CN103666551B - Catalytic processing method and catalytic processing device of high-temperature Fischer-Tropsch synthetic oil - Google Patents
Catalytic processing method and catalytic processing device of high-temperature Fischer-Tropsch synthetic oil Download PDFInfo
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Abstract
The invention discloses a catalytic processing method and a catalytic processing device of high-temperature Fischer-Tropsch synthetic oil. The method comprises the following steps: separating the high-temperature Fischer-Tropsch synthetic oil to obtain a high-temperature condensate, a low-temperature condensate and gaseous hydrocarbon; introducing the gaseous hydrocarbon and the high-temperature condensate into a first riser reactor for catalytic conversion; introducing the low-temperature condensate into a second riser reactor for catalytic conversion. The device comprises a reactor, a regenerator and a spent catalyst mixture heat exchanger. The method for processing the high-temperature Fischer-Tropsch synthetic oil provided by the invention is high in propylene yield.
Description
Technical field
The present invention relates to a kind of working method and device of high temperature fischer-tropsch synthetic oil.
Background technology
Petroleum hydrocarbon is the main source of the industrial chemicals such as motor spirit and propylene, increasingly exhausted along with the constantly soaring of international oil price and petroleum resources, the substitute energy of countries in the world positive search for oil.Fischer-Tropsch (F-T) synthesis that Germanization scholar FFischer and HTropsch invented in nineteen twenty-three, to comprise the synthetic gas of carbon monoxide and hydrogen for raw material, hydro carbons is generated under the effect of synthetic catalyst, and synthetic gas can transform generation, wide material sources by coal, Sweet natural gas, coal-seam gas and biomass etc.
F-T synthesis comprises high temperature F-T and synthesizes (HTFT) and low temperature F-T synthesis (LTFT) two kinds.The temperature of reaction of Low Temperature Fischer Tropsch synthesis is lower than 250 DEG C, and the temperature of reaction of high temperature fischer-tropsch synthesis is generally 250 DEG C ~ 375 DEG C, generally more than 300 DEG C.The Fischer-Tropsch synthesis oil that F-T synthesis obtains and natural oil cut have larger difference in hydrocarbon composition and main character, and the Fischer-Tropsch synthesis oil composition that different methods obtains and character also exist larger difference.The naphtha fraction of Low Temperature Fischer Tropsch synthetic oil not sulfur-bearing, nitrogen substantially, oxygen level is high, and alkane wherein and the alkene overwhelming majority are straight chain, and octane value is low, is difficult to directly allotment and is met the vehicle fuel that standard (such as DB11/238-2007) requires; The diesel oil distillate sulphur of low temperature F-T synthetic oil, nitrogen and aromaticity content are extremely low, and cetane value is very high, and condensation point is high, and low-temperature fluidity is poor, is not suitable for directly being used as vehicle fuel.Gasoline fraction and the diesel oil distillate olefin(e) centent of high temperature fischer-tropsch synthetic oil are higher, are not suitable for directly being used as vehicle fuel.Therefore, the product that F-T synthesis obtains, usually through further processing, uses the fuel of specification to obtain meeting or prepares industrial chemicals.
CN1854265A, CN1854266A and CN101812321A disclose with hydrogenation upgrading increasing output of diesel oil for main purpose method for modifying, and the method is not suitable for producing alkene.CN101027378A discloses a kind of method being prepared light alkene by Fischer-Tropsch synthetic, under the method is included in diluent gas material existent condition, evaporating a part of product is gas fraction and liquid distillate, and separating liquid cut and residual gas oil mixt, the remaining gas of further heating utilize steam cracking furnace to carry out thermal conversion step to obtain light alkene under oil mixt to raised temperature, the method utilizes thermal transition Fischer-Tropsch synthesis oil to produce low-carbon alkene.But above method mainly concentrates on the processing and utilization aspect to Low Temperature Fischer Tropsch synthetic oil, does not relate to the processing and utilization utilizing high temperature fischer-tropsch synthetic oil.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of catalysis processing method of high temperature fischer-tropsch synthetic oil, and the method is carried out catalyzed conversion to high temperature F-T synthetic method products therefrom and prepared low-carbon alkene, has higher productivity of propylene.
A kind of high temperature fischer-tropsch synthetic oil catalysis processing method, comprising:
(1) high temperature fischer-tropsch synthetic product is separated, obtains high temperature condensation product, the gentle state hydrocarbon of low temperature cold condensate;
(2) described hydrocarbon gas and described high temperature condensation product are introduced in the first riser reactor react with the catalyst exposure in introducing first riser reactor, form the first oil agent mixture;
(3) oil gas in the first described contaminated product agent compound and carbon deposited catalyst are carried out gas solid separation, the carbon deposited catalyst after separation introduces fluidized-bed reactor and/or stripper, and oil gas introduces product separation system;
(4) described low temperature cold condensate is introduced in the second riser reactor react with the catalyst exposure of introducing second riser reactor, form the second oil agent mixture; Then react in the fluidized-bed reactor described in the second oil agent mixture being introduced, reacted carbon deposited catalyst introduces stripper stripping, and reacted oil gas introduces product separation system;
Described catalyzer contains the zeolite that aperture is less than 0.7nm.
The catalysis processing method of high temperature fischer-tropsch synthetic oil provided by the invention, according to the feature of high temperature fischer-tropsch synthetic product, taking into full account fraction distribution, the productive rate of different boiling range product, olefin(e) centent, on the basis of the composition and properties such as oxygen level and reactivity worth, high temperature fischer-tropsch synthesis technique synthetic product is divided into hydrocarbon gas, high temperature condensation product and low temperature cold condensate three kinds of cuts, then selective conversion is carried out to different fractions oil, catalytic cracking technology is utilized to carry out catalytic reforming to high temperature F-T technique products therefrom, hydrocarbon gas, high temperature condensation product enters the first riser reactor and carries out catalyzed conversion, low temperature cold condensate and freshening pyrolysis gasoline cut enter combination bed reactor and transform, construct the processing variation route of a high temperature fischer-tropsch synthesis technique synthetic oil, there is higher productivity of low carbon olefin hydrocarbon and productivity of propylene, can obtain that there is lower olefin(e) centent and higher octane, meet the high-quality clean gasoline of environmental regulation, also can while low value products such as minimizing coke etc. the unbalanced problem of the not enough reaction heat of solving device green coke.
High temperature fischer-tropsch synthetic oil catalysis processing unit (plant) provided by the invention, comprises reactor, stripper, revivifier, settling vessel and catalyst mix heat-exchanger rig; Wherein, reactor adopts double lifting leg to add the combined reactor configuration of fluidized-bed formation, second riser reactor and fluidized-bed reactor combination bed reactor in series and the first riser reactor are in parallel and arrange, and described combination bed reactor is arranged with stripper height connected in series further; The shell side of described catalyst mix heat-exchanger rig is connected with stripper, tube side is connected with regenerated flue gas, the catalyst mix room of its underpart is connected with revivifier, make reuse regenerated catalyst can in the shell side of interchanger with regenerated flue gas heat exchange, and mix with regenerated catalyst in catalyst mix room, catalyst mix room is also communicated with the second riser reactor, makes mixed catalyst wherein can enter the second riser reactor.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet of catalysis processing method provided by the invention.Wherein 1 is riser reactor, and 2 is riser reactor, and 3 is fluidized-bed reactor, and 7 is stripper, and 8 is settling vessel, and 62 is product separation device, and 10 is revivifier, and 60 is catalyst mix interchanger.14 and 18 is reclaimable catalyst inclined tube (by guiding valve aperture control catalyst flow wherein, not marking in figure), and 15 and 17 is regenerated catalyst inclined tube (by guiding valve aperture control catalyst flow wherein, not marking in figure), and 16 is mixed catalyst transfer lime.Riser tube 2 and fluidized-bed 3 are coaxially connected in series through settling vessel 8 and realize being arranged in juxtaposition with riser tube 1, are connected with stripper 7 height is coaxial simultaneously; Riser tube 2 is connected with stripper 7 height is coaxial.
Embodiment
The catalysis processing method of high temperature fischer-tropsch synthetic oil provided by the invention, described high temperature fischer-tropsch synthetic oil synthesizes by existing method, usually, synthetic gas reacts by the method under certain pressure, temperature and catalyst action, then the reaction product obtained after reaction drawn reactor and be separated, obtaining hydrocarbon gas, low temperature cold condensate and high temperature condensation product.In described synthetic gas, the mol ratio of hydrogen/carbon monoxide is preferably 0.5 ~ 3.5, and the temperature of reaction of high temperature fischer-tropsch synthesis is preferably 260 ~ 375 DEG C, and more preferably 340 ~ 360 DEG C, reaction pressure is preferably 1.5 ~ 6MPa.Described high temperature fischer-tropsch synthesis can adopt paste state bed reactor, fixed-bed reactor, fluidized-bed reactor or magnetically stabilized bed reactor etc.Described Fischer-Tropsch synthesis oil product is the product that Fischer-Tropsch synthesis effluent mid-boiling point is not less than-2.3 DEG C.
In the catalysis processing method of high temperature fischer-tropsch synthetic oil provided by the invention, in wherein said hydrocarbon gas, the boiling point of material is not higher than 83 DEG C, and its boiling range is between-2.3 DEG C ~ 83 DEG C usually; In described low temperature cold condensate, the boiling range of material is between 40 DEG C ~ 300 DEG C; In described high temperature condensation product, the boiling point of material is not less than 210 DEG C, and usually described high temperature condensation product boiling range is between 210 DEG C ~ 600 DEG C.Reaction product separation is obtained described hydrocarbon gas by the method by fractionation, low temperature cold condensate and high temperature condensation product, method separation also by the method (the present invention is called natural separation) be directly separated by spontaneous for Fischer-Tropsch synthesis process product liquid obtains described material hydrocarbon gas, low temperature cold condensate and high temperature condensation product, the method is at the distinct device of high temperature fischer-tropsch synthesis process, obtain the logistics with differing temps, high temperature condensate stream, its temperature is 100 ~ 300 DEG C, pressure is 0.1 ~ 5.0MPa, this high temperature condensation product is at 20 DEG C, it is liquid state under 101.3kPa pressure, the logistics of low temperature cold condensate, its temperature is 0 ~ 60 DEG C, and pressure is 0.1 ~ 5.0MPa, and described low temperature cold condensate, at 20 DEG C, is liquid state under 101.3kPa pressure.Residue Fischer-Tropsch synthetic logistics after being separated after low temperature cold condensate and high temperature condensation product is further separated, isolate C3 hydrocarbon and the hydrocarbon mixture logistics be less than after C3 hydrocarbon component is described hydrocarbon gas, described hydrocarbon gas, at 20 DEG C, is gas-liquid mixture under 101.3kPa pressure
Normally, described synthetic gas transforms and generates synthetic oil in Fischer-Tropsch synthesis device, reaction product flows out reactive system, can will be that the product of liquid and the product of gas are drawn from the difference outlet of reactor under temperature of reaction and pressure, the product liquid of drawing is high temperature condensation product, the temperature of this liquid product stream is generally 100 ~ 300 DEG C, and pressure is 0.1 ~ 5.0MPa(gauge pressure); The high pressure condenser that the gaseous reaction product logistics of drawing introduces temperature lower is separated, be separated the liquid stream obtained and be low temperature cold condensate, the temperature of this liquid stream is generally 0 ~ 60 DEG C, pressure is 0.1 ~ 5.0MPa(gauge pressure), uncooled gaseous product is isolated wherein unconverted synthetic gas, C3 hydrocarbon wherein further and is less than C3 hydrocarbon (in hydrocarbon molecule, carbonatoms is less than 3), and the material that the boiling point obtained is greater than-2.3 DEG C is hydrocarbon gas.The reaction product of Fischer-Tropsch synthesis device also can all introduce high temperature condensation separator, liquid and high temperature condensation product and uncooled gaseous product is obtained in high temperature condensation separator, the temperature of liquid and high temperature condensate stream is generally 100 ~ 300 DEG C, and pressure is 0.1 ~ 5.0MPa(gauge pressure); Above-mentioned uncooled gaseous product introduces cryogenic condensation separator, be separated the liquid and low temperature cold condensate extraction cryogenic condensation separator that obtain, usually the temperature of this liquid stream is 0 ~ 60 DEG C, pressure is 0.1 ~ 5.0MPa(gauge pressure), uncooled gaseous product is isolated wherein after unconverted synthetic gas, isolate C3 hydrocarbon wherein again and be less than C3 hydrocarbon (in hydrocarbon molecule, carbonatoms is less than 3), obtaining the component that boiling point is greater than-2.3 DEG C is hydrocarbon gas.
The catalysis processing method of high temperature fischer-tropsch synthetic oil provided by the invention, preferably, after the synthetic product that described high temperature fischer-tropsch synthesis technique obtains draws Fischer-Tropsch synthesis device, separation obtains three fraction section: (1) first paragraph is called hydrocarbon gas (or being called HTFT hydrocarbon gas), its final boiling point is preferably 40 ~ 83 DEG C, initial boiling point is not less than-2.3 DEG C usually, and olefin(e) centent is very high; (2) second segment is called low temperature cold condensate (or being called HTFT low temperature cold condensate), and boiling range is placed in the middle, its initial boiling point preferably between 40 ~ 83 DEG C, final boiling point preferably between 210 ~ 300 DEG C, its olefin(e) centent and oxygen level higher; (3) the 3rd sections are called high temperature condensation product (or being called HTFT high temperature condensation product), and its boiling point is the highest, its initial boiling point preferably between 210 ~ 300 DEG C, final boiling point preferably more than 600 DEG C, olefin(e) centent and oxygen level higher.Preferred described separation makes high temperature condensation product account for 5 ~ 20 % by weight of described high temperature fischer-tropsch synthetic product, low temperature cold condensate accounts for 50 ~ 60 % by weight of described high temperature fischer-tropsch synthetic product, hydrocarbon gas accounts for 20 ~ 40 % by weight of described high temperature fischer-tropsch synthetic product, and its boiling range of described Fischer-Tropsch synthetic can be-2.3 ~ 600 DEG C.
Boiling range of the present invention is under absolute pressure is 101.3kPa condition, the boiling spread of oil or other hydrocarbon products.
In the catalysis processing method of high temperature fischer-tropsch synthetic oil provided by the invention, described hydrocarbon gas and high temperature condensation product can charging simultaneously or the different heights position chargings from the first riser tube, when while charging time can by the two mixing after introduce the first riser reactor, also can in the identical height location charging of the first riser tube.Preferably, first hydrocarbon gas is introduced in first riser reactor, then high temperature condensation product is introduced, preferably, the method comprises: be that the high-temperature regenerated catalyst of about 600 ~ 730 DEG C is incorporated into bottom the first riser tube by regenerator sloped tube by the temperature from revivifier, up under the effect promoting medium such as water vapour; Described hydrocarbon gas is disperseed and is introduced the first riser reactor under atomizing steam effect, contacts cracking reaction occurs with the described high-temperature regenerated catalyst of introducing first riser reactor, forms hydrocarbon gas and catalyst reaction mixture; Then in the first riser reactor, high temperature condensation product is introduced, with described hydrocarbon gas and catalyst reaction mixture contact reacts; By the first riser tube end tripping device, oil gas is separated with carbon deposited catalyst after reaction, oil gas is introduced product separation system separation and is obtained cracked gas, pressure gasoline, cracking light oil, after reaction, carbon deposition catalyst enters stripper or is introduced into fluidized-bed reactor and then enters stripper, after stripping, reclaimable catalyst part enters revivifier regeneration, and part enters catalyst heat exchange mixing tank.Described oil gas and catalyst separation device are fast separating device, in order to by reaction oil gas and carbon deposited catalyst sharp separation, can adopt existing fast separating device, and preferred fast packing is set to slightly revolves a point separator.By the first riser reactor end fast separating device, oil gas is separated with carbon deposited catalyst after reaction, dry gas yied can be reduced, suppress low-carbon alkene especially propylene transforming again after generating, improve small-numerator olefin productive rate, there are excessive hydrogen transference, aromatization etc. in the pyrolysis gasoline that simultaneously also can reduce generation, improve the olefin(e) centent of pyrolysis gasoline product, for pyrolysis gasoline second pyrolysis improves good raw material.The pyrolytic cracking catalyzer of described introducing first riser reactor and the weight ratio (being defined as the agent-oil ratio of hydrocarbon gas) of described introducing first riser reactor hydrocarbon gas are 7 ~ 39, preferably 10 ~ 30.The time of reacting with hydrocarbon gas described before high temperature condensate contact and described catalyst exposure is 0.0 ~ 1.0 second, is preferably 0.01 ~ 0.91 second.
In the catalysis processing method of high temperature fischer-tropsch synthetic oil provided by the invention, the first riser reactor reaction conditions is: temperature of reaction (outlet temperature of riser) is 490 ~ 600 DEG C, is preferably 530 ~ 580 DEG C; Total agent-oil ratio of the first riser reactor (introduce the ratio of catalyzer in the first riser reactor and the hydrocarbon gas in introducing first riser reactor and high temperature condensation product gross weight, the present invention claims the first agent-oil ratio) is 5 ~ 25, is preferably 7 ~ 20; Preferably, between the first riser reactor gaseous hydrocarbon inlet and outlet, introduce described high temperature condensation product, to contact with hydrocarbon gas the mixture formed with cracking catalyst and mix and react, then leave the first riser reactor, carry out gas solid separation.Before the first riser tube introduced by high temperature condensation product, hydrocarbon gas and catalyst exposure reaction times are 0.0 ~ 1.0 second, preferably 0.0 ~ 0.91 second, it can be such as 0.1 ~ 0.8 second or 0.2 ~ 0.6 second, high temperature condensation product is 0.50 ~ 10 second (calculating from the first riser tube introduced by high temperature condensation product) in the reaction times of the first riser reactor, is preferably 2 ~ 6 seconds; The atomized water steam of hydrocarbon gas accounts for 2 ~ 50 % by weight of its inlet amount, be preferably 10 ~ 25 % by weight, the atomized water steam of high temperature condensation product accounts for 2 ~ 50 % by weight of its inlet amount, is preferably 10 ~ 25 % by weight, reaction pressure is 0.15 ~ 0.3MPa, is preferably 0.18 ~ 0.25MPa.
The first hydrocarbon gas contact reacts under high agent-oil ratio condition with accounting for combined feed total feed 20 ~ 40 % by weight of the highly active regenerated catalyst of high temperature, ensure that the Efficient Conversion of hydrocarbon gas on the one hand, post catalyst reaction carbon deposit is little, and catalyzer still has very high reaction activity; The catalyst entrainment reaction oil gas reducing temperature on the other hand continues up, high temperature condensate contact heavy with accounting for combined feed total feed 5 ~ 20% again reacts, ensure that high temperature condensation product Efficient Conversion under high agent-oil ratio, the initial contact temperature of catalyzer and high temperature condensation product reduces, the overcracking of high temperature condensation product can be reduced, reduce green coke and dry gas, the high temperature condensation product of injection also stops small molecules hydro carbons Quench such as the propylene that hydrocarbon gas generates, transforming again after preventing its generation.
Containing the impurity of excess metal in described high temperature condensation product, described high temperature condensation product before entering the first riser reactor preferably through a hydrodemetallisation step, with remove with excess metal impurity.Described excess metal impurity refers to that in high temperature condensation product, content is greater than 6ppm(with metallic gauge) a certain metal or metallic compound, metal or the metallic compounds such as described metal such as iron, nickel, vanadium, sodium, potassium, cobalt, calcium.Described hydrodemetallisation step to select petroleum hydrocarbon process for demetalizating known in the art, can be the combination of one or more of electric desalting demetal process, absorption demetal process, hydrodemetallation (HDM) technique etc.The content of the arbitrary metallic impurity in described high temperature condensation product is such as no more than 5 μ g/g preferably more than 6 μ g/g.To accounting for the total logistics of sintetics about 5 ~ 20% weight, and the higher high temperature condensation product of heavy metal content enters alone demetalization device/desalting plant, remove the metallic impurity that it is excessive, reduce on the one hand metallic impurity from F-T synthesis device to the toxic action of catalyzer, extend the work-ing life of catalyzer, another side, the gentle state hydrocarbon of low temperature cold condensate of the present invention is without the need to directly entering catalysis processing unit (plant) through demetal process, less to charging, the high temperature condensation product that heavy metal content is higher enters alone demetalization device can reduce demetallated energy consumption, thus be conducive to the total energy consumption reducing device.After adopting demetalization process, Fischer-Tropsch synthetic has low-sulfur, low nitrogen, low metallic character, for follow-up catalytic pyrolysis conversion process provides the charging of high-quality, effectively reduces the running cost in catalytic conversion process and product subsequent operations cost.
In the catalysis processing method of high temperature fischer-tropsch synthetic oil provided by the invention, low temperature cold condensate is introduced the bottom of the second riser tube, react with the catalyst exposure of introducing second riser tube, then catalyzer and oil gas leave the second riser reactor and enter fluidized-bed reactor reaction.The temperature of reaction (temperature out) of the second riser reactor is preferably 490 ~ 600 DEG C, more preferably 535 ~ 575 DEG C; Operation agent-oil ratio is 10 ~ 30, and be preferably 12 ~ 20, the riser tube reaction times is 0.10 ~ 1.5 second, preferably 0.40 ~ 1.1 second.The temperature of reaction of fluidized-bed reactor is 500 ~ 600 DEG C, is preferably 525 ~ 565 DEG C; Weight hourly space velocity is 1 ~ 35 hour
-1, be preferably 3 ~ 15 hours
-1; Reaction pressure is 0.15 ~ 0.3MPa(absolute pressure), be preferably 0.18 ~ 0.25MPa(absolute pressure).
In the catalysis processing method of high temperature fischer-tropsch synthetic oil provided by the invention, reaction oil gas is separated with carbon deposited catalyst by the tripping device of the first riser reactor end, and oil gas product is introduced product separation system and is separated; The carbon deposited catalyst that separation obtains directly can be introduced stripping system and carry out stripping, also can first introduce in fluidized-bed reactor, with the catalyst mix in fluidized-bed reactor, participate in reaction in a fluidized bed reactor, and then enter stripping system and carry out stripping, enter stripper again after preferably first introducing fluidized-bed reactor and carry out stripping.The reacted oil gas of fluidized-bed reactor, from fluidized-bed Base top contact, is introduced into settling vessel, after the settlement separate catalyzer going out wherein to carry, then enters product separation system; The reacted catalyzer of fluidized-bed reactor leaves from the bottom of fluidized-bed, enters stripper and carries out stripping.Like this, two strands of catalyzer stripping in same stripper of the first riser reactor and introducing the second riser reactor is introduced.Revivifier regeneration all introduced by catalyzer in stripper after stripping, or a part introduces catalyst mix interchanger, a part introduces revivifier regeneration, and catalyst recirculation to the first riser reactor after regeneration and the second riser reactor recycle.Two strands of oil gas products are isolated to cracked gas, pyrolysis gasoline, cracking light oil and cracking masout etc.The oil gas product of the first riser reactor and the oil gas product of fluidized-bed reactor share product separation system.Described product separation system is prior art, and the present invention does not have particular requirement.
Catalyzer (reclaimable catalyst) after the stripping that stripper is drawn is containing carbon deposit, and it partly or entirely introduces revivifier regeneration with removing coke wherein, and the catalyst recirculation after regeneration uses.When revivifier regeneration all introduced by the catalyzer after the stripping of drawing from stripper time, because the content of high temperature condensation product is lower, catalyzer after the stripping that stripper is drawn, coke content is low compared with conventional catalytic cracking, in order to ensure regeneration effect and provide enough heat of reaction to reactive system, need to heat in regenerative process, can be heated by existing method, such as, in revivifier, spray into oil fuel.
In order to improve regeneration effect and reduce energy consumption, reuse to the second riser reactor after a part for the reclaimable catalyst after the stripping of drawing from stripper heats up by the present invention.Like this, the carbon content entering the reclaimable catalyst of revivifier can suitably improve, and the amount of regenerated catalyst reduces, and can reduce regeneration air consumption, keeps higher regeneration temperature to ensure regeneration effect, surprisingly can also improve the productive rate of propylene.Under preferable case, by the overheated flue gas heating that the reclaimable catalyst revivifier of reuse produces, after then mixing with regenerated catalyst, introduce the second riser reactor.A part for reclaimable catalyst is introduced the second riser reactor and low temperature cold condensate reacts after heating up, namely the catalyzer introducing the second riser reactor comprises reclaimable catalyst and regenerated catalyst, the weight ratio of wherein said reclaimable catalyst and described regenerated catalyst is 1:100 ~ 100:1, is preferably 20:80 ~ 80:20.Introduce the second riser reactor by after reclaimable catalyst and regenerated catalyst mixing, mixed catalyst temperature is 550 ~ 700 DEG C, preferably 580 ~ 690 DEG C.Under preferable case, be 0.01 ~ 1.00 % by weight from the carbon content of the reclaimable catalyst of stripper extraction; More preferably, carbon content is 0.20% ~ 0.60 % by weight.
Lower from the temperature of the reclaimable catalyst of stripper extraction, be generally about 400 ~ 560 DEG C, when the reclaimable catalyst of reuse and the ratio of regenerated catalyst lower time, its temperature can be raised by mixing with regenerated catalyst, but when its content is higher time, the catalyst temperature entering the second riser tube can be caused lower, need to heat it for this reason, or oil fuel generation heat can be utilized to heat by electrically heated, in order to reduce energy consumption, can be heated by regenerated flue gas.Carry out heating with regenerated flue gas and can carry out heat exchange by catalyst mix heat-exchange system, described catalyst mix heat-exchange system at least comprises catalyst heat exchange part and catalyst mix part.Catalyst heat exchange part can adopt the combination of one or more in the forms such as recuperative heat exchanger, direct contact heat exchanger, tube and shell heat exchanger, double-pipe exchanger, plate-type heat exchanger.Catalyst mix part can adopt container to mix, and passes into loosening gas in a reservoir with the mixing of promoting catalyst.Described catalyst mix part can be arranged on catalyst heat exchange device bottom, perpendicular series connection formation entirety, also can arrange separately, be connected with interchanger by pipeline, preferably catalyst mixing zone is set in catalyst heat exchange device vertical lower and carry out catalyst mix.Preferably, described heating makes the temperature of the catalyzer after the stripping of reuse and regeneration catalyzing agent composition be 550 ~ 700 DEG C, preferably 580 ~ 690 DEG C.The selective catalysis reactive behavior that this method can effectively utilize the dump energy of this device generation flue gas and reclaimable catalyst to possess, improve the initial reaction temperature of reclaimable catalyst/or the mixed catalyst entered in the second riser reactor, for the efficient selective conversion of low temperature cold condensate and freshening petroleum naphtha provides excellent reaction environment and adequate reaction heat.Also solve because each raw material of high temperature fischer-tropsch product accounts for the feature (heavy constituent high temperature condensation product only accounts for 5 ~ 20% weights of combined feed total feed) of weight distribution in total logistics simultaneously, cause whole reaction-regeneration system green coke not enough but double lifting leg adds fluidized-bed forms combined reactor and need more reaction heat to cause the unbalanced problem of reaction-regeneration system heat, ensure can provide sufficient reaction heat for auxiliary riser line reactor charging and meet the heat balance of whole device while reducing the low value products such as coke.
A kind of concrete mode heated by catalyzer after the stripping of reuse as shown in Figure 1, reclaimable catalyst from reclaimable catalyst transfer lime 14 enters in the shell side of catalyst mix interchanger 60 top and from up to down flows, draw one high-temperature flue gas of more than 700 DEG C from regenerator overhead regenerated flue gas outlet line 41 and enter mixed heat exchanger 60 through pipeline 79, from bottom to top by the tube side of described interchanger 60, mixed heat exchanger 60 bottom is entered after the reclaimable catalyst of reuse and the abundant heat exchange of high-temperature flue gas, mixed heat exchanger 60 lower position is introduced in high temperature regeneration agent from regenerated catalyst 17, the bottom of catalyst mix interchanger 60 is catalyst mix room, under the effect of loosening gas 61, reclaimable catalyst after regenerated catalyst and heat exchange fully mixes, mixed catalyst enters the second riser reactor 2 by transfer lime 16, contact with low temperature cold condensate and carry out conversion reaction or also contact with freshening petroleum naphtha carrying out conversion reaction.
In order to low-carbon olefines high-output, improve productivity of propylene, partial cracking petroleum naphtha from product separation system is introduced the second riser reactor from the bottom of the second riser reactor or middle and lower part react, postmedian or the fluidized-bed that also the cracking masout from fractionating system can be introduced the second riser reactor participate in reaction simultaneously.Reacted hydrocarbon product is introduced product separation system and is obtained cracked gas, pyrolysis gasoline, cracking light oil and cracking masout, and carbon deposited catalyst introduces revivifier regeneration after stripper stripping.In combination bed reactor, riser tube temperature of reaction (temperature out) is 490 ~ 600 DEG C, preferably 535 ~ 575 DEG C; Agent-oil ratio (introducing the catalyzer of the second riser reactor and the introducing described low temperature cold condensate of the second riser reactor and the weight ratio of described petroleum naphtha sum) is 10 ~ 30, is preferably 12 ~ 20; The riser tube reaction times is 0.10 ~ 1.5 second, preferably 0.40 ~ 1.1 second.The temperature of reaction of fluidized-bed reactor is 500 ~ 600 DEG C, is preferably 525 ~ 565 DEG C; Weight hourly space velocity is 1 ~ 35 hour
-1, be preferably 3 ~ 15 hours
-1; Reaction pressure (top hole pressure, absolute pressure) is 0.15 ~ 0.3MPa(absolute pressure), be preferably 0.18 ~ 0.25MPa(absolute pressure).Cracking masout is introduced the second riser reactor and is transformed, realize on the one hand heavy oil twice transformation improve whole device the heavy oil conversion degree of depth, utilize cracking masout cut propylene enhancing, the Quench of low temperature cold condensate and the reaction of cracking petroleum naphtha is stopped simultaneously, suppress low-carbon alkene, especially the conversion reaction again after propylene generation, thus reduce dry gas and coke yield further while effectively keeping high productivity of propylene.
In the catalysis processing method of high temperature fischer-tropsch synthetic oil provided by the invention, what described catalyzer contained that mean pore size is less than 0.7 nanometer selects shape zeolite, the shape zeolite of selecting that described mean pore size is less than 0.7 nanometer is selected from ZSM series zeolite, ZRP zeolite, ferrierite, chabazite, dachiardite, erionite, A zeolite, epistilbite, lomontite, and one or more the mixture among the above-mentioned zeolite obtained after physics and/or chemical process process.Described ZSM series zeolite is selected from one or more the mixture in the zeolite of ZSM-5, ZSM-8, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, ZSM-38, ZSM-48 and other similar structures.About the more detailed description of ZSM-5 is see USP3702886, about the more detailed description of ZRP is see USP5232675, CN1211470A, CN1611299A.
The described shape-selective zeolite catalysts being less than 0.7 nanometer containing mean pore size can be the combination of one or more of the cracking catalyst provided by prior art, can be purchased or prepare according to existing method.Described catalyzer contains zeolite, inorganic oxide and optional clay, wherein contain: 5 ~ 50 % by weight zeolites, 5 ~ 95 % by weight inorganic oxides and 0 ~ 70 % by weight clay, what described zeolite comprised that mean pore size is less than 0.7 nanometer selects shape zeolite and optional large pore zeolite, described mean pore size is less than select that shape zeolite accounts for zeolite total amount 25 ~ 100 % by weight of 0.7 nanometer, preferably 50 ~ 100 % by weight, large pore zeolite accounts for 0 ~ 75 % by weight of zeolite total amount, and preferably 0 ~ 50 % by weight.
Described large pore zeolite is the zeolite of the cavernous structure with at least 0.7 nano-rings opening, is selected from one or more the mixture in y-type zeolite, zeolite beta, zeolite L, rare earth Y type zeolite (REY), rare earth hydrogen y-type zeolite (REHY), ultrastable Y－type zeolite (USY), extremely steady y-type zeolite of rare earth (REUSY).
Described inorganic oxide, as caking agent, is selected from silicon-dioxide (SiO
2) and/or aluminium sesquioxide (Al
2o
3).Described clay is as matrix, i.e. carrier, can be selected from kaolin and/or halloysite.
In the catalysis processing method of high temperature fischer-tropsch synthetic oil provided by the invention, described riser reactor be selected from equal diameter riser tube, etc. a kind of in linear speed riser tube and variable diameters riser tube or the wherein combination of two kinds, the riser reactor wherein in auxiliary riser line reactor and combination bed reactor can adopt identical pattern also can adopt different patterns.Described fluidized-bed reactor is selected from the combination of one or more in fixed fluidized bed, dispersion fluidized bed, bubbling bed, turbulent bed, fast bed, conveying bed and dense bed reactor.
In the catalysis processing method of high temperature fischer-tropsch synthetic oil provided by the invention, the conversion system used at least comprises reactor part, regenerator section, product separation system and catalyst mix heat-exchange system, the combined reactor configuration that reactor adopts double lifting leg and fluidized-bed to be formed, one of them riser tube is arranged in juxtaposition mutually with another one riser tube after coaxially connecting with fluidized-bed reactor, and described subsidiary riser with the coaxial cascaded structure of fluidized-bed reactor further with stripper coaxial height coupled arrangement.
Described riser tube is with the coaxial series combination of fluidized-bed reactor, and leg outlet preferably arranges low tension outlet sparger, and its pressure drop is less than 10KPa.Described low tension outlet sparger such as arch sparger.
Below in conjunction with accompanying drawing, method provided by the present invention is further described:
The synthetic product of high temperature fischer-tropsch synthesizer is separated, obtain hydrocarbon gas, low temperature cold condensate and high temperature condensation product, as shown in Figure 1, hydrocarbon gas introduces the riser reactor 1 of catalytic convention design by pipeline 24, and low temperature cold condensate introduces catalytic convention design riser reactor 2 by pipeline 23; High temperature condensation product makes the content of wherein arbitrary metallic impurity preferably all be no more than 6 μ g/g through demetalization system (not marking in figure) process, preferably more than 5 μ g/g, then introduces riser reactor 1 by pipeline 25.
High-temperature regenerated catalyst from revivifier 10 divides secondary air to reactor assembly, first stock-traders' know-how regenerator inclined tube 15 enters bottom riser reactor 1, accelerate upwards to flow under the pre-lift medium effect of being injected by pipeline 46, second stock-traders' know-how regenerator inclined tube 17 introduces catalyst mix interchanger 60 bottom position, to introduce in the shell side of catalyst mix interchanger 60 top through transfer lime 14 from the reclaimable catalyst part after the stripping of stripper 7 and from up to down flow, introduce the tube side of catalyst mix interchanger 60 through pipeline 79 from one high-temperature flue gas of regenerator overhead outlet extraction, from bottom to top by catalyst mix interchanger 60, high-temperature flue gas after heat exchange is drawn by pipeline 80, after the reclaimable catalyst of reuse and the abundant heat exchange of high-temperature flue gas, enter the bottom of mixed heat exchanger 60, mix with the regenerated catalyst from regenerator inclined tube 17 under the loosening gas introduced through pipeline 61 (can be rare gas element, water vapour) effect, mixed catalyst enters bottom riser reactors 2 via transfer lime 16, accelerates upwards to flow under the pre-lift medium effect of being injected by pipeline 45.
Hydrocarbon gas and high temperature condensation product can be introduced in riser reactor 1 in riser reactor 1 middle and lower part, the two can introduce riser reactor 1 in the equal height position of riser reactor 1, also can be to introduce riser reactor 1 in the different heights position of riser reactor 1.Introduce in equal height position, can be introduce after the two mixing, also can be the two introduced from different intakes.Preferably, the hydrocarbon gas being delivered to riser reactor 1 through pipeline 24 injects riser reactor 1 bottom under from the atomizing steam effect of pipeline 50, contact with the regenerated catalyst introducing riser reactor 1, reaction, oil gas carries catalyzer and upwards flows, with be delivered to riser reactor 1 through pipeline 25 and the high temperature condensate contact injecting riser reactor 1 under from the atomizing steam effect of pipeline 53 carries out cracking reaction, reaction oil gas and catalyst mixture are introduced and are separated with carbon deposited catalyst after reaction by oil gas with the fast separating device of riser reactor 1 outlet, isolated carbon deposited catalyst is introduced stripper 7 or is first introduced fluidized-bed reactor 3 and enters stripper from fluidized-bed reactor 3 again, stripping is clean as much as possible by the reaction oil gas entrained by carbon deposited catalyst for the stripping steam injected through pipeline 46, stripping oil gas enters reacting-settler 8 after fluidized-bed 3, after top cyclone separation system is collected, draw reactor through pipeline 29 and enter product separation system 62 together with other oil gas.
Injecting lift pipe reactor 2 bottom after the low temperature cold condensate of pipeline 23 conveying mixes with the atomizing steam from pipeline 52, with the catalyst exposure introduced in riser reactor 2, reaction, the oil gas formed and catalyst mixture enter fluidized-bed reactor 3 subsequently and react, the oil gas leaving fluidized-bed reactor 3 enters settling vessel 8, and the catalyzer leaving fluidized-bed reactor 3 enters stripper 7.
In order to propylene enhancing, cracking petroleum naphtha injects riser reactor 2 through pipeline 36 under from a certain proportion of atomizing steam effect of pipeline 51, preferred decanting point is in the middle and lower part (described middle and lower part is between the catalyst inlet of 1/2 place of riser tube 2 height to riser tube 2) of riser reactor 2, react with the catalyst exposure in riser reactor 2, reaction oil gas and catalyst mixture upwards flow along riser tube 2, reaction oil gas and catalyst mixture continue reaction after the outlet distributor of riser reactor 2 enters fluidized-bed reactor 3, oil gas enters settling vessel 8 and carries out being separated of oil gas and catalyzer from the top of fluidized-bed reactor 3.The cracking masout of drawing through pipeline 33 injects combination cot layer reactor (riser reactor 2 and fluidized-bed 3 are also referred to as combination bed reactor) under atomizing steam effect, carries out cracking reaction.All hydrocarbon oil product, are comprised the oil gas of riser reactor 1 and are all collected by settling vessel top cyclone separation system from the oil gas that fluidized-bed reactor 3 flows out, introducing subsequent product separation system 62 by pipeline 29.In product separation system 62, catalytic cracking production is separated into reacted gas (being drawn by pipeline 30), pyrolysis gasoline (being drawn by pipeline 31), cracking light oil (being drawn by pipeline 32), cracking masout (being drawn by pipeline 33) and cracking slurry oil (being drawn by pipeline 34).The reacted gas that pipeline 30 is drawn is separated at subsequent product, refining after can obtain polymerization-grade propylene product and be rich in the C 4 fraction of alkene.The pyrolysis gasoline that pipeline 31 is drawn can be separated into pyrolysis gasoline (boiling range is 30 ~ 85 DEG C), cracking heavy petrol further, pyrolysis gasoline returns to riser tube 2 bottom or middle and lower part transforms again, and cracking heavy petrol or pyrolysis gasoline can be used as clean gasoline blend component or as aromatics extraction raw material; The cracking light oil that pipeline 32 is drawn can be used as clean fuel oil or as clean diesel blend component.
Introduce stripper 7 through the isolated carbon deposited catalyst of the fast separating device of riser reactor 1 end or introduce oil gas that fluidized-bed reactor 3 and riser reactor 2 export and catalyzer mix, react after introduce stripper 7.The stripped vapor that pipeline 46 injects in stripper and catalyzer counter current contact, by the reaction oil gas entrained by carbon deposited catalyst, stripping is clean as much as possible, and stripped oil gas flows into reacting-settler 8, introduces product separation system 62 together with other oil gas through pipeline 29.Catalyst member after stripping sends into revivifier 10 coke burning regeneration by spent agent inclined tube 18, and the catalyst member after stripping is sent into catalyst mix interchanger 60 with high-temperature flue gas heat exchange by spent agent inclined tube 14 and entered riser reactor 2 after mixing with second strand of regenerated catalyst.
Oxygen-containing gas such as air injects revivifier 10 through pipeline 42, and regenerated flue gas is drawn through pipeline 41.Catalyzer after regeneration returns riser reactor 1 respectively through regenerator inclined tube 15,17 and riser reactor 2 recycles.
Introduce pre-lift medium by pipeline 46,45 respectively to riser tube 1, riser tube 2, introduce loosening gas medium by pipeline 61 to catalyst mix exchanger base.Described pre-lift medium and loosening gas medium are known for those skilled in the art, can be selected from one or more in water vapour, C1 ~ C4 hydro carbons or Conventional catalytic cracking dry gas.
The following examples will be further described the present invention.
The raw material used in embodiment and comparative example comprises raw material 1-1, raw material 1-2, raw material 1-3 and raw material 2-1.Raw material 1-1 is hydrocarbon gas, and raw material 1-2 is low temperature cold condensate, and raw material 1-3 is high temperature condensation product, and raw material 2-1 is the pyrolysis gasoline product that embodiment 2 products obtained therefrom is isolated to, and specific nature is in table 1.The catalyzer adopted is the trade names that Sinopec catalyzer asphalt in Shenli Refinery produces is the cracking catalyst of MMC-2, and its specific nature is in table 2, and what this catalyzer was less than 0.7nm containing mean pore size selects shape zeolite.The synthesis temperature of this Fischer-Tropsch synthetic is 350 DEG C, and pressure is 2.0MPa, fixed-bed reactor, and catalyzer is fused iron catalyst.High temperature condensation product be from Fischer-Tropsch synthesis device draw synthetic product pressure is 0.4MPa, temperature is the product liquid separated at 300 DEG C, low temperature cold condensate is that reactant flow after isolating high temperature condensation product is at pressure 0.1MPa, temperature is that the light pressure separator at 60 DEG C is separated the liquid obtained, and hydrocarbon gas is the synthetic product after not condensate in light pressure separator isolates F-T synthesis raw material.
Regenerated catalyst the present invention is also called for short regenerator, and reclaimable catalyst the present invention is also called for short spent agent.Second riser tube and the present invention of fluidized-bed tandem reactor are also referred to as combining bed reactor.
Embodiment 1
The present embodiment, in order to illustrate that high temperature fischer-tropsch synthesis technique is obtained sintetics and is separated into different fractions section raw material by method provided by the invention, enters differential responses district catalytic pyrolysis effect separately.
Experiment is carried out in middle scale riser catalytic cracking unit.As shown in Figure 1, this middle-scale device riser reactor 1 internal diameter is 16 millimeters, length is 3800 millimeters, the internal diameter of riser reactor 2 is 16 millimeters, length is 3200 millimeters, and riser reactor 2 exports and connects dense fluidized bed bioreactor, and the internal diameter of fluidized-bed reactor is 64 millimeters, height 600 millimeters, test adopts the operation of one way pass-through mode.The high temperature regeneration agent of 700 DEG C is introduced bottom riser reactor 1 and 2 by revivifier respectively through regenerator sloped tube, and upwards flows under the effect of pre-lift medium.Raw material 1-1 through be preheated to 60 DEG C mix with atomized water steam after, enter riser reactor 1 by feed nozzle to contact carry out catalytic conversion reaction with the regenerator of heat, the mixture of reaction oil gas and catalyzer is up, raw material 1-3 through be preheated to 150 DEG C mix with atomized water steam after, enter to contact with catalyst mixture with described up oil gas in the middle part of riser reactor 1 by feed nozzle and carry out catalytic conversion reaction, the mixture of reaction oil gas and catalyzer continues to carry out gas solid separation along the up sharp separation equipment by outlet of riser reactor 1, reaction oil gas is introduced settling vessel and is then introduced product separation system separation.Raw material 1-2 through be preheated to 90 DEG C mix with atomized water steam after, enter riser reactor 2 bottom by feed nozzle to contact carry out catalytic conversion reaction with the regenerator of heat, the mixture of reaction oil gas and catalyzer enters fluidized-bed reactor 3 continuation participation cracking reaction along riser reactor 2 is up by riser reactor 2 outlet, and then reaction oil gas introducing settling vessel is introduced product separation system and be separated into gas and product liquid.From riser reactor 1 the catalyzer (spent agent) containing coke because of action of gravity first fall into fluidized-bed reactor 3 with from the catalyzer of riser reactor 2 and air-fuel mixture, then enter the stripper 7 communicated with fluidized-bed, water stripping steam stripping goes out spent agent enters settling vessel by fluidized-bed after adsorbs hydrocarbons product to carry out gas solid separation.Spent agent after stripping enters revivifier by spent agent inclined tube, is contacted with 700 DEG C of high temperature coke burning regenerations with air.Catalyzer after regeneration returns in riser reactor through regenerator sloped tube and recycles.The mode that revivifier passes through to spray into combustion oil in revivifier for the energy maintained needed for regeneration temperature is supplemented, and the amount of made-up fuel oil is equivalent to 2.7% ~ 3.0% of device total feed.
Embodiment 2
The present embodiment illustrates that the catalyzer introducing riser reactor 2 is the effect of the mixed catalyst of regenerator and spent agent.
Experimental installation is roughly the same with embodiment 1.Raw material 1-1 through be preheated to 120 DEG C mix with atomized water steam after, enter riser reactor 1 by feed nozzle contact with the regenerator of heat and carry out catalytic conversion reaction, the mixture of reaction oil gas and catalyzer is up, raw material 1-3 through be preheated to 250 DEG C mix with atomized water steam after, enter in riser reactor 1 to contact with catalyst mixture with described up reaction oil gas by feed nozzle and carry out catalytic conversion reaction, the reaction oil gas formed and the mixture of catalyzer continue up along riser reactor 1, the sharp separation equipment exported by being arranged on riser reactor 1 carries out gas solid separation, reaction oil gas after separation is introduced product separation system and is separated into gas and product liquid, catalyzer after separation enters fluidized-bed reactor 3.Raw material 1-2 through be preheated to 195 DEG C mix with atomized water steam after, enter riser reactor 2 by feed nozzle and introduce reclaimable catalyst wherein and to contact with the mixture of regenerated catalyst and carry out catalytic conversion reaction, the mixture of reaction oil gas and catalyzer enters fluidized-bed reactor 3 by riser reactor 2 outlet proceed cracking reaction along riser reactor 2 is up, the reaction oil gas of fluidized-bed reactor 3 introduces settling vessel, then introduces product separation system and is separated into gas and product liquid.
Riser reactor 1 containing after catalyzer and the gas-oil separation of coke, first fall into fluidized-bed reactor 3 because of action of gravity and the catalyzer that exports from riser reactor 2 and air-fuel mixture; The catalyzer containing coke in fluidized-bed reactor 3 flows into stripper 7 because of action of gravity, and water stripping steam stripping goes out spent agent enters settling vessel by fluidized-bed after adsorbs hydrocarbons product to carry out gas solid separation; Spent agent after stripping, together introduces in riser reactor 2 after part mix with regenerator by catalyst mix interchanger 60 heat exchange intensification, partly to be contacted with air by inclined tube introducing revivifier to be generated and carries out high temperature coke burning regeneration.Catalyst recirculation after regeneration uses.The mass ratio entering spent agent and regenerator in the catalyzer of riser reactor 2 is 50:50.
Comparative example 1
This comparative example illustrates that high temperature fischer-tropsch synthesis technique obtains raw material and adds bed reactor catalysis cracker reaction result at Conventional riser.
Experiment is carried out in middle scale riser catalytic cracking unit.The internal diameter of this middle-scale device riser reactor is 16 millimeters, is highly 3200 millimeters, and leg outlet connects fluidized-bed reactor, and the internal diameter of fluidized-bed reactor is 64 millimeters, height 600 millimeters.Test adopts the operation of one way pass-through mode.The high temperature regeneration agent of 700 DEG C is introduced bottom riser reactor by revivifier through regenerator sloped tube, and upwards flows under the effect of pre-lift medium.Raw material 1-1, raw material 1-2, raw material 1-3 are after preheating mixes with atomized water steam, jointly enter riser reactor bottom by feed nozzle to contact with hot regenerator and carry out catalytic conversion reaction, the mixture of reaction oil gas and catalyzer enters fluidized-bed reactor 3 continuation participation cracking reaction along riser reactor 2 is up by outlet, and then reaction oil gas introducing settling vessel is introduced product separation system and be separated into gas and product liquid.The catalyzer (spent agent) containing coke from fluidized-bed reactor 3 flows into stripper 7 stripping because of action of gravity, flow into settling vessel through fluidized-bed reactor after water stripping steam stripping goes out the hydrocarbon product that reclaimable catalyst adsorbs and carry out gas solid separation, spent agent after stripping enters revivifier by inclined tube to be generated, contacts carry out high temperature coke burning regeneration with air.Catalyzer after regeneration returns in riser reactor through regenerator sloped tube and recycles.
Embodiment 3
As described in Example 2, riser reactor 2 bottom (introducing at identical height location with raw material 1-2) is introduced afterwards unlike being mixed with raw material 1-2 by freshening pyrolysis gasoline (boiling range 32 ~ 88 DEG C).The mixture of reaction oil gas and catalyzer enters fluidized-bed reactor 3 continuation participation cracking reaction along riser reactor 2 is up by riser reactor 2 outlet, and reaction oil gas introduces settling vessel, then introduces product separation system and is separated into gas and product liquid.The part by weight that freshening pyrolysis gasoline accounts for combined feed total feed (comprising raw material 1-1, raw material 1-2 and raw material 1-3) is 10%.
Embodiment 4
As described in Example 3, unlike raw material 1-1(hydrocarbon gas) with raw material 1-3(high temperature condensation product) mix after introduce the first riser reactor bottom and participate in reacting.
Comparative example 2
As described in Example 3, introduce the second riser reactor bottom unlike raw material 1-1 (hydrocarbon gas) and participate in reaction.
Comparative example 3
As described in Example 1, the ratio of raw material 1-1, raw material 1-2, raw material 1-3 charging is 30:15:55.
Embodiment 5 and embodiment 6
As described in Example 3, the weight ratio unlike the reclaimable catalyst entered in the second riser reactor and regenerated catalyst is respectively 80:20 and 20:80.The present embodiment further illustrates and utilizes method provided by the invention to obtain the effect of different fractions section raw material at differential responses district catalytic pyrolysis to high temperature fischer-tropsch synthesis technique, and the reaction effect of the part by weight scope of the reclaimable catalyst entered in the second riser reactor and regenerated catalyst.Under this experiment condition, embodiment 5 is by after high-temperature flue gas and reclaimable catalyst heat exchange, further with raw material 1-1, the heat exchange of raw material 1-2 lighter hydrocarbons, ensure that the thermal equilibrium of whole device, without the need to increasing external heat source heating, as sprayed into external fuel wet goods in a regenerator, maintaining device simultaneously and obtaining comparatively high productivity of propylene.Embodiment 6 is obtained outside part of heat energy by flue gas heat exchange, also needs to spray into revivifier the oil fuel being equivalent to device feed weight 1.5% ~ 2% further, but this numerical value is lower than the quantity 2.7% ~ 3.0% of extra fuel oil during smokeless heat-exchanging process in embodiment 1.
Embodiment 7 and embodiment 8
As described in Example 3, the temperature unlike the mixed catalyst entered in the second riser tube is respectively 580 DEG C and 640 DEG C.The present embodiment further illustrates and utilizes method provided by the invention to obtain the effect of different fractions section raw material at differential responses district catalytic pyrolysis to high temperature fischer-tropsch synthesis technique, and enters the preferred start temperature ranges of mixed catalyst in the second riser reactor.Under this experiment condition, embodiment 8 is by after high-temperature flue gas and reclaimable catalyst heat exchange, further with raw material 1-1, raw material 1-2 heat exchange, ensure that the thermal equilibrium of whole device, without the need to increasing external heat source heating (such as spraying into external fuel wet goods in a regenerator), maintaining device simultaneously and obtaining comparatively high productivity of propylene.Embodiment 7 obtains outside part of heat energy by flue gas heat exchange, also need to spray into revivifier the 1.3% ~ 1.6%(weight being equivalent to device inlet amount further) oil fuel, but this numerical value is lower than quantity 2.7% ~ 3.0%(weight of extra fuel oil during smokeless heat-exchanging process in embodiment 1).
Embodiment 1 ~ 2, comparative example 1 the results are shown in Table 3;
Embodiment 3 ~ 4, comparative example 2 ~ 3 the results are shown in Table 4;
Embodiment 5 ~ 8 the results are shown in Table 5.
Embodiment 9
The catalyzer that the present invention introduces the second riser tube is all reclaimable catalyst.
From table 3 ~ table 5, the inventive method has higher propene yield, and can reduce dry gas and coke yield.Such as embodiment 1 is compared with comparative example 1, and productivity of propylene increases by 2.71 weight percent points, and total low-carbon alkene (C2 ~ C4) adds 5.4 weight percent points, and the productive rate of low-value product dry gas and coke declines 0.19 and 0.95 weight percent point respectively.Under this experiment condition, embodiment 2, embodiment 3, embodiment 4, embodiment 5, embodiment 8, embodiment 9 by high-temperature flue gas in reclaimable catalyst mixed heat exchanger after heat exchange, ensure that the thermal equilibrium of whole device, such as spraying into external fuel wet goods in a regenerator without the need to increasing external heat source heating, maintaining device simultaneously and obtaining higher conversion and productivity of propylene.Embodiment 6 and embodiment 7 obtain outside part of heat energy by flue gas heat exchange, also need further to revivifier spray into be equivalent to device inlet amount 1.5% ~ 2% oil fuel, but this numerical value is lower than the quantity 2.7% ~ 3.0% of extra fuel oil during smokeless heat-exchanging process in embodiment 1.
Table 1
Table 2
Table 3
| Case | Comparative example 1 | Embodiment 1 | Embodiment 2 |
| Feed weight ratio: raw material 11/ raw material 1-2/ raw material 1-3 | 30:55:15 | 30:55:15 | 30:55:15 |
| Pyrolysis gasoline is to the recycle ratio/% of catalysis combined feed total feed | / | / | / |
| Catalyzer | MMC-2 | MMC-2 | MMC-2 |
| Regeneration temperature/DEG C | 700 | 700 | 700 |
| Reaction pressure (table), atm | 1.1 | 1.1 | 1.1 |
| Riser tube 1 temperature of reaction/DEG C | / | 560 | 560 |
| Riser tube 1 reacts total agent-oil ratio/weight ratio | / | 10 | 10 |
| Raw material 1-1 agent-oil ratio/weight ratio | / | 15 | 15 |
| Raw material 1-1 atomized water steam rates/% by weight | 12 | 12 | 12 |
| Raw material 1-3 atomized water steam rates weight/% | 24 | 24 | 24 |
| The riser tube 1 raw material 1-3 reaction times, second | / | 2.53 | 2.53 |
| The reaction times of raw material 1-1 before contact raw material 1-3, second | / | 0.31 | 0.31 |
| Raw material 1-2 atomized water steam rates/% by weight | 24 | 24 | 24 |
| Riser tube 2 temperature out/DEG C | 575 | 575 | 545 |
| The riser tube 2 reactor reaction time, second | 0.83 | 0.84 | 0.84 |
| Fluidized-bed reaction temperature/DEG C | 565 | 565 | 540 |
| Fluidized-bed reactor reaction velocity/(1/h) | 8 | 8 | 8 |
| The spent agent of riser tube 2 and the weight ratio of regenerator | 0:100 | 0:100 | 50:50 |
| Introduce riser tube 2 catalyzer temperature/DEG C | 670 | 670 | 635 |
| Spent agent carbon content/% by weight | / | / | 0.40 |
| Material balance/% by weight | |||
| Dry gas | 11.17 | 10.97 | 10.09 |
| Liquefied gas | 42.15 | 45.76 | 45.21 |
| C5+ gasoline | 35.81 | 33.32 | 35.54 |
| Diesel oil | 3.77 | 4.00 | 3.66 |
| Slurry oil | 0.00 | 0.00 | 0.00 |
| Coke | 5.61 | 4.66 | 3.99 |
| Water+loss | 1.51 | 1.51 | 1.51 |
| Amount to | 100.00 | 100.00 | 100.00 |
| Transformation efficiency/% by weight | 96.23 | 96.00 | 96.34 |
| Gas yield/% by weight | |||
| Ethylene yield | 6.56 | 7.29 | 6.90 |
| Productivity of propylene | 19.07 | 21.77 | 21.91 |
| Butylene productive rate | 14.57 | 16.54 | 16.48 |
| Petrol hydrocarbon types composition/% by weight | |||
| Normal paraffin | 8.37 | 8.06 | 7.52 |
| Isoparaffin | 15.57 | 13.67 | 13.10 |
| Alkene | 29.80 | 34.29 | 34.98 |
| Naphthenic hydrocarbon | 2.82 | 3.29 | 3.25 |
| Aromatic hydrocarbons | 43.24 | 40.49 | 41.04 |
| Oxygenatedchemicals and other | 0.22 | 0.19 | 0.11 |
| Add up to | 100.00 | 100.00 | 100.00 |
Table 4
Table 5
| Case | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 |
| Feed weight ratio-raw material 1-1/ raw material 1-2/ raw material 1-3 | 30:55:15 | 30:55:15 | 30:55:15 | 30:55:15 | 30:55:15 |
| Pyrolysis gasoline is to the recycle ratio/% of catalysis combined feed total feed | 10 | 10 | 10 | 10 | 10 |
| Catalyzer | MMC-2 | MMC-2 | MMC-2 | MMC-2 | MMC-2 |
| Regeneration temperature/DEG C | 700 | 700 | 700 | 700 | 700 |
| Reaction pressure (table), atm | 1.1 | 1.1 | 1.1 | 1.1 | 1.1 |
| Riser tube 1 temperature of reaction/DEG C | 560 | 560 | 560 | 560 | 560 |
| Riser tube 1 reacts total agent oil quality ratio | 10 | 10 | 10 | 10 | 10 |
| Raw material 1-1 atomized water steam rates/% | 12 | 12 | 12 | 12 | 12 |
| Raw material 1-3 atomized water steam rates/% | 24 | 24 | 24 | 24 | 24 |
| The riser tube 1 raw material 1-3 reaction times, second | 2.53 | 2.53 | 2.53 | 2.53 | 2.53 |
| The initial response time of raw material 1-1 before contact raw material 1-3, second | 0.31 | 0.31 | 0.31 | 0.31 | 0.31 |
| Combination bed reactor atomized water steam rates/% | 24 | 24 | 24 | 24 | 24 |
| Riser tube 2 temperature out/DEG C | 545 | 545 | 535 | 560 | 539 |
| The riser tube 2 reactor reaction time, second | 0.81 | 0.81 | 0.81 | 0.81 | 0.81 |
| Fluidized-bed reaction temperature/DEG C | 540 | 540 | 530 | 555 | 535 |
| Fluidized-bed reactor reaction velocity/(1/h) | 8 | 8 | 8 | 8 | 8 |
| The spent agent of riser tube 2 and the weight ratio of regenerator | 80:20 | 20:80 | 50:50 | 50:50 | 100:1 |
| Introduce riser tube 2 catalyzer temperature/DEG C | 635 | 670 | 610 | 650 | 617 |
| Spent agent carbon content, % | 0.36 | 0.42 | 0.38 | 0.40 | 0.34 |
| Material balance/% | |||||
| Dry gas | 10.85 | 10.93 | 9.92 | 11.83 | 10.35 |
| Liquefied gas | 48.54 | 49.32 | 46.27 | 49.91 | 47.37 |
| C5+ gasoline | 31.72 | 29.77 | 34.68 | 28.33 | 33.80 |
| Diesel oil | 3.46 | 3.91 | 3.46 | 3.98 | 3.21 |
| Slurry oil | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| Coke | 3.92 | 4.57 | 4.16 | 4.44 | 3.76 |
| Water+loss | 1.51 | 1.50 | 1.51 | 1.51 | 1.51 |
| Amount to | 100.00 | 100.00 | 100.00 | 100.00 | 100.00 |
| Transformation efficiency/% | 96.54 | 96.09 | 96.54 | 96.02 | 96.79 |
| Gas yield/% | |||||
| Ethylene yield | 7.52 | 7.48 | 6.61 | 8.03 | 7.16 |
| Productivity of propylene | 23.91 | 23.74 | 21.89 | 24.60 | 23.27 |
| Butylene productive rate | 17.59 | 17.68 | 16.86 | 18.03 | 17.26 |
| Petrol hydrocarbon types composition/% | |||||
| Normal paraffin | 8.57 | 9.71 | 9.50 | 8.53 | 8.41 |
| Isoparaffin | 13.31 | 14.83 | 17.54 | 13.26 | 13.88 |
| Alkene | 23.36 | 21.34 | 24.39 | 19.75 | 25.27 |
| Naphthenic hydrocarbon | 4.00 | 4.06 | 4.44 | 4.97 | 3.85 |
| Aromatic hydrocarbons | 50.58 | 49.87 | 43.98 | 53.37 | 48.46 |
| Oxygenatedchemicals and other | 0.18 | 0.19 | 0.15 | 0.13 | 0.14 |
| Add up to | 100.00 | 100.00 | 100.00 | 100.00 | 100.00 |
Claims (22)
1. a catalysis processing method for high temperature fischer-tropsch synthetic oil, comprising:
(1) high temperature fischer-tropsch synthetic product is separated, obtains high temperature condensation product, the gentle state hydrocarbon of low temperature cold condensate;
(2) described hydrocarbon gas and described high temperature condensation product are introduced in the first riser reactor react with the catalyst exposure in introducing first riser reactor, form the first oil agent mixture;
(3) by the oil gas in the first oil agent mixture and catalyst separating, the catalyzer after separation introduces fluidized-bed reactor and/or stripper, and the oil gas after separation introduces product separation system;
(4) described low temperature cold condensate is introduced in the second riser reactor react with the catalyst exposure in introducing second riser reactor, form the second oil agent mixture; Then react in the fluidized-bed reactor described in the second oil agent mixture being introduced, stripper stripping introduced by reacted catalyzer, and reacted oil gas introduces product separation system;
Described catalyzer contains the zeolite that aperture is less than 0.7nm.
2. according to the catalysis processing method of high temperature fischer-tropsch synthetic oil according to claim 1, it is characterized in that, the boiling range of described hydrocarbon gas is between-2.3 ~ 83 DEG C; The boiling range of described high temperature condensation product is between 210 DEG C ~ 600 DEG C, and the boiling range of described low temperature cold condensate is between 40 ~ 300 DEG C.
3. according to the catalysis processing method of the high temperature fischer-tropsch synthetic oil described in claim 1 or 2, it is characterized in that, the final boiling point of described hydrocarbon gas is 40 ~ 83 DEG C, the initial boiling point of described low temperature cold condensate is 40 ~ 83 DEG C, the final boiling point of described low temperature cold condensate is 210 ~ 300 DEG C, and described high temperature condensation product initial boiling point is 210 ~ 300 DEG C.
4. according to the catalysis processing method of high temperature fischer-tropsch synthetic oil according to claim 1, it is characterized in that, described high temperature fischer-tropsch synthetic product to be separated, described high temperature condensation product is made to account for 5 ~ 20 % by weight of described high temperature fischer-tropsch synthetic product gross weight, described low temperature cold condensate accounts for 50 ~ 60 % by weight of described high temperature fischer-tropsch synthetic product gross weight, and described hydrocarbon gas accounts for 20 ~ 40 % by weight of described high temperature fischer-tropsch synthesis gross weight.
5., according to the catalysis processing method of high temperature fischer-tropsch synthetic oil according to claim 1, wherein said high temperature condensation product and described hydrocarbon gas are introduced the first riser reactor simultaneously or after described hydrocarbon gas, are introduced the first described riser reactor.
6. according to the catalysis processing method of high temperature fischer-tropsch synthetic oil according to claim 5, it is characterized in that, before described high temperature condensate contact, described hydrocarbon gas and the described catalyzer catalytic time in the first riser reactor is 0.0 ~ 1 second, and the described catalyzer of introducing first riser reactor and the mass ratio of described hydrocarbon gas are 7 ~ 39.
7. according to the catalysis processing method of high temperature fischer-tropsch synthetic oil according to claim 6, it is characterized in that, before high temperature condensation product described in introducing, catalyzer catalytic time in the first riser reactor in described hydrocarbon gas and described introducing first riser reactor is 0.0 ~ 0.91 second, and the catalyzer in described introducing first riser reactor and the mass ratio of described hydrocarbon gas are 10 ~ 30.
8. according to claim 1, 2, 4, the catalysis processing method of the high temperature fischer-tropsch synthetic oil described in 5 or 6, it is characterized in that, the reaction conditions of described first riser reactor comprises: temperature of reaction is 490 ~ 600 DEG C, described high temperature condensation product is 0.50 ~ 10 second in the reaction times of the first riser reactor, total agent-oil ratio of described first riser reactor is 5 ~ 25, reaction pressure is 0.15 ~ 0.3MPa, total agent-oil ratio of described first riser reactor refers to the ratio of the described catalyst quality of introducing first riser reactor and described high temperature condensation product and hydrocarbon gas total mass.
9. according to the catalysis processing method of high temperature fischer-tropsch synthetic oil according to claim 8, it is characterized in that, the temperature of reaction of the first riser reactor is 530 ~ 580 DEG C, described high temperature condensation product is 2 ~ 6 seconds in the reaction times of the first riser reactor, and total agent-oil ratio of described first riser reactor is 7 ~ 20.
10. according to the catalysis processing method of high temperature fischer-tropsch synthetic oil according to claim 1, it is characterized in that, the reaction conditions that described low temperature cold condensate reacts at the second riser reactor comprises: agent-oil ratio is 10 ~ 30, and the reaction times is 0.10 ~ 1.5 second, and temperature of reaction is 490 ~ 600 DEG C; The reaction conditions of fluidized-bed reactor: temperature of reaction is 500 ~ 600 DEG C, reaction pressure is 0.15 ~ 0.3MPa, and weight hourly space velocity is 1 ~ 35 hour
-1.
11. according to the catalysis processing method of high temperature fischer-tropsch synthetic oil according to claim 10, it is characterized in that, the agent-oil ratio of the second riser reactor is the reaction times of the 12 ~ 20, second riser reactor is 0.4 ~ 1.1 second, and the temperature of reaction of the second riser reactor is 535 ~ 575 DEG C; The temperature of reaction of fluidized-bed reactor is 525 ~ 565 DEG C, and the weight hourly space velocity of fluidized-bed reactor is 3 ~ 15 hours
-1.
12. according to the catalysis processing method of high temperature fischer-tropsch synthetic oil according to claim 1, it is characterized in that, the catalyzer of described introducing second riser reactor is the regenerated catalyst from revivifier, the reclaimable catalyst from stripper or the mixture of the two.
13. according to the catalysis processing method of high temperature fischer-tropsch synthetic oil according to claim 12, and it is characterized in that, the carbon content of described reclaimable catalyst is 0.2 ~ 0.9 % by weight.
14. according to the catalysis processing method of high temperature fischer-tropsch synthetic oil according to claim 12, it is characterized in that, the catalyzer introducing the second riser reactor is the mixture of reclaimable catalyst or reclaimable catalyst and regenerated catalyst, and wherein the weight ratio of regenerated catalyst and reclaimable catalyst is 0:100 ~ 100:1.
15. according to the catalysis processing method of high temperature fischer-tropsch synthetic oil according to claim 14, and it is characterized in that, in the catalyzer of described introducing second riser reactor, the weight ratio of regenerated catalyst and reclaimable catalyst is 20:80 ~ 80:20.
16., according to the catalysis processing method of high temperature fischer-tropsch synthetic oil according to claim 14, is characterized in that, described reclaimable catalyst regenerated flue gas heat temperature raising.
17. according to the catalysis processing method of the arbitrary described high temperature fischer-tropsch synthetic oil of claim 14 ~ 16, and it is characterized in that, the temperature introducing the catalyzer of the second riser tube is 550 ~ 720 DEG C.
18. according to the catalysis processing method of high temperature fischer-tropsch synthetic oil according to claim 17, and it is characterized in that, the temperature of the catalyzer of described introducing second riser tube is 580 ~ 690 DEG C.
19. according to the catalysis processing method of high temperature fischer-tropsch synthetic oil according to claim 1, and it is characterized in that, the gasoline fraction that product separation system obtains introduces the second riser reactor.
20. according to the catalysis processing method of the high temperature fischer-tropsch synthetic oil described in claim 1 or 19, and it is characterized in that, the cracking masout that product separation system obtains introduces the second riser reactor or described fluidized-bed reactor.
21., according to the catalysis processing method of high temperature fischer-tropsch synthetic oil according to claim 1, is characterized in that, introduce the first riser reactor after described high temperature condensation product demetalization.
The catalysis processing unit (plant) of 22. 1 kinds of high temperature fischer-tropsch synthetic oils, comprise: riser reactor (1), riser reactor (2), fluidized-bed reactor (3), stripper (7), settling vessel (8), revivifier (10) and catalyst mix interchanger (60), wherein riser reactor (1) connects gas-solid separating device, the catalyst outlet of gas-solid separating device communicates with fluidized-bed reactor (3), being communicated with the top of stripper (7) of fluidized-bed reactor (3) bottom, the top of fluidized-bed reactor (3) is communicated with settling vessel (8), stripper (7) is communicated with revivifier (10) by catalyst transfer line (18), stripper (7) is communicated with catalyst heater (60) by catalyst transfer line (14), revivifier (10) is communicated with catalyst heater (60) by regenerated catalyst transfer limes (17), catalyst mix interchanger (60) is communicated with riser reactor (2) by catalyst transfer line (16), revivifier (10) is communicated with riser reactor (1) by regenerated catalyst transfer limes (15), the bottom of riser reactor (1) is provided with the first oil gas entrance in order to introduce reaction raw materials, is provided with the second oil gas entrance in order to introduce reaction raw materials between the first oil gas entrance and the outlet of riser reactor (1).
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