CN1891790A - Hydrocarbon raw material catalytic cracking conversion reactor - Google Patents
Hydrocarbon raw material catalytic cracking conversion reactor Download PDFInfo
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- CN1891790A CN1891790A CN 200510017771 CN200510017771A CN1891790A CN 1891790 A CN1891790 A CN 1891790A CN 200510017771 CN200510017771 CN 200510017771 CN 200510017771 A CN200510017771 A CN 200510017771A CN 1891790 A CN1891790 A CN 1891790A
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Abstract
The invention relates to hydrocarbon material catalytic cracking transformation reactor. It belongs to petroleum refining technical field. It is compound riser reactor which is made up of lower part catalytic cracking section and upper part modification transformation section. The lower section is divided into material oil and cycle stock slurry oil catalytic cracking riser tubes whose upper ends are by passed. The former is interpenetrated with the modification transformation section. The invention can increase light oil yield by 1%-2%, and reduce alkene content by more than 15% in produced gasoline.
Description
Technical field
The invention belongs to the petroleum refining technology field, particularly a kind of hydrocarbon raw material catalytic cracking conversion reactor.
Background technology
Catalytic cracking unit is one of visual plant of refinery stock oil secondary processing, and the catalytic cracking reaction process realizes in riser reactor.In the conventional catalytic cracking unit, riser reactor only is a common pipe, always is about 40 meters.Stock oil after nozzle atomization by the speed about average 12-15 meter per second, was finished reaction through 3 seconds left and right sides time.Result of study shows that the reaction result of catalytic cracking directly depends on the structure and the design variable of riser reactor.
Over past ten years, catalytic cracking technology has been obtained very much progress.Going deep into Reaction Mechanisms research mainly given the credit in these progress.Discover that different fractions has nothing in common with each other at the catalyzer environment therapeutic method to keep the adverse qi flowing downwardization, cracking process in the stock oil, and also can the phase mutual interference under the common environment.Cracking reaction mainly occurs in the zone of riser tube bottom 1/5th to 1/4th, and catalyzer is rapid inactivation in this zone also, and its activity is general in most of zone at rear portion also to be had only originally 50%, and riser tube latter half efficient is very low; Recycle stock and slurry oil are easier to gasification than stock oil and are adsorbed by catalyzer, make catalyst active center's inactivation very soon, influence the cracking of other cuts; And gasoline fraction forms higher olefin(e) centent again under the influence of other oil gas compositions.In view of the above, proposed to design the mentality of designing of reaction conditions by cut.
Stock oil and circulation slurry oil separately enter riser tube at different positions scheme has at first appearred.The slurry oil (downstream) above stock oil that normally circulates is introduced riser tube.Make regenerated catalyst earlier with the stock oil reaction, and then with circulation slurry oil contact reacts, avoided the slurry oil influence of absorption too early.The MED technology and the Chinese patent application 01119807.9 of domestic a large amount of uses are typical example.
Further develop in the process, people have proposed " two-stage catalytic cracking " scheme.Promptly directly design two riser reactors, make different raw materials, solved mutual interferential problem completely at different riser tube internal reactions.The core of two sections designs is: (1) shortens the reaction times, and (2) press the feedstock property torpedo.
Interfere with each other problem in order to solve the reaction of stock oil, circulation slurry oil and gasoline simultaneously, Chinese patent application 0311944109 has proposed to build three reactors, respectively in order to the scheme of the oil that processes raw material, turning oil and gasoline.
Though more than separate the cracking scheme by raw material and can solve, each cut long preferably and disturb low, the ropy problem of the purpose product yield that brings mutually because of the reaction times, but the measure of taking is to repeat to increase device basically, implement on the actual engineering to be restricted, what have almost can not implement.In addition, each riser reactor adopts conventional pattern usually in the top scheme, still has the very low problem of reactor top reaction efficiency.The riser tube that Chinese patent application 99213769.1,00134054.9 proposes is relay cascade reaction scheme up and down, make riser reactor be divided into two sections layouts of serial connection up and down, first section (riser reactor of bottom) is used for the stock oil cracking, reaction product is after isolating catalyzer, oil gas upwards enters second riser reactor on top, further reacts.In second riser tube, replenish new low-temp recovery catalyzer again.This has been divided into two all short riser tubes up and down to conventional riser tube with regard to equaling, and has solved the inefficient problem in conventional riser reactor top.Similar, the catalyzer that Chinese patent application 99109193.0,200410060430.9 has proposed will not react is told, and only replenishes the low-temp recovery catalyzer at the middle part, suitably improves riser tube second half section catalyst activity, improves the way of riser tube efficient.But in these inventions, each riser reactor is conventional structure, and the quality of reactor product is still undesirable, and especially content of olefin in gasoline is higher.
At existing stock oil, in the two-stage catalytic cracking technology of recycle stock, circulation slurry oil torpedo, because recycle stock and circulation slurry oil temperature be all more than 300 ℃, the reagent oil ratio can only maintain the level of 3-4, is difficult to obtain the ideal product.
Along with going deep into of reactive group reason research, find that the structure of reactor has great effect to reaction result, multiple catalytic cracking riser reactor has appearred in succession.Chinese patent application 98125665.1 proposes to equate substantially reactor cross-section highly is designed to upwards the curve form of increase gradually vertically by the gas phase flow velocity, and the height for reactor first mate is reduced, but this scheme is difficult to realize on engineering.Chinese patent application 99105903.4,99105904.2,99105905.0,99109196.5,99109193.0 also the riser tube structure is improved, its core is that riser tube is divided into a, b, four districts of c, d (pre lift zone, first, second, third conversion zone), with enlarged-diameter, generally enlarge 2 to 3 times in the c district at middle part.It is low to distinguish the gas prompt drop in the feasible reaction, and temperature of reaction reduces, the density of catalyst increase.This district imports and exports undergauge respectively up and down, to connect with b, d district; The undergauge degree is controlled by cone angle, β separately.A, b, d three districts still are conventional riser tube.Though this scheme has taken into full account the reaction process processing requirement, the structure of reactor is reasonable not enough, and catalyst recirculation amount and density are difficult for regulating control, and the device operating restraint is narrow, and its c district inlet region catalyzer refluxes obviously, and back-mixing is serious.Chinese patent application 96106441.2,98125665.1 and 99118229.4 has also proposed the structure formation of riser reactor, its improvement mainly is at pre lift zone and stock oil feed zone, in pre lift zone, establish the catalyst transport conduit, make catalyzer force to be distributed in the riser tube central section, adopt the way of limit wall tonifying Qi to reduce the landing that catalyzer promotes tube edge wall district.The initial action section (b district) of reactor feed place is designed to taper, adapts because of the reactant volumetric expansion that the high speed cracking causes with this district.Purpose is to reduce the back-mixing that raw material enters the district, improves the finish contact efficiency.But the rear portion reaction zone of this invention riser tube, promptly c district and d district still are conventionally form, can not the reaction of this part be improved.
In the existing catalyst cracker, directly contact with reaction raw materials from the high temperature catalyst of revivifier, limited the agent-oil ratio raising, the while high temperature catalyst has also caused more side reaction, produces unnecessary dry gas and coke, has influenced the benefit of installing.
In addition, in the existing multiple riser scheme, all be provided with pipeline between each riser reactor and the revivifier, on each pipeline guiding valve be housed, with the control catalyst internal circulating load for catalyst recirculation.Several riser tubes are arranged, just form the circulation of several roads.Some also will establish independent settling vessel and catalyst stripping section, and structure is quite complicated.
Summary of the invention
The object of the invention is to provide a kind of can realize the requirement of two-stage catalytic, can satisfy the hydrocarbon raw material catalytic cracking reactor of producing the low-alkene gasoline processing condition again.
For reaching above-mentioned purpose, the present invention adopts following technical scheme: a kind of hydrocarbon raw material catalytic cracking conversion reactor, comprise the compound riser reactor of forming by the upgrading conversion zone on the catalytic cracking section of bottom and top, the catalytic cracking section of bottom is divided into stock oil catalytic cracking riser and recycle stock, slurry oil catalytic cracking riser, stock oil catalytic cracking riser and upgrading conversion zone up/down perforation, two riser tubes upper end also connects.
Two riser tube joints are provided with the quenching medium import.
The upgrading conversion zone is provided with the catalyst recirculation return line.
Upgrading conversion zone top and the junction hole enlargement of catalyzer return line.
The upgrading conversion zone is the riser tube pattern, and diameter is 1.2-2 a times of below catalytic cracking section diameter.
The shared catalyst regeneration device of two riser tubes.
Two riser tubes are made up of catalyzer precooling zone and catalytic cracking reaction section from bottom to top, and reaction raw materials autocatalysis agent precooling zone top enters reactor.
The riser tube that the present invention makes stock oil enter reactor lower part carries out catalytic cracking reaction, and another riser reactor that circulation slurry oil, freshening wet goods secondary reaction raw material enter reactor lower part carries out catalytic cracking reaction.After reaction oil gas in two riser tubes mixes, upwards enter shared mixing section (district) and mix, and mix with quenching medium, lowered the temperature by quenching medium in this district.Reactant flow then upwards flows into upgrading conversion zone (product upgrading riser tube) and carries out the upgrading reaction.After the oil gas outlet of reactor head is drawn reactor, enter subsequent handling.
The recycle stock of catalytic cracking section of the present invention, slurry oil reaction riser tube and stock oil reaction riser tube height are less than 1/2nd of reactor length overall.Both can guarantee the requirement of catalytic cracking time, also overcome the inefficient shortcoming of riser reactor latter half.Cryogenic product upgrading section adopts the riser tube structure, in this section, is suppressed from the cracking reaction of the oil gas of pyrolytic cracking section, carries out the product upgrading under low temperature, high catalyst density environment, helps the content of olefin in gasoline reduction.This section diameter is generally 1.2-2 times of lower feed oil catalytic cracking riser.More than be mixing section between two conversion zones, highly be 1-2 rice, oily steam flow speed 8-15 meter per second is used to make the raw material oil gas from bottom differential responses riser tube to mix, and introduces quenching medium in this district, makes the oil gas cooling, suppresses cracking reaction.For strengthening upgrading district upgrading effect, partly establish the catalyzer return line at the upgrading riser tube, draw the part catalyzer from the riser tube top and be back in the upgrading riser tube, increase the agent-oil ratio in it.So, from the catalyst recirculation measuring angle, low agent-oil ratio and two kinds of environment of top high solvent-oil ratio of bottom have been formed.Reaction oil gas and recycling catalyst enter settling vessel and internal cyclone separators thereof through the outlet pipe outflow reactor, and catalyzer is isolated from oil gas, enters stripper.Enter the catalytic amount of cyclone separator and stripper and equate, do not increase the load of follow-up equipment with the catalytic amount that enters riser reactor through the regeneration standpipe.Be that the interior high solvent-oil ratio of reactor is realized at reactor itself, also only cause the change of riser tube itself.Product oil gas enters follow-up product separation unit at settling vessel top discharger.The heat transfer tube that is provided with in the catalyzer precooling zone of catalytic cracking riser bottom can be taken the heat of part catalyzer away, reduces temperature, and the agent-oil ratio in cracking reaction district is increased, and reduces olefin(e) centent in the gasoline, improves the purpose product yield.Used water is made heat-eliminating medium in the heat transfer tube.
The temperature of reaction of stock oil catalytic cracking reaction riser tube of the present invention is 510-560 ℃, and the reaction times is 0.6-1.2 second; Freshening wet goods secondary material riser cracking temperature of reaction is 400-530 ℃; The temperature of reaction of upgrading riser tube is 490-530 ℃, and the reaction times is 3-6 second; The fuel oil preheating temperature is 200-250 ℃, and the secondary raw material temperature is 250-360 ℃.Upgrading section catalyzer reflux ratio is 0.3-1.5.
Because the catalytic cracking reaction zone territory below reactor is provided with two riser tubes, and be provided with the catalyzer pre-cooler, can realize that stock oil and secondary reaction raw material (as circulation slurry oil, freshening wet goods) separately carry out catalytic cracking reaction, the control respectively and the optimization of realization response condition and reaction raw materials improve transformation efficiency and purpose product yield; The reactor latter half is designed to the riser tube pattern of fast fluidization, promptly is formed with the high solvent-oil ratio condition that is beneficial to hydrogen transference and isomerization reaction, less again back-mixing.Both solve long, the latter half of inefficient problem of conventional riser reactor, reduced olefin(e) centent in the gasoline again, improved quality product.Because the upgrading section is that two the riser tube reaction oil gas in bottom are shared, and equipment is more simplified, and invests lower.
The simple frame mode of the present invention instead-again installs the cracking reaction requirement that has realized short riser tube, short reaction time simultaneously in routine, has also realized separately reaction of different material, has also realized the requirement of decreasing by gasoline olefin.Can improve light oil yield 1-2%, the upgrading riser tube can make the content of olefin in gasoline of being produced reduce by 10 percentage points, upgrading riser tube catalyzer backflow effect can make gasoline olefin reduce 5-10 percentage point, and total can reduce content of olefin in gasoline more than 15 percentage points.Except that riser tube changes, do not increase equipment (not establishing settling vessel, stripping stage etc. in addition), do not change the load and the operation of original device settling vessel, cyclone and stripping stage.
Working process of the present invention is: the pre-cooler of distinguishing incoming stock oil riser reactors and circulation wet goods secondary reaction material riser reactors bottom from the catalyzer of revivifier through two regeneration standpipes, after these catalyzer are cooled to the temperature of requirement, under the effect of pre-lifting steam or dry gas, upwards flow, enter catalytic cracking reaction zone.Stock oil and secondary reaction material such as recycle stock enter reaction zone through atomizing nozzle separately, carry out cracking reaction under the catalyzer environment; After finishing cracking reaction, cooled off by shock chilling medium, stop cracking reaction at mixing section; Enter the upgrading riser tube then, carry out the product upgrading and transform.Reaction oil gas and recycling catalyst enter settling vessel through the outlet pipe at top, join with cyclone in it, carry out gas solid separation.Reaction oil gas is drawn through gas pipeline at the settling vessel top, enters follow-up product separation device.The catalyzer that cyclonic separator is told is introduced into stripping stage, displaced entrained oil gas by steam after, enter revivifier, under the temperature about 700 ℃,, remove the carbon distribution that forms in reaction process with oxygen reaction, recover active.Catalyzer after the regeneration enters riser tube through the regeneration standpipe.
Description of drawings
Fig. 1 is a structure of reactor synoptic diagram of the present invention;
Fig. 2 for use of the present invention anti--refill the interposed structure synoptic diagram;
Embodiment
In stock oil catalytic cracking riser 1, catalyzer pre-cooler 11 is located at the bottom, is provided with heat removing tube 12 in it, logical softening water 19 in the heat removing tube; Pre-cooler 11 tops are stock oil catalytic cracking reaction section 13, and stock oil 16 enters from the sidewall import in this section bottom; Fluidizing medium (steam or dry gas) 15 enters pre-cooler 11 from the lower end import, both has been used for realizing conducting heat, and also is used for realizing carrying catalyzer to conversion zone; Be introduced into pre-cooler 11 through regeneration standpipe 17 from the regenerated catalyst 14 of revivifier, under fluidizing medium 15 effects, send into catalytic cracking reaction section 13, realize cracking reaction.
In recycle stock, circulation slurry oil catalytic cracking riser 2, catalyzer precooling zone 21 is located at the bottom, is provided with heat removing tube 22 in it, logical softening water 29 in the heat removing tube; The precooling zone top is a secondary material catalytic cracking reaction section 23, and reaction mass 26 enters from sidewall in this section bottom; Fluidizing medium 25 enters precooling zone from the lower end import, both has been used for realizing conducting heat, and also is used for realizing carrying catalyzer to conversion zone.Be introduced into precooling zone 21 through regeneration standpipe 27 from the regenerated catalyst 24 of revivifier, under fluidizing medium 25 effects, send into catalytic cracking reaction section 23 then, realize cracking reaction.
After the catalytic cracking section was finished reaction, the reactant flow in two riser tubes entered mixing section 3, mixed, lowered the temperature with quenching medium 31 simultaneously.
Reaction oil gas after the cooling upwards enters upgrading riser tube 4 and carries out upgrading reaction, simultaneously this with contact through return line 6 round-robin backflow catalyzer 61.Gasoline in reaction oil gas alkene behind upgrading reduces by 20 percentage points.
Reaction oil gas and with the cyclonic separator 71 of catalyzer through fairlead 5 enters settling vessel 7 in of regenerator standpipe 17, the 27 sum equivalent of flowing through, isolate catalyzer after, oil gas is sent instead-again through pipeline 72 and is installed the product separation part that enters the back.Cyclonic separator 71 isolated catalyzer then flow into stripper 8 downwards, contact with stripped vapor, displace the oil gas of catalyst entrainment after, flow into revivifier 9, oxygen 91 reactions with from the regenerator bottoms import recover to enter reactor 1,2 again after the activity, finish reaction cycle.97 is external warmer.(settling vessel, gas are carried device, revivifier and partly are reflected among Fig. 2, omit in Fig. 1)
At a cover amount of finish 100 * 10
4Adopted above-mentioned reactor in t/a, the catalytic cracking unit, 50 meters of reactor height overalls, 15 meters of stock oil catalytic cracking riser 1 length, 1.0 meters of diameters, 1.5 meters of pre-cooler 11 diameters based on production gasoline and diesel oil.14 meters of recycle stock catalytic cracking riser 2 length, 0.35 meter of diameter, 0.7 meter of pre-cooler 21 diameter.5.0 meters of settling vessel 7 diameters, 9.0 meters of revivifier 9 diameters, 2.5 meters of stripper 8 diameters.1500 millimeters of mixing section 4 diameters, high 2.0 meters, 1.4 meters of upgrading riser tube 5 diameters, high 33.5 meters.1200 millimeters of oil gas fairlead 5 diameters, 500 millimeters of catalyzer return line 6 diameters.
200 ℃ of fuel oil preheating temperature, 350 ℃ of recycle stock, circulation slurry oil temperature, 510 ℃ of stock oil cracking reaction temperature, 515 ℃ of circulation slurry oil cracking reaction temperature; 490 ℃ of upgrading section temperature.Chilled water consumption 10.0t/h.The pre-cooler of stock oil cracking riser tube makes 80 ℃ of cooling catalysts, and recycle stock cracking riser tube pre-cooler makes 120 ℃ of cooling catalysts.
Catalyst recirculation amount through regeneration standpipe 17 incoming stock oil riser reactors is 1000t/h, and the catalyst recirculation amount that enters the recycle stock riser reactor through regeneration standpipe 27 is 200t/h, and the catalytic amount that returns the upgrading section through return line is 600t/h; The catalytic amount that enters settling vessel cyclone, stripper and revivifier through reactor outlet is 1200t/h.Settling vessel 7 working pressure 0.30MPa (a) (a-absolute pressure), revivifier 9 working pressure 0.38MPa (a).
Product is respectively: gasoline 42.4%, and diesel oil 33%, liquefied petroleum gas (LPG) 12%, dry gas adds loss 3%, coke 7.6%, slurry oil 2%.Content of olefin in gasoline 33% (v).
200 ℃ of fuel oil preheating temperature, 350 ℃ of circulation slurry oil temperature, 530 ℃ of stock oil cracking reaction temperature, 530 ℃ of recycle stock and slurry carcking temperature of reaction; 505 ℃ of upgrading section temperature.Chilled water consumption 13.0t/h.The precooling zone of stock oil catalytic cracking riser makes 60 ℃ of cooling catalysts, and secondary raw material cracking cracking riser tube precooling zone makes 80 ℃ of cooling catalysts.
Catalyst recirculation amount through regeneration standpipe 17 incoming stock oily catalytic cracking risers is 1200t/h, and the catalyst recirculation amount that enters the recycle stock catalytic cracking riser through regeneration standpipe 27 is 600t/h, and the catalytic amount that returns the upgrading section through return line is 1000t/h; The catalytic amount that enters settling vessel, cyclonic separator, stripper and revivifier through the reactor outlet pipe is 1800t/h.Riser tube top operational pressure 0.30MPa (a), revivifier working pressure 0.38MPa (a).
Product is respectively: gasoline 35%, and diesel oil 25%, liquefied petroleum gas (LPG) 24%, dry gas adds loss 3.5%, coke 9.0%.Slurry oil 3.5%, content of olefin in gasoline 25% (v).
Claims (7)
1, a kind of hydrocarbon raw material catalytic cracking conversion reactor, comprise the compound riser reactor of forming by the upgrading conversion zone on the catalytic cracking section of bottom and top, it is characterized in that, the catalytic cracking section of bottom is divided into stock oil catalytic cracking riser and recycle stock, slurry oil catalytic cracking riser, stock oil catalytic cracking riser and upgrading conversion zone up/down perforation, two riser tubes upper end also connects.
2, reactor as claimed in claim 1 is characterized in that, two riser tube joints are provided with the quenching medium import.
3, reactor as claimed in claim 1 or 2 is characterized in that, the upgrading conversion zone is provided with the catalyst recirculation return line.
4, reactor as claimed in claim 3 is characterized in that, upgrading conversion zone top and the junction hole enlargement of catalyzer return line.
5, reactor as claimed in claim 4 is characterized in that, the upgrading conversion zone is the riser tube pattern, and diameter is 1.2-2 a times of below catalytic cracking section diameter.
6, reactor as claimed in claim 5 is characterized in that, the shared catalyst regeneration device of two riser tubes.
7, reactor as claimed in claim 6 is characterized in that, two riser tubes are made up of catalyzer precooling zone and catalytic cracking reaction section from bottom to top, and reaction raw materials autocatalysis agent precooling zone top enters reactor.
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| CNB2005100177712A CN100415853C (en) | 2005-07-07 | 2005-07-07 | Hydrocarbon raw material catalytic cracking conversion reactor |
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| CNB2005100177712A CN100415853C (en) | 2005-07-07 | 2005-07-07 | Hydrocarbon raw material catalytic cracking conversion reactor |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101932672A (en) * | 2007-08-09 | 2010-12-29 | 中国石油化工股份有限公司 | A process of catalytic conversion |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1438296A (en) * | 2003-03-13 | 2003-08-27 | 中国石油天然气股份有限公司 | Three-section lift pipe catalytic cracking process |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101932672A (en) * | 2007-08-09 | 2010-12-29 | 中国石油化工股份有限公司 | A process of catalytic conversion |
| CN101932672B (en) * | 2007-08-09 | 2015-01-21 | 中国石油化工股份有限公司 | A process of catalytic conversion |
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Assignee: QINGDAO JINGRUN PETROCHEMICAL ENGINEERING CO., LTD. Assignor: Luoyang Petro-Chemical Equipment Inst. Contract fulfillment period: 2008.9.23 to 2013.10.1 contract change Contract record no.: 2008410000240 Denomination of invention: Hydrocarbon raw material catalytic cracking conversion reactor Granted publication date: 20080903 License type: Exclusive license Record date: 20081222 |
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Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2008.9.23 TO 2013.10.1; CHANGE OF CONTRACT Name of requester: QINGDAO JINGRUN PETROCHEMICAL ENGINEERING CO., LTD Effective date: 20081222 |
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Address after: Three road high tech Zone 471003 Henan city of Luoyang province Luoyang Tsinghua Science Park 609 large stone Jingrun Petrochemical Engineering Company Limited Patentee after: Luoyang Petro-Chemical Equipment Inst. Address before: 471003 Zhongzhou West Road, Henan, China, No. 27, No. Patentee before: Luoyang Petro-Chemical Equipment Inst. |
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Granted publication date: 20080903 Termination date: 20130707 |