalyst separating in the centre of riser reactor, has simplified technical process widely and has reduced equipment.The present invention need only adopt the riser tube of a routine, is divided into two conversion zones, and structure is comparatively simple.Because directly entering second conversion zone, the catalyzer of first conversion zone continues to participate in reaction, add and introduce half active higher regenerated catalyst, make agent-oil ratio total in second conversion zone be higher than the agent-oil ratio of described riser reactor second conversion zone of CN1302843A from first revivifier from the middle part of riser reactor.Because agent-oil ratio is big, catalyzed reaction is strengthened, and disadvantageous heat cracking reaction is inhibited; The long and is that the cracked product selectivity is good, and dry gas yied is low, and the pressure gasoline olefin(e) centent is low.
In a word, adopt technical scheme of the present invention, the purpose that can realize reducing catalytic cracking unit dry gas yied, increase cracking level, reduction pressure gasoline alkene simplely and reduce the pressure gasoline sulphur content.Compare with conventional riser catalytic cracking technology, 0.05～0.50 weight percent point of dry gas yied decline of the present invention, cracking level improves 1.5～4.5 weight percent points, pressure gasoline alkene reduces by 10～25 volume percentage points, the pressure gasoline sulphur content reduces by 5～25% relatively, and the pressure gasoline research octane number (RON) remains unchanged or slightly increases.
The present invention is further detailed explanation below in conjunction with accompanying drawing, embodiment and embodiment.Accompanying drawing, embodiment and embodiment do not limit the scope of protection of present invention.
Description of drawings
Fig. 1 is the structure and layout synoptic diagram of riser reactor-revivifier of the present invention.
Reference numeral among Fig. 1 is represented:
The 1-settling vessel; The 2-riser reactor;
201-riser reactor first conversion zone; 202-riser reactor second conversion zone;
203-riser tube bottom catalyst inlet; 204-riser tube middle part catalyst inlet;
3-first revivifier; 4-second revivifier;
The 5-first revivifier external warmer; The 6-second revivifier external warmer;
7-stock oil inlet; 701-stock oil
Two sections catalyst transports of 8-; One section catalyst transport of 9-;
10-inclined tube to be generated; 11-half regenerated catalyst;
One section pre-gas (medium is dry gas or water vapor) that promotes of 12-; 13-cracking reaction oil gas;
Two sections pre-gas (medium is dry gas or water vapor) that promote of 14-; The 15-main air of regenerating;
The 16-regenerated flue gas; 17-is effusive by the first revivifier external warmer
Heat-obtaining medium (medium is a high-temperature vapor);
It is effusive by the second revivifier external warmer that 18-flows into the heat-obtaining 19-of the first revivifier external warmer
Medium (medium is water or water at low temperature steam); Heat-obtaining medium (medium is a high-temperature vapor);
20-flows into the heat-obtaining 21-second revivifier external warmer recirculated air of the second revivifier external warmer.
Medium (medium is water or water at low temperature steam);
Embodiment
Structure and layout synoptic diagram referring to riser reactor-revivifier of the present invention shown in Figure 1.Riser fluid catalytic cracking of the present invention comprises riser reactor 2, settling vessel 1, first revivifier 3 and second revivifier 4, the first revivifier external warmer 5 and the second revivifier external warmer 6 (also have fractionating system in addition, accompanying drawing and explanation are omitted).
The bottom of riser reactor 2 is provided with stock oil inlet 7, bottom catalyst inlet 203, and the top is provided with outlet, is positioned at settling vessel 1.The middle part of riser reactor 2 is provided with middle part catalyst inlet 204, and middle part catalyst inlet 204 to the distance of riser reactor bottom catalyst inlet 203 is 20～80% of riser reactor 2 total lengths, is preferably 30～70%.Specification sheets regulation of the present invention, the height of bottom catalyst inlet 203 is zero, riser reactor top exit height is decided to be 100% of riser reactor total length.Link to each other by two sections catalyst transports 8 between middle part catalyst inlet 204 and the first revivifier external warmer 5, link to each other by one section catalyst transport 9 between riser reactor bottom catalyst inlet 203 and second revivifier 4, be equipped with the regeneration guiding valve on one section catalyst transport 9 and two sections catalyst transports 8, to control the flow of corresponding catalyzer; Be equipped with pre-lifting gas inlet on the two-stage catalytic agent transfer lime.Be provided with half regenerated catalyst 11 between two revivifiers.
Referring to Fig. 1, first revivifier 3 and second revivifier 4 adopt the layout of eclipsed form.Inclined tube 10 to be generated is stretched into by settling vessel 1 and is provided with half regenerated catalyst, 11, the first revivifiers 3 between first revivifier, 3, the first revivifiers 3 and second revivifier 4 and is provided with the first revivifier external warmer, 5, the second revivifiers 4 and is provided with the second revivifier external warmer 6.Also be respectively equipped with parts such as cyclonic separator, main air sparger in first revivifier 3 and second revivifier 4 in addition.Because the structure of first revivifier 3 and second revivifier 4 and layout and prior art are basic identical, so only carry out above-mentioned brief description.
It is as follows to adopt riser reactor-regenerator system shown in Figure 1 to carry out the method for riser catalytic cracking of the present invention: the stock oil 701 after the preheating enters the bottom of riser reactor 2 by stock oil inlet 7 after nozzle atomization, contact up reaction with the holomorphosis catalyzer that comes from second revivifier 4.The reaction conditions of first conversion zone 201 is: 450～580 ℃ of temperature of reaction, preferred 480～560 ℃; 0.5～2 second oil gas residence time, preferred 0.6～1 second; Agent-oil ratio is 4～8, preferred 5～8.(illustrate: the temperature of reaction of first conversion zone 201 is meant the terminal temperature of first conversion zone, that is the front end temperature of the catalyst inlet of the middle part catalyst inlet 204 or second conversion zone 202; The agent-oil ratio of first conversion zone 201 is meant the ratio that is entered catalyst weight with the stock oil weight of first conversion zone 201 by bottom catalyst inlet 203).The middle part of riser reactor 2 catalyst inlet 204 through two sections catalyst transports 8 introduce from first revivifier 3 through half regenerated catalyst behind the first revivifier external warmer, 5 heat-obtainings, mix with oil gas with up catalyzer from first conversion zone 201, enter second conversion zone 202 of riser reactor 2, up reaction.The reaction conditions of second conversion zone 202 is: temperature of reaction is 430～540 ℃, preferred 450～530 ℃; Oil gas is 1～5 second when stopping, preferred 1.5～3 seconds; Total agent-oil ratio is 8～18, preferred 8～15.(illustrate: the temperature of reaction of second conversion zone 202 is meant the top exit temperature of the top exit that is second conversion zone 202 of riser reactor 2; Total agent-oil ratio of second conversion zone 202 is meant by bottom catalyst inlet 203 and enters the catalyzer of first conversion zone 201 and entered the ratio of gross weight and the weight of stock oil of the catalyzer of second conversion zone 202 by middle part catalyst inlet 204).The temperature of reaction of second conversion zone 202 is hanged down 5～50 ℃, preferred 10～30 ℃ than the temperature of reaction of first conversion zone 201.Reacted oil gas and reclaimable catalyst are flowed out by the outlet at riser reactor 2 tops and enter settling vessel 1 and separate.The isolated reaction oil gas 13 of settling vessel enters separation column and carries out fractionation (figure slightly).
Referring to Fig. 1, isolated reclaimable catalyst stripping carries out coke burning regeneration after inclined tube to be generated 10 enters in first revivifier 3 in settling vessel 1.The regeneration temperature of first revivifier 3 is 500～700 ℃, preferred 550～650 ℃; Catalyzer carbon content after the regeneration is 0.15～0.3w% (representing weight percentage with w% in the specification sheets of the present invention).Participate in reaction by second conversion zone 202 that two sections catalyst transports 8 are delivered to riser reactor through first revivifier, 3 regenerated catalyzer parts behind the first revivifier external warmer, 5 heat-obtainings, another part enters into second revivifier 4 through half regenerated catalyst 11 and further regenerates.The regeneration temperature of second revivifier 4 is 600～720 ℃, preferred 620～710 ℃; Regenerated catalyst carbon content after the regeneration is lower than 0.05w%.Enter the bottom of riser reactor 2 through second revivifier, 4 regenerated catalyzer through two sections catalyst transports 9 and bottom catalyst inlet 203, enter first conversion zone 201 and participate in reaction.The size of the heat-obtaining amount by controlling the first revivifier external warmer 5 guarantees to enter the temperature of half regenerator of riser tube second conversion zone 202.Guarantee to enter the holomorphosis catalyst temperature of riser tube first conversion zone 201 by the heat-obtaining amount of controlling the second revivifier external warmer 6.
In above-mentioned two-stage regeneration process, regeneration main air 15 at first enters from the bottom of second revivifier 4.Because the carbon content of need on half regenerated catalyst that second revivifier 4 is burnt seldom, so the catalyst regeneration process in second revivifier 4 obviously are the regenerative processes of an oxygen enrichment.Because second revivifier 4 is carried out oxygen enrichment regeneration, there is a large amount of excess oxygen to exist, so regeneration effect is fine, regenerated catalyst carbon content after the regeneration is less than 0.05w%, the outer setting second revivifier external warmer 6 at second revivifier 4 carries out heat-obtaining, the catalyst temperature that enters the riser tube bottom with assurance is unlikely too high, and the first conversion zone agent-oil ratio is higher, is beneficial to the vaporization of heavy raw oil and the cracking of last running.First revivifier 3 is connected with second revivifier, 4 flue gases, and the flue gas that second revivifier 4 burns generation enters first revivifier 3 as main air; Because flue-gas temperature is higher, and is very favourable to the regeneration effect of first revivifier 3.All the other step conditions of above-mentioned regenerative operation (for example operation of the first revivifier external warmer 5, the second revivifier external warmer 6), because of basic identical with prior art, explanation is omitted.
Among Fig. 1, the meaning of NM Reference numeral can be referring to the explanation of " description of drawings " part in the above description for all.
Riser catalytic cracking method of the present invention is not particularly limited the catalyzer trade mark and the kind that adopts.Can be HY type, REY type, REHY type, also can be USY type or REUSY type; Can be conventional catalytic cracking catalyst, also can be the catalyzer of voluminous gasoline and liquefied gas, the catalyzer of high-yield diesel oil, or the like.The stock oil kind that the present invention processed can be decompressed wax oil, long residuum, vacuum residuum, also can be wax tailings, solvent-deasphalted oils, hydrocracking tail oil etc.
Embodiment
The embodiment test is carried out on the medium-sized riser tube testing apparatus of two-part.The stock oil that test is adopted is that the decompressed wax oil (VGO) that oil transportation is rather managed in the Shandong is mixed vacuum residuum (being called for short the defeated mixed oil of the peaceful pipe in Shandong), grand celebration long residuum and the Central Plains long residuum of refining 10% (weight), and catalyzer is the industrial poiser of the LRC-99 cracking catalyst of the industrial poiser of the Sinopec Chang Ling branch office catalyst plant CC-20D cracking catalyst of producing and CNPC's Catalyst Factory of Lanzhou Petrochemical Company production.In order to contrast, also carried out the test of conventional riser tube simultaneously.Height (being total length), the diameter of conventional riser reactor are identical with the medium-sized riser tube testing apparatus of two-part of the present invention, and unit capacity is also identical; Different is that catalyzer all is the regenerated catalyst from second revivifier, enters from the bottom of riser tube.The character of stock oil and catalyzer sees Table 1 and table 2.
Embodiment 1
The catalyst inlet of present embodiment second conversion zone (being the middle part catalyst inlet of riser reactor) to the distance of riser reactor bottom catalyst inlet is 50% of a riser reactor total length.Table 3 has provided the main operational condition of embodiment 1 and Comparative Examples 1 and product distributes and the concrete data of quality of gasoline.
The catalyzer that present embodiment adopts is CC-20D, stock oil is the defeated mixed oil of the peaceful pipe in Shandong, operational condition is: the regeneration temperature of first revivifier is 600 ℃, half regenerated catalyst carbon content after the regeneration is 0.25w%, a part half regenerator temperature behind the first revivifier external warmer, 5 heat-obtainings is reduced to 520 ℃, enters riser tube by riser tube middle part catalyst inlet 204 and participates in reaction.Another part regenerator enters second revivifier by half regenerated catalyst 11 and continues regeneration.The regeneration temperature of second revivifier is 680 ℃, through the catalyzer carbon content of the second revivifier holomorphosis less than 0.05w%, two again holomorphosis catalyzer enter the riser tube bottom by riser tube bottom catalyst inlet 203 and participate in reaction, and the holomorphosis catalyst temperature that enters the riser tube bottom is 680 ℃.The reaction conditions of riser reactor first conversion zone is: 540 ℃ of riser tube bottom finish mixing temperatures, the first conversion zone latter end temperature of reaction (referring to be close to the temperature of catalyst inlet 204 lower ends, riser tube stage casing) is 520 ℃, the oil gas residence time is 1.86 seconds, and agent-oil ratio is 6.5.The reaction conditions of riser reactor second conversion zone is: the riser tube temperature out is 510 ℃, the oil gas residence time is 1.53 seconds, and total agent-oil ratio (adding the catalyzer summation that inlet 203 catalyzer that enter and middle part catalyst inlet 204 enter by riser tube bottom catalyzer) is 9.2.Operating method is passed through for the stock oil one way.
Comparative Examples 1: stock oil is identical with embodiment 1 with catalyzer, the device operational condition is: the regeneration temperature of first revivifier is 680 ℃, the regeneration temperature of second revivifier is 680 ℃, and the temperature that regenerated catalyst enters riser reactor is 680 ℃, and the regenerated catalyst carbon content is 0.05w%.Regenerated catalyst enters riser reactor by the bottom, 540 ℃ of riser tube bottom finish mixing temperatures, agent-oil ratio in the riser reactor is 6.43, and riser reactor top exit temperature is 510 ℃, and the residence time of oil gas in riser reactor is 3.21 seconds.Operating method is passed through for the stock oil one way.
By table 3 data as can be seen, technology provided by the invention is after the riser tube middle part replenishes the partial regeneration catalyzer, the transformation efficiency of stock oil is greatly improved, show the increase of the reduction of heavy oil productive rate, gasoline and reacted gas productive rate, heavy oil is reduced to 6.10% from 10.48%, gasoline yield is increased to 48.18% from 44.68%, reacted gas is increased to 21.86% from 20.58%, and the increase of reacted gas mainly shows in the increase of liquefied gas, and the productive rate of dry gas does not only increase, also, be reduced to 1.63% from 1.99% than not reducing before the tonic.The pressure gasoline sulphur content drops to 1041 μ g/g by 1191 μ g/g, and alkene is reduced to 29.3v% by 44.2v%, has reduced by 14.9 volume percentage points; Research octane number (RON) is constant substantially.
The catalyst inlet of present embodiment second conversion zone (being the middle part catalyst inlet of riser reactor) to the distance of riser reactor bottom catalyst inlet is 50% of a riser reactor total length.Table 4 has provided the main operational condition of embodiment 2 and Comparative Examples 2 and product distributes and the concrete data of quality of gasoline.
The catalyzer that present embodiment adopts is a LRC-99 industry equilibrium catalyst, stock oil is the grand celebration long residuum, operational condition is: the regeneration temperature of first revivifier is 620 ℃, half regenerated catalyst carbon content after the regeneration is 0.28w%, a part half regenerator temperature behind the first revivifier external warmer, 5 heat-obtainings is reduced to 520 ℃, enters riser tube by riser tube middle part catalyst inlet 204 and participates in reaction.Another part regenerator enters second revivifier by half regenerated catalyst 11 and continues regeneration.The regeneration temperature of second revivifier is 720 ℃, through the carbon content of the regenerated catalyst of the second revivifier holomorphosis less than 0.05w%, two again holomorphosis catalyzer enter the riser tube bottom by riser tube bottom catalyst inlet 203 and participate in reaction, and the holomorphosis catalyst temperature that enters the riser tube bottom is 700 ℃.The reaction conditions of riser reactor first conversion zone is: 520 ℃ of riser tube bottom finish mixing temperatures, the first conversion zone latter end temperature of reaction (referring to be close to the temperature of catalyst inlet 204 lower ends, riser tube stage casing) is 500 ℃, the oil gas residence time is 2.17 seconds, and agent-oil ratio is 6.1.The reaction conditions of riser reactor second conversion zone is: the riser tube temperature out is 490 ℃, the oil gas residence time is 1.61 seconds, and total agent-oil ratio (the catalyzer summation that catalyzer that catalyst inlet 203 enters bottom riser tube and middle part catalyst inlet 204 enter) is 8.8.Operating method is passed through for the stock oil one way.
Comparative Examples 2: stock oil is identical with embodiment 1 with catalyzer, the device operational condition is: the regeneration temperature of first revivifier is 650 ℃, the regeneration temperature of second revivifier is 700 ℃, and the temperature that regenerated catalyst enters riser reactor is 700 ℃, and the regenerated catalyst carbon content is 0.05w%.Regenerated catalyst enters riser reactor by the bottom, 520 ℃ of riser tube bottom finish mixing temperatures, agent-oil ratio in the riser reactor is 6.25, and riser reactor top exit temperature is 490 ℃, and the residence time of oil gas in riser reactor is 3.76 seconds.Operating method is passed through for the stock oil one way.
By table 4 data as can be seen, the heavy oil productive rate of embodiment 2 is 8.25%, has reduced by 2.98 percentage points than the heavy oil productive rate 11.23% of Comparative Examples 2, and gasoline yield is increased to 45.35% by 42.38% of Comparative Examples 2, has increased by 2.97 percentage points.Although the reacted gas productive rate is increased to 17.96% from 16.15%, 1.81 percentage points have been increased, but dry gas yied does not only increase, decrease on the contrary, be reduced to 1.96% from 2.38%, reduced by 0.42 percentage point, the increase of reacted gas productive rate shows that mainly the increasing degree of liquefied gas yield is very big, this mainly is because technology of the present invention has been introduced a part of half regenerator at the riser tube middle part, improved the agent-oil ratio of whole riser tube, catalyzed reaction increases, and the disadvantageous heat cracking reaction of product is suppressed, and product is distributed improve.Compare with Comparative Examples 2, the pressure gasoline alkene of process implementing example 2 of the present invention is also lower, and the former is 52.7v%, and the latter is 31.6v%, has reduced by 21.1 percentage points.The sulphur content of the pressure gasoline of embodiment 2 is also low than Comparative Examples 2, and the former is 116 μ g/g, and the latter is 152 μ g/g, has reduced by 36 μ g/g.Research octane number (RON) embodiment 2 is 91.2, and Comparative Examples is 90.7, has increased by 0.5 unit.
The catalyst inlet of present embodiment second conversion zone (being the middle part catalyst inlet of riser reactor) to the distance of riser reactor bottom catalyst inlet is 50% of a riser reactor total length.Table 5 has provided the main operational condition of embodiment 3 and Comparative Examples 3 and product distributes and the concrete data of quality of gasoline.
The catalyzer that present embodiment adopts is a LRC-99 industry equilibrium catalyst, stock oil is the Central Plains long residuum, operational condition is: the regeneration temperature of first revivifier is 630 ℃, half regenerated catalyst carbon content after the regeneration is 0.23w%, a part half regenerator temperature behind the first revivifier external warmer, 5 heat-obtainings is reduced to 505 ℃, enters riser tube by riser tube middle part catalyst inlet 204 and participates in reaction.Another part regenerator enters second revivifier by half regenerated catalyst 11 and continues regeneration.The regeneration temperature of second revivifier is 700 ℃, through the carbon content of the regenerated catalyst of the second revivifier holomorphosis less than 0.05w%, two again holomorphosis catalyzer enter the riser tube bottom by riser tube bottom catalyst inlet 203 and participate in reaction, and the holomorphosis catalyst temperature that enters the riser tube bottom is 700 ℃.The reaction conditions of riser reactor first conversion zone is: 520 ℃ of riser tube bottom finish mixing temperatures, the first conversion zone latter end temperature of reaction (referring to be close to the temperature of catalyst inlet 204 lower ends, riser tube stage casing) is 505 ℃, the oil gas residence time is 1.78 seconds, and agent-oil ratio is 6.32.The reaction conditions of riser reactor second conversion zone is: the riser tube temperature out is 490 ℃, the oil gas residence time is 1.67 seconds, and total agent-oil ratio (the catalyzer summation that catalyzer that catalyst inlet 203 enters bottom riser tube and middle part catalyst inlet 204 enter) is 9.15.Operating method is passed through for the stock oil one way.
Comparative Examples 3: stock oil is identical with embodiment 1 with catalyzer, the device operational condition is: the regeneration temperature of first revivifier is 630 ℃, the regeneration temperature of second revivifier is 700 ℃, and the temperature that regenerated catalyst enters riser reactor is 700 ℃, and the regenerated catalyst carbon content is 0.05w%.Regenerated catalyst enters riser reactor by the bottom, 520 ℃ of riser tube bottom finish mixing temperatures, agent-oil ratio in the riser reactor is 6.45, and riser reactor top exit temperature is 490 ℃, and the residence time of oil gas in riser reactor is 3.63 seconds.Operating method is passed through for the stock oil one way.
By table 5 data as can be seen, the heavy oil productive rate of embodiment 3 is 10.24%, has reduced by 5.32 percentage points than the heavy oil productive rate 15.56% of Comparative Examples 3, and gasoline yield is increased to 44.25% by 42.54% of Comparative Examples 3, has increased by 1.71 percentage points.Total reacted gas productive rate is increased to 16.21% from 14.05%, has increased by 2.16 percentage points, and wherein dry gas yied 2.12% is reduced to 1.78%, has reduced by 0.34 percentage point, and liquefied gas yield is increased to 14.43% from 11.93%, has increased by 2.50 percentage points.The pressure gasoline alkene of embodiment 3 is 26.7%, has reduced by 22.1 percentage points than the pressure gasoline alkene 48.8% of Comparative Examples 3.The sulphur content of the pressure gasoline of embodiment 3 is 827 μ g/g, has reduced by 159 μ g/g than the sulphur content 986 μ g/g of the pressure gasoline of Comparative Examples 3.Research octane number (RON) embodiment 3 is 92.4, and Comparative Examples 3 is 92.1, has increased by 0.3 unit.
Embodiment 4
The catalyst inlet of present embodiment second conversion zone (being the middle part catalyst inlet of riser reactor) to the distance of riser reactor bottom catalyst inlet is 30% of a riser reactor total length.Table 6 has provided the main operational condition of embodiment 4 and Comparative Examples 4 and product distributes and the concrete data of quality of gasoline.
The catalyzer that present embodiment adopts is CC-20D, stock oil is the defeated mixed oil of the peaceful pipe in Shandong, operational condition is: the regeneration temperature of first revivifier is 580 ℃, half regenerated catalyst carbon content after the regeneration is 0.31w%, a part half regenerator temperature behind the first revivifier external warmer, 5 heat-obtainings is reduced to 530 ℃, enters riser tube by riser tube middle part catalyst inlet 204 and participates in reaction.Another part regenerator enters second revivifier by half regenerated catalyst 11 and continues regeneration.The regeneration temperature of second revivifier is 680 ℃, through the carbon content of the regenerated catalyst of the second revivifier holomorphosis less than 0.05w%, two again holomorphosis catalyzer enter the riser tube bottom by riser tube bottom catalyst inlet 203 and participate in reaction, and the holomorphosis catalyst temperature that enters the riser tube bottom is 680 ℃.The reaction conditions of riser reactor first conversion zone is: 510 ℃ of riser tube bottom finish mixing temperatures, the first conversion zone latter end temperature of reaction (referring to be close to the temperature of catalyst inlet 204 lower ends, riser tube stage casing) is 490 ℃, the oil gas residence time is 0.87 second, and agent-oil ratio is 5.5.The reaction conditions of riser reactor second conversion zone is: the riser tube temperature out is 495 ℃, the oil gas residence time is 2.35 seconds, and total agent-oil ratio (the catalyzer summation that catalyzer that catalyst inlet 203 enters bottom riser tube and middle part catalyst inlet 204 enter) is 8.96.Operating method is passed through for the stock oil one way.
Comparative Examples 4: stock oil is identical with embodiment 4 with catalyzer, the device operational condition is: the regeneration temperature of first revivifier is 630 ℃, the regeneration temperature of second revivifier is 680 ℃, and the temperature that regenerated catalyst enters riser reactor is 680 ℃, and the regenerated catalyst carbon content is 0.05w%.Regenerated catalyst enters riser reactor by the bottom, 510 ℃ of riser tube bottom finish mixing temperatures, agent-oil ratio in the riser reactor is 5.80, and riser reactor top exit temperature is 510 ℃, and the residence time of oil gas in riser reactor is 3.46 seconds.Operating method is passed through for the stock oil one way.
By table 6 data as can be seen, the heavy oil productive rate of embodiment 4 is 8.23%, has reduced by 5.08 percentage points than the heavy oil productive rate 13.31% of Comparative Examples 4, and gasoline yield is increased to 45.78% by 41.64% of Comparative Examples 4, has increased by 4.14 percentage points.Total reacted gas productive rate is increased to 19.36% from 17.63%, has increased by 1.73 percentage points, and wherein dry gas yied 1.98% is reduced to 1.69%, has reduced by 0.29 percentage point, and liquefied gas yield is increased to 17.67% from 15.65%, has increased by 2.02 percentage points.The pressure gasoline alkene of embodiment 4 is 32.4%, has reduced by 11.4 percentage points than the pressure gasoline alkene 43.8% of Comparative Examples 4.The sulphur content of the pressure gasoline of embodiment 4 is 927 μ g/g, has reduced by 127 μ g/g than the sulphur content 1054 μ g/g of the pressure gasoline of Comparative Examples 4.Research octane number (RON) embodiment 4 is 95.2, and Comparative Examples 4 is 94.8, has increased by 0.6 unit.
Embodiment 5
The catalyst inlet of present embodiment second conversion zone (being the middle part catalyst inlet of riser reactor) to the distance of riser reactor bottom catalyst inlet is 70% of a riser reactor total length.Table 7 has provided embodiment 5 and the main operational condition of Comparative Examples 5 and the concrete data of product distribution and quality of gasoline.
The catalyzer that present embodiment adopts is CC-20D, stock oil is the defeated mixed oil of the peaceful pipe in Shandong, operational condition is: the regeneration temperature of first revivifier is 600 ℃, half regenerated catalyst carbon content after the regeneration is 0.27w%, a part half regenerator temperature behind the first revivifier external warmer, 5 heat-obtainings is reduced to 560 ℃, enters riser tube by riser tube middle part catalyst inlet 204 and participates in reaction.Another part regenerator enters second revivifier by half regenerated catalyst 11 and continues regeneration.The regeneration temperature of second revivifier is 660 ℃, through the carbon content of the regenerated catalyst of the second revivifier holomorphosis less than 0.05w%, two again holomorphosis catalyzer enter the riser tube bottom by riser tube bottom catalyst inlet 203 and participate in reaction, and the holomorphosis catalyst temperature that enters the riser tube bottom is 640 ℃.The reaction conditions of riser reactor first conversion zone is: 490 ℃ of riser tube bottom finish mixing temperatures, the first conversion zone latter end temperature of reaction (referring to be close to the temperature of catalyst inlet 204 lower ends, riser tube stage casing) is 470 ℃, the oil gas residence time is 2.34 seconds, and agent-oil ratio is 6.6.The reaction conditions of riser reactor second conversion zone is: the riser tube temperature out is 500 ℃, the oil gas residence time is 0.84 second, and total agent-oil ratio (the catalyzer summation that catalyzer that catalyst inlet 203 enters bottom riser tube and middle part catalyst inlet 204 enter) is 10.68.Operating method is passed through for the stock oil one way.
Comparative Examples 5: stock oil is identical with embodiment 5 with catalyzer, the device operational condition is: the regeneration temperature of first revivifier is 610 ℃, the regeneration temperature of second revivifier is 710 ℃, and the temperature that regenerated catalyst enters riser reactor is 680 ℃, and the regenerated catalyst carbon content is 0.05w%.Regenerated catalyst enters riser reactor by the bottom, 490 ℃ of riser tube bottom finish mixing temperatures, agent-oil ratio in the riser reactor is 6.54, and riser reactor top exit temperature is 460 ℃, and the residence time of oil gas in riser reactor is 3.64 seconds.Operating method is passed through for the stock oil one way.
By table 7 data as can be seen, the heavy oil productive rate of embodiment 5 is 8.18%, is 13.40% to have reduced by 5.22 percentage points than the heavy oil productive rate of Comparative Examples 5, and gasoline yield is increased to 45.11% by 41.98% of Comparative Examples 5, has increased by 3.13 percentage points.Total reacted gas productive rate is increased to 17.39% from 15.85%, has increased by 1.50 percentage points, and wherein dry gas yied 0.98% is reduced to 0.91%, has reduced by 0.07 percentage point, and liquefied gas yield is increased to 16.48% from 14.87%, has increased by 1.59 percentage points.The pressure gasoline alkene of embodiment 5 is 30.7%, has reduced by 13.9 percentage points than the pressure gasoline alkene 44.6% of Comparative Examples 5.The sulphur content of the pressure gasoline of embodiment 5 is 898 μ g/g, has reduced by 98 μ g/g than the sulphur content 996 μ g/g of the pressure gasoline of Comparative Examples 5.Research octane number (RON) embodiment 5 is 94.6, and Comparative Examples 5 is 94.4, has increased by 0.2 unit.
Table 1 stock oil character
| Project | The grand celebration long residuum | The Central Plains long residuum | The defeated mixed oil of Lu Ningguan |
| Density (20 ℃), g/cm
3Viscosity: 80 ℃, mm
2/s 100℃，mm
2/ s zero pour, ℃ carbon residue, w% molecular-weight average ultimate analysis C, w% H, w% S, w% N, w% metal content Fe, μ g/g Ni, μ g/g v, μ g/g Na, μ g/g group composition stable hydrocarbon, w% aromatic hydrocarbons, w% colloid+bituminous matter, the w% boiling range, ℃ | 0.8943 45.18 25.30 36 4.66 586 86.46 12.66 0.11 0.17 11.58 3.80 ＜0.10 6.40 63.1 20.6 16.3 230 356 557 685 690 | 0.9144 73.73 37.34 47 7.82 527 86.50 12.67 0.61 0.30 25.56 4.69 2.62 10.46 52.5 19.4 28.1 246 381 510 676 685 | 0.9196 17.66 12.37 26 1.93 350 86.25 12.31 0.66 0.35 3.1 4.3 1.8 1.8 58.0 30.8 11.2 318 373 445 594 612 |
Table 2 catalyst property
The table 3 Shandong defeated mixing oil cracked product of peaceful pipe distributes and the pressure gasoline quality
| Embodiment 1 (technology of the present invention) | Comparative Examples 1 (conventional riser tube technology) | |
| Catalyzer | CC-20D | |
| Stock oil | The defeated mixed oil of Lu Ningguan | |
| Main operational condition reaction pressure, Mpa riser tube temperature out, ℃ riser tube tonic mouth temperature, ℃ riser tube bottom temp, inclined tube temperature ℃ again and again, ℃ two inclined tube temperature again, ℃ raw material preheating temperature, ℃ oil inlet quantity, the kg/h water yield that atomizes, the kg/h reaction times, second agent-oil ratio (C/O), m/m riser tube epimere riser tube hypomere | 0.015 510 520 540 520 680 305 1.83 0.18 3.39 9.20 6.50 | 0.008 510 540 680 300 1.81 0.18 3.21 6.43 6.43 |
| Product distributes, % reacted gas (≤C 4) wherein: dry gas H 2 CH 4 C 2H 4 C 2H 6Liquefied gas C 3H 6 C 3H 8 C 4H 8 C 4H 10Gasoline (C 5～205 ℃) diesel oil (205～350C) heavy oil (＞350 ℃) coke loss | 21.86 1.63 0.13 0.48 0.65 0.37 20.23 7.60 0.72 8.49 3.42 48.18 16.44 6.10 6.69 0.73 | 20.58 1.99 0.12 0.63 0.80 0.44 18.59 7.08 0.66 8.31 2.54 44.68 17.61 10.48 6.02 0.63 |
| Gasoline property density (20 ℃), (50 ℃ of g/cm3 corrosion, 3 hours) inductive phase, the min sulphur content, μ g/g nitrogen content, μ g/g bromine valency, the gBr/100ml existent gum, the g/100ml vapour pressure, the kPa group composition, v% alkane alkene aromatic hydrocarbons boiling range, ℃ initial boiling point 10% 50% 90% final boiling point RON | 0.7647 3b 317 1041 34 62.2 3.0 26.1 32.7 29.3 38.0 38 67 115 175 199 95.6 | 0.7618 3a 370 1191 43.3 78.5 2.0 40.2 24.4 44.2 31.4 38 67 112 171 193 95.5 |
Table 4 grand celebration long residuum cracked product distributes and the pressure gasoline quality
| Embodiment 2 (technology of the present invention) | Comparative Examples 2 (conventional riser tube technology) | |
| Catalyzer | LRC-99 | |
| Stock oil | The grand celebration long residuum | |
| Main operational condition reaction pressure, Mpa riser tube temperature out, ℃ riser tube tonic mouth temperature, ℃ riser tube bottom temp, inclined tube temperature ℃ again and again, ℃ two inclined tube temperature again, ℃ raw material preheating temperature, ℃ oil inlet quantity, the kg/h water yield that atomizes, the kg/h reaction times, second agent-oil ratio (C/O), m/m riser tube epimere riser tube hypomere | 0.012 490 500 520 500 700 280 1.81 0.18 3.78 8.80 6.10 | 0.010 490 520 700 280 1.81 0.18 3.76 6.25 6.25 |
| Product distributes, % reacted gas (≤C 4) wherein: dry gas H 2 CH 4 C 2H 4 C 2H 6Liquefied gas C 3H 6 C 3H 8 C 4H 8 C 4H 10Gasoline (C 5～205 ℃) loss of diesel oil (205～350 ℃) heavy oil (＞350 ℃) coke | 17.96 1.96 0.15 0.58 0.81 0.42 16.00 6.18 1.12 6.32 2.38 45.35 18.64 8.25 8.68 1.12 | 16.15 2.38 0.18 0.72 1.02 0.46 13.77 5.25 0.86 5.47 2.19 42.38 21.43 11.23 8.25 0.56 |
| Gasoline property density (20 ℃), (50 ℃ of g/cm3 corrosion, 3 hours) inductive phase, the min sulphur content, μ g/g nitrogen content, μ g/g bromine valency, the gBr/100ml existent gum, the g/100ml vapour pressure, the kPa group composition, v% alkane alkene aromatic hydrocarbons boiling range, ℃ initial boiling point 10% 50% 90% final boiling point RON | 0.7352 2a 425 116 24 56.8 1.6 29.4 44.9 31.6 23.5 29 72 112 176 198 91.2 | 0.7411 2a 386 152 34 64.1 1.8 31.2 31.0 52.7 16.3 31 68 116 181 202 90.7 |
Table 5 Central Plains long residuum cracked product distributes and the pressure gasoline quality
| Embodiment 3 (technology of the present invention) | Comparative Examples 3 (conventional riser tube technology) | |
| Catalyzer | LRC-99 | |
| Stock oil | The grand celebration long residuum | |
| Main operational condition reaction pressure, Mpa riser tube temperature out, ℃ riser tube tonic mouth temperature, ℃ riser tube bottom temp, inclined tube temperature ℃ again and again, ℃ two inclined tube temperature again, ℃ raw material preheating temperature, ℃ oil inlet quantity, the kg/h water yield that atomizes, the kg/h reaction times, second agent-oil ratio (C/O), m/m riser tube epimere riser tube hypomere | 0.012 490 505 520 505 700 270 2.10 0.18 3.45 9.15 6.32 | 0.013 490 520 700 270 2.10 0.18 3.63 6.45 6.45 |
| Product distributes, % reacted gas (≤C 4) wherein: dry gas H 2 CH 4 C 2H 4 C 2H 6Liquefied gas C 3H 6 C 3H 8 C 4H 8 C 4H 10Gasoline (C 5～205) diesel oil (205～350 ℃) heavy oil (＞350 ℃) coke loss | 16.21 1.78 0.14 0.50 0.62 0.52 14.43 5.38 1.62 5.12 2.31 44.25 18.29 10.24 10.23 0.78 | 14.05 2.12 0.18 0.65 0.71 0.58 11.93 4.62 1.18 4.56 1.57 42.54 17.35 15.56 9.48 1.02 |
| Gasoline property density (20 ℃), (50 ℃ of g/cm3 corrosion, 3 hours) inductive phase, the min sulphur content, μ g/g nitrogen content, μ g/g bromine valency, the gBr/100ml existent gum, the g/100ml vapour pressure, the kPa group composition, v% alkane alkene aromatic hydrocarbons boiling range, ℃ initial boiling point 10% 50% 90% final boiling point RON | 0.7458 2b 358 827 32 51 1.8 28.7 45.9 26.7 27.4 36 74 115 178 201 92.4 | 0.7425 2b 344 986 29 58 2.1 28.4 33.7 48.8 17.5 36 73 117 179 200 92.1 |
The table 6 Shandong defeated mixing oil cracked product of peaceful pipe distributes and the pressure gasoline quality
| Embodiment 4 (technology of the present invention) | Comparative Examples 4 (conventional riser tube technology) | |
| Catalyzer | CC-20D | |
| Stock oil | The defeated mixed oil of Lu Ningguan | |
| Main operational condition reaction pressure, Mpa riser tube temperature out, ℃ riser tube tonic mouth temperature, ℃ riser tube bottom temp, inclined tube temperature ℃ again and again, ℃ two inclined tube temperature again, ℃ raw material preheating temperature, ℃ oil inlet quantity, the kg/h water yield that atomizes, the kg/h reaction times, second agent-oil ratio (C/O), m/m riser tube epimere riser tube hypomere | 0.013 495 495 510 530 680 255 1.82 0.18 3.22 8.96 5.51 | 0.012 480 510 680 255 1.82 0.18 3.46 5.80 5.80 |
| Product distributes, % reacted gas (≤C 4) wherein: dry gas H 2 CH 4 C 2H 4 C 2H 6Liquefied gas C 3H 6 C 3H 8 C 4H 8 C 4H 10Gasoline (C 5～205 ℃) loss of diesel oil (205～350 ℃) heavy oil (＞350 ℃) coke | 19.36 1.69 0.16 0.52 0.63 0.38 17.67 6.77 0.61 7.47 2.82 45.78 19.74 8.23 6.11 0.78 | 17.63 1.98 0.21 0.63 0.48 0.66 15.65 5.92 0.57 7.04 2.12 41.64 21.20 13.31 5.33 0.89 |
| Gasoline property density (20 ℃), (50 ℃ of g/cm3 corrosion, 3 hours) inductive phase, the min sulphur content, μ g/g nitrogen content, μ g/g bromine valency, the gBr/100ml existent gum, the g/100ml vapour pressure, the kPa group composition, v% alkane alkene aromatic hydrocarbons boiling range, ℃ initial boiling point 10% 50% 90% final boiling point RON | 0.7556 2a 396 927 35.6 64.5 2.4 36 32.0 32.4 35.6 36 69 113 178 201 95.2 | 0.7534 2a 380 1054 41.5 69.6 1.8 38 27.7 43.8 28.5 36 68 114 175 198 94.8 |
The table 7 Shandong defeated mixing oil cracked product of peaceful pipe distributes and the pressure gasoline quality
| Embodiment 5 (technology of the present invention) | Comparative Examples 5 (conventional riser tube technology) | |
| Catalyzer | CC-20D | |
| Stock oil | The defeated mixed oil of Lu Ningguan | |
| Main operational condition reaction pressure, Mpa riser tube temperature out, ℃ riser tube tonic mouth temperature, ℃ riser tube bottom temp, inclined tube temperature ℃ again and again, ℃ two inclined tube temperature again, ℃ raw material preheating temperature, ℃ oil inlet quantity, the kg/h water yield that atomizes, the kg/h reaction times, second agent-oil ratio (C/O), m/m riser tube epimere riser tube hypomere | 0.013 500 470 490 560 640 254 1.82 0.18 3.18 10.68 6.60 | 0.010 460 490 680 254 1.82 0.18 3.64 6.54 6.54 |
| Product distributes, % reacted gas (≤C 4) wherein: dry gas H 2 CH 4 C 2H 4 C 2H 6Liquefied gas C 3H 6 C 3H 8 C 4H 8 C 4H 10Gasoline (C 5～205 ℃) loss of diesel oil (205～350 ℃) heavy oil (＞350 ℃) coke | 17.39 0.91 0.13 0.22 0.17 0.39 16.48 5.84 0.63 6.49 3.52 45.11 21.57 8.18 6.24 1.51 | 15.85 0.98 0.14 0.26 0.37 0.21 14.87 5.27 0.56 6.38 2.66 41.98 21.78 13.40 5.77 1.22 |
| Gasoline property density (20 ℃), (50 ℃ of g/cm3 corrosion, 3 hours) inductive phase, the min sulphur content, μ g/g nitrogen content, μ g/g bromine valency, the gBr/100ml existent gum, the g/100ml vapour pressure, the kPa group composition, v% alkane alkene aromatic hydrocarbons boiling range, ℃ initial boiling point 10% 50% 90% final boiling point RON | 0.7487 2a 426 898 34.9 46.2 2.4 36 37.1 30.7 32.2 37 70 116 176 201 94.6 | 0.7456 2a 412 996 38.7 67.5 2.3 38 29.4 44.6 26.0 35 66 113 172 203 94.4 |
Claims (5)
1. riser catalytic cracking method, stock oil (701) and catalytic cracking catalyst be the inlet of the stock oil bottom riser reactor (2) (7) respectively, riser tube bottom catalyst inlet (203) enters riser reactor (2), be in contact with one another and along the up catalytic cracking reaction that carries out of riser reactor (2), reaction oil gas and reclaimable catalyst are flowed out by the outlet at riser reactor (2) top and enter settling vessel (1), reclaimable catalyst enters behind stripping in first revivifier (3) and second revivifier (4) regenerates, recycle, it is characterized in that: be provided with middle part catalyst inlet (204) at the middle part of riser reactor (2), introducing is 400～600 ℃ half regenerated catalyst from the temperature through behind first revivifier external warmer (5) heat-obtaining of first revivifier (3), the regeneration temperature of first revivifier (3) is 500～700 ℃, the catalyzer that enters riser reactor bottom catalyst inlet (203) is 600～720 ℃ holomorphosis catalyzer for the temperature from second revivifier (4), the regeneration temperature of second revivifier (4) is 600～720 ℃, holomorphosis catalyzer from second revivifier (4) contacts the back along the up catalytic cracking reaction that carries out of first conversion zone (201) of the riser reactor (2) under the described middle part catalyst inlet (204) with stock oil (701), the temperature of reaction of first conversion zone (201) is 450～580 ℃, the oil gas residence time is 0.5～2 second, agent-oil ratio is 4～8, half regenerated catalyst of being introduced by described middle part catalyst inlet (204) mixes with oil gas with the up catalyzer from first conversion zone (201), enter second conversion zone (202) of the riser reactor (2) on the middle part catalyst inlet (204), continue the up catalytic cracking reaction that carries out, the temperature of reaction of second conversion zone (202) is 430～540 ℃, oil gas is 1～5 second when stopping, the temperature of reaction that total agent-oil ratio is 8～18, second conversion zone (202) is hanged down 5～50 ℃ than the temperature of reaction of first conversion zone (201).
2. catalyst cracking method according to claim 1, it is characterized in that: the temperature of reaction of first conversion zone (201) is 480～560 ℃, the oil gas residence time is 0.6～1 second, agent-oil ratio is 5～8, the temperature of described holomorphosis catalyzer is 620～710 ℃, the regeneration temperature of second revivifier (4) is 620～710 ℃, the temperature of reaction of second conversion zone (202) is 450～530 ℃, oil gas is 1.5～3 seconds when stopping, total agent-oil ratio is 8～15, the temperature of reaction of second conversion zone (202) is hanged down 10～30 ℃ than the temperature of reaction of first conversion zone (201), described temperature through half regenerated catalyst behind first revivifier external warmer (5) heat-obtaining is 450～550 ℃, and the regeneration temperature of first revivifier (3) is 550～650 ℃.
3. riser fluid catalytic cracking of realizing the described method of claim 1, comprise riser reactor (2), first revivifier (3) and second revivifier (4), the bottom of riser reactor (2) is provided with stock oil inlet (7), bottom catalyst inlet (203), the top is provided with outlet, be positioned at settling vessel (1), it is characterized in that: the middle part of riser reactor (2) also is provided with middle part catalyst inlet (204), first revivifier (3) is provided with the first revivifier external warmer (5), be provided with two sections catalyst transports (8) between the first revivifier external warmer (5) and the middle part catalyst inlet (204), the two or two revivifier (4) is provided with the second revivifier external warmer (6), be provided with one section catalyst transport (9) between described riser reactor bottom catalyst inlet (203) and second revivifier (4), riser reactor under the middle part catalyst inlet (204) constitutes first conversion zone (201), and the riser reactor on the middle part catalyst inlet (204) constitutes second conversion zone (202).
4. riser fluid catalytic cracking according to claim 3 is characterized in that: described middle part catalyst inlet (204) to the distance of riser reactor bottom catalyst inlet (203) is 20～80% of riser reactor (a 2) total length.
5. riser fluid catalytic cracking according to claim 4 is characterized in that: described middle part catalyst inlet (204) to the distance of riser reactor bottom catalyst inlet (203) is 30～70% of riser reactor (a 2) total length.
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| WO2011054265A1 (en) * | 2009-11-04 | 2011-05-12 | Shi Baozhen | Catalytic conversion process of petroleum hydrocarbon in double reactor and apparatus thereof |
| CN102268291A (en) * | 2010-06-02 | 2011-12-07 | 中国石油化工集团公司 | Catalytic cracking technology and device for reducing olefins in gasoline |
| CN102276393A (en) * | 2010-06-11 | 2011-12-14 | 中国石油化工股份有限公司 | Method for getting regenerated catalyst back to reactor in regeneration system of reaction for preparing alkene from methanol |
| CN101275081B (en) * | 2007-03-30 | 2012-06-27 | 中国石油化工股份有限公司 | Method for reducing catalytic cracking dry gas |
| CN102746893A (en) * | 2011-04-19 | 2012-10-24 | 中国石油化工股份有限公司 | Catalytic cracking method and device |
| CN102746892A (en) * | 2011-04-19 | 2012-10-24 | 中国石油化工股份有限公司 | Catalytic cracking method and device |
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| CN1118539C (en) * | 2000-12-13 | 2003-08-20 | 中国石油天然气股份有限公司 | Catalytic cracking technology with two-stage lift pipe |
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| CN101275081B (en) * | 2007-03-30 | 2012-06-27 | 中国石油化工股份有限公司 | Method for reducing catalytic cracking dry gas |
| WO2011054265A1 (en) * | 2009-11-04 | 2011-05-12 | Shi Baozhen | Catalytic conversion process of petroleum hydrocarbon in double reactor and apparatus thereof |
| CN102268291A (en) * | 2010-06-02 | 2011-12-07 | 中国石油化工集团公司 | Catalytic cracking technology and device for reducing olefins in gasoline |
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| CN102746893A (en) * | 2011-04-19 | 2012-10-24 | 中国石油化工股份有限公司 | Catalytic cracking method and device |
| CN102746892A (en) * | 2011-04-19 | 2012-10-24 | 中国石油化工股份有限公司 | Catalytic cracking method and device |
| CN103087768A (en) * | 2011-11-02 | 2013-05-08 | 中国石油化工股份有限公司 | Catalytic cracking method |
| CN103788993A (en) * | 2012-10-29 | 2014-05-14 | 中国石油化工集团公司 | Catalytic cracking unit |
| CN103788993B (en) * | 2012-10-29 | 2016-06-08 | 中国石油化工集团公司 | A kind of catalytic cracking unit |
| CN104073283A (en) * | 2013-03-28 | 2014-10-01 | 中国石油天然气股份有限公司 | Method for catalytic processing of petroleum |
| CN104073283B (en) * | 2013-03-28 | 2017-02-01 | 中国石油天然气股份有限公司 | Method for catalytic processing of petroleum |
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