CN102286291B - Catalytic conversion method of shale oil - Google Patents
Catalytic conversion method of shale oil Download PDFInfo
- Publication number
- CN102286291B CN102286291B CN201010202781.4A CN201010202781A CN102286291B CN 102286291 B CN102286291 B CN 102286291B CN 201010202781 A CN201010202781 A CN 201010202781A CN 102286291 B CN102286291 B CN 102286291B
- Authority
- CN
- China
- Prior art keywords
- reaction zone
- reaction
- catalyzer
- fluidized bed
- oil
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Abstract
The invention relates to a catalytic conversion method of shale oil, which comprises a step of performing a catalytic cracking reaction on shale oil raw materials and unconverted oil in a catalytic cracking reactor. The catalytic cracking reactor comprises at least two reaction zones. The unconverted oil and a first strand of catalyst are contacted in the first reaction zone to perform the catalytic cracking reaction; and then the obtained product is introduced into the second reaction zone connected in series with the first reaction zone to perform a reaction and the shale oil raw materials is introduced into the second reaction zone to perform a reaction. Due to the adoption of the catalytic conversion method of the shale oil, the conversion rate of the shale oil can be improved and the yield of a light product can be improved.
Description
Technical field
The present invention relates to a kind of catalysis conversion method of hydrocarbon ils, more particularly, the present invention relates to a kind of catalyzed conversion method for transformation of shale oil.
Background technology
Shale oil be resinous shale after hot-work, the product that its organic decomposes generates, similar natural oil, but contain more unsaturated hydrocarbons than natural oil, and the non-hydrocarbons organic compound such as nitrogenous, sulphur, oxygen.Whole world oil shale reserves is approximately equivalent to 4 000 hundred million tons of shale oil, considerably beyond natural oil total reserves.China's oil shale resources are very abundant, and its reserves occupy the 4th, the world, are equivalent to 16,000,000,000 tons of shale oil.Shale oil industry is an important component part of energy industry, is also a kind of supplementary energy of natural oil.Yet shale oil is except a small amount of production pharmaceutical chemicals at present, and major part is directly sold as oil fuel without secondary processing, be therefore necessary the more technology of efficiently utilizing shale oil of exploitation.
US4342641 discloses a kind of method for processing shale oil, first full cut shale oil is carried out to hydrotreatment, hydrotreatment generates the cut of 249 ℃ of being less than obtaining after oil content heats up in a steamer can be directly as rocket engine fuel, and the cut of 249 ℃ of being greater than obtaining carries out hydrocracking again, to produce rocket engine fuel.Wherein hydrotreatment is carried out in two steps, first with the low catalyzer of Ni-Mo content, carries out pre-refining, more further refines with the high catalyzer of Ni-Mo content.The method hydrogenation process is many, and hydrogen consumption is high, and process cost is high, and construction investment is high.
CN1011067089A discloses a kind of working method of shale oil, shale oil first obtains hydrogenated oil through hydrotreatment, hydrogenated oil is separated into hydrogenation heavy oil and light-end products, hydrogenation heavy oil obtains dry gas, liquefied gas, gasoline, diesel oil and catalytic heavy after catalyzed conversion, and diesel oil can return to hydrotreating step.The method is carried out hydrofining by shale oil, and the refining heavy oil obtaining, as the raw material of existing catalytic cracking technology, changes into light-end products.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of new shale oil catalytic method for transformation.
Shale oil catalytic method for transformation provided by the invention comprises: shale oil raw material and unconverted oil are carried out to catalytic cracking reaction in catalyst cracker; Described catalyst cracker comprises at least two reaction zones, unconverted oil contacts and carries out catalytic cracking reaction with first strand of catalyzer in the first reaction zone, then introduce the second reaction zone of connecting with the first reaction zone, with the shale oil raw material contact reacts of introducing second reaction zone.
The present invention also provides a kind of catalytic cracking reaction device that can be used for shale oil catalytic method for transformation provided by the invention, the fast bed reaction zone of comprise riser reaction zone, connecting with riser reaction zone, the diameter of fast bed reaction zone reaction tubes is 1.05～1.7: 1 with the diameter ratio of riser reaction zone reaction tubes.
The catalysis conversion method of shale oil provided by the invention, can improve the transformation efficiency of shale oil, increases the yield of liquefied gas and gasoline; When further comprising fluidized-bed reactor, while using the catalyzer that contains five-membered ring structure zeolite, can also improve the productivity of propylene that shale oil transforms.
Accompanying drawing explanation
Accompanying drawing 1 and Fig. 2 are shale oil catalytic method for transformation schematic flow sheet provided by the invention.Wherein
1-riser reactor,
11-carries the transfer lime of regenerated catalyst to riser reactor 1,
Regenerated catalyst flowrate control valve on 12-transfer lime 11,
The unconverted oil feed nozzle of 13-riser reactor 1;
2-fast bed reactor,
The shale oil raw material feed nozzle of 21-fast bed reactor 2,
22-reactor 2 outlet spargers;
3-fluidized-bed reactor;
4-stripper;
The reclaimable catalyst transfer lime of 41-stripper 4,
On 42-reclaimable catalyst transfer lime 41, control the control valve of catalyst flow;
5-settling vessel;
6-revivifier;
7-carries the transfer lime of regenerated catalyst to fluidized-bed reactor 3;
The regenerated catalyst flowrate control valve of 71-transfer lime 7.
Embodiment
In shale oil catalytic method for transformation provided by the invention, make shale oil raw material and unconverted oil in catalyst cracker, carry out catalytic cracking reaction, described catalyst cracker comprises at least two reaction zones, unconverted oil contacts and carries out catalytic cracking reaction with first strand of catalyzer in the first reaction zone, and reacted oil gas is introduced the second reaction zone of connecting with the first reaction zone with catalyzer; Shale oil raw material is introduced second reaction zone, with oil gas and catalyst mix from the first reaction zone and react; In second reaction zone, shale oil raw material carries out cracking reaction, and simultaneously wherein contained nitrogenous compound is adsorbed in catalyzer, thereby reduces the nitrogen content in cracking oil gas product.The reaction conditions of the first reaction zone comprises: temperature of reaction is 480～650 ℃ preferably 490～600 ℃, pressure is preferably 0.18～0.35MPa (absolute pressure) of 0.15～0.4MPa, agent-oil ratio (weight ratio of catalyzer and shale oil raw material) is 4～30, reaction times is 0.5～4s, preferably 0.8～3s; The reaction conditions of second reaction zone comprises: temperature of reaction is 450～620 ℃ and is preferably 480～580 ℃, pressure is preferably 0.18～0.35MPa (absolute pressure) of 0.15～0.4MPa, enter the catalyzer of second reaction zone and the weight ratio of shale oil raw material is 4～30, reaction times is 0.5～6s, preferably 1～4s.First strand of catalyzer is regenerated catalyst and/or live catalyst.
The first described reaction zone is preferably riser reaction zone, and second reaction zone is preferably fast bed reaction zone.Shale oil raw material sprays into fast bed reactor, contact with the catalyzer from riser reaction zone (the first reaction zone), macromolecule compound is cracked into the compound of intermediate molecular weight, and the nitrogenous compound in adsorbing and removing oil, the chilling effect of shale oil raw material simultaneously can be controlled the reaction depth of riser reaction zone oil gas, prevents the generation of cracking reaction.Described riser reaction zone (or claim riser reactor) for equal diameter riser tube, etc. linear speed riser tube and straighten one or more in the riser tube of footpath.Preferred the first reaction zone is equal diameter riser reaction zone, described second reaction zone is preferably isodiametric tubular type fast bed reaction zone, the ratio of its diameter and the first riser reaction zone, reaction zone diameter is preferably 1.05～1.7: 1, more preferably 1.1～1.6: 1, the ratio of its length and the first riser reaction zone, reaction zone length is preferably 0.2～1: 1, more preferably 0.3～0.8: 1.
The reacted oil gas in second reaction zone and catalyzer, can directly introduce the 3rd reaction zone without separation and react; Or catalyzer is separated at settling vessel with oil gas, catalyzer is introduced to stripper stripping, oil gas is introduced to fractionating system fractionation or introduce the 3rd reaction zone and react.
A kind of embodiment of the present invention, described the first reaction zone is riser reaction zone, second reaction zone is fast bed reaction zone, also comprise that the 3rd reaction zone of connecting with second reaction zone (also can be called the 3rd reactor, the first reaction zone also can be described as the first reactor, second reaction zone also can be described as the second reactor), the oil gas that leaves second reaction zone reacts with carbon deposited catalyst introducing the 3rd reaction zone, and described the 3rd reaction zone is riser reaction zone or fluidized bed reaction zone.Second strand of catalyzer preferably also introduced in the 3rd described reaction zone, and to improve the catalytic activity of the 3rd reaction zone, second strand of catalyzer can be regenerator and/or fresh dose.From the 3rd reaction zone, introduce second strand of catalyzer, be conducive to improve transformation efficiency, improve the selectivity of liquefied gas and gasoline.Second strand of catalyzer introducing the 3rd reaction zone is 5～70: 100 with the weight ratio of introducing first strand of catalyzer of the first reaction zone.Preferably, the first reaction zone is riser reaction zone, and second reaction zone is fast bed reaction zone, and the 3rd reaction zone is fluidized bed reaction zone.The 3rd reaction zone is the low-carbon alkene productivity of propylene for example that fluidized bed reaction zone is conducive to improve shale oil feedstock conversion; While also introducing second strand of catalyzer in the 3rd reaction zone, leave the oil gas of second reaction zone and catalyzer from the introducing fluidized bed reaction zone, bottom of fluidized bed reaction zone, leaving the catalyzer of fluidized bed reaction zone draws from the bottom of fluidized bed reaction zone, leave the oil gas of fluidized bed reaction zone from its Base top contact, second strand of catalyzer is from the first half (fluidized bed layer height 1/2 is to the position between bed top) or introducing fluidized bed reaction zone, top of fluidized bed reaction zone, to improve transformation efficiency and the productivity of propylene of shale oil.From the top of fluidized bed reaction zone, introduce second strand of catalytic cracking catalyst, catalyzer can be caused to top, fluidized bed reaction zone (fluidized-bed bed top charge level) locates, or described catalyzer is caused to the top at top, fluidized bed reaction zone, make catalyzer by the effect of gravity, be settled down to the top of fluidized bed reaction zone, then enter in fluidized bed reaction zone.The 3rd reacted oil gas in reaction zone is introduced settling vessel, introduces fractionating system after isolating the catalyzer of wherein carrying secretly; Reacted catalyzer is introduced stripper, introduces revivifier regeneration after the hydrocarbons that stripping goes out to adsorb.Reaction conditions when the 3rd reaction zone is fluidized bed reaction zone is: temperature of reaction is 480～650 ℃, pressure 0.15～0.4MPa (absolute pressure), weight hourly space velocity 0.5～30h
-1, the weight ratio 5～70: 100 of second strand of catalyzer and first strand of catalyzer.Described fluidized bed reaction zone is one or more of dispersion fluidized bed reaction zone, bubbling bed reaction zone or turbulent bed reaction zone.
In the catalysis conversion method of shale oil provided by the invention, the reacted oil gas in second reaction zone is introduced product fractionating system or introduces in the 3rd reaction zone and further react by settling vessel and introduce product fractionating system through settling vessel.In settling vessel, most of catalyzer is in settling vessel rapid subsidence, cyclonic separation is passed through in the partially catalyzed agent that oil gas carries, the catalyzer that the catalyzer of sedimentation and cyclonic separation obtain enters the 3rd reaction zone, and then enter stripper, after the hydrocarbons that goes out absorption through stripping, introduce revivifier regeneration, the catalyzer after regeneration can be used as first strand of catalyzer or also as second burst of catalyst recirculation, uses.Oil gas is introduced product fractionating system, through fractionation, can obtain liquefied gas, gasoline, cracking light oil and heavy oil fraction, all or part of of cracking light oil and heavy oil (the present invention is referred to as unconverted oil) introduced the first reactor and further transformed (freshening).The pressure fuel that these nitrogen contents are lower and/or cracking strippings or all as unconverted oil, introduce (freshening to) first reaction zone and contact with first strand of described catalyzer, under the effect of active greater catalytic agent, further transform, be conducive to avoid cause because shale oil raw material nitrogen content is too high the rapid inactivation of cracking catalyst, make unconverted oil change into more low molecular hydrocarbon, improve transformation efficiency and the light-end products selectivity of shale oil, improve the yield of liquefied gas and gasoline.
Described shale oil raw material is shale oil, shale heavy oil or one or more in hydrorefined shale heavy oil.The normal pressure initial boiling point of described unconverted oil is not less than 200 ℃, and preferably its boiling range is between 300～550 ℃.
It is an acidic catalyst that shale oil of the present invention transforms catalyzer used (described first strand of catalyzer and second strand of catalyzer), and first strand of catalyzer and second strand of catalyzer are catalyzer of the same race.Described an acidic catalyst is known by those skilled in the art, for example, contain Y-series zeolite and/or other optional molecular sieve, the cracking catalyst of inorganic oxide and clay.Described Y-series zeolite comprises Y type and derivative or modified zeolite thereof, is selected from one or more the mixture in Y, HY, REY, REHY, USY, REUSY.One or more in mesopore zeolite, Beta zeolite and SAPO molecular sieve of described other molecular screening.Described mesopore zeolite comprises ZSM series zeolite and derivative or modified zeolite, the mixture of one or more among the zeolite of ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, ZSM-38, ZSM-48 and other similar structures for example, the more detailed description of relevant ZSM-5 is referring to US3,702,886.The series modified zeolite of described ZSM is ZRP series (rare earth modified ZSM-5 zeolite), ZSP series (iron modified ZSM-5 zeolite) for example, and the more detailed description of relevant ZRP is referring to US5, and 232,675.Described inorganic oxide is selected from one or more the mixture in aluminum oxide, silicon oxide, amorphous silicon aluminium, and clay is that kaolin is or/and halloysite.Described an acidic catalyst, the gross weight of catalyzer of take is benchmark, its molecular sieve that contains 1～60 % by weight, in the heat-resistant inorganic oxide of oxide compound 5%～99% and 0～70% clay; In preferred embodiment, the gross weight of described refining shale heavy oil conversion catalyzer of take is benchmark, molecular sieve, the heat-resistant inorganic oxide of 10～70 % by weight and the clay of 0～60 % by weight that described refining shale heavy oil conversion catalyzer contains 10～50 % by weight.Catalyzer of the present invention can be purchased or prepare according to existing method.When utilizing method provided by the invention to produce propylene, described catalyzer preferably contains five-membered ring structure zeolite (pentasil type zeolite), the described preferred mesopore zeolite of five-membered ring structure zeolite and/or Beta zeolite, described mesopore zeolite is the ZSM-5 zeolite of changing into property preferably, for example one or more in ZRP zeolite, ZSP zeolite and HZSM-5 zeolite.
In refining shale method for catalytic conversion of heavy oil provided by the invention, for reducing oil gas dividing potential drop in reactor, in the process of carrying out described catalytic conversion reaction, can in described reactor, inject thinner, described thinner is selected from one or more in water vapour, nitrogen and C1～C4 alkane, be preferably water vapour, the weight ratio of water vapour and shale oil raw material is preferably 0.01～1: 1.
A kind of catalytic convention design that can be used for shale oil method for transformation of the present invention, as shown in Figure 1, comprise riser reaction zone 1, fast bed reaction zone 2, fluidized bed reaction zone 3, stripper 4, settling vessel 5 and revivifier 6, described stripper 4 is positioned at the below of described fluidized bed reaction zone (or claiming fluidized-bed reactor) 3, and described stripper 4 is directly communicated with the bottom of described fluidized bed reaction zone 3, (or the fast bed bioreactor of expressing one's gratification) 2 the outlet of described fast bed reaction zone and the optional position, bottom of described fluidized bed reaction zone 3 are communicated with, and the top exit of described fluidized bed reaction zone 3 is communicated with the entrance of gas-solid separation equipment in settling vessel 5.Shale oil raw material enters fast bed reaction zone 2 by feed nozzle 21, contacts and reacts with oil gas with the catalyzer from riser reaction zone 1, and then the sparger 22 by 2 exits, fast bed reaction zone enters fluidized bed reaction zone 3 and further reacts, in fluidized bed reaction zone 3, reacted carbon deposited catalyst enters stripper 4 by bottom, fluidized bed reaction zone, after stripping, by reclaimable catalyst transfer lime 41, enter revivifier 6 regeneration, the reacted oil gas in fluidized bed reaction zone 3 enters settling vessel 5 by the top of fluidized bed reaction zone 3, through cyclonic separator, remove the catalyzer wherein carrying again and enter fractionation plant fractionation, the heavy oil that fractionation obtains and/or light oil distillate are partly or entirely as unconverted oil, by nozzle 13, introduce riser reaction zone 1, with the regenerated catalyst contact reacts of introducing by catalyst transport 11, through high temperature, short-time contact reaction, unconverted oil is converted into the light-end products of high value, reacted catalyzer further reacts without the separated fast bed reaction zone 2 of directly introducing with oil gas.In addition, because stripper 4 is communicated with fluidized bed reaction zone 3 gas-solids, therefore, by regulating stripper, to revivifier, discharge the flowrate control valve of reclaimable catalyst, can directly control the charge level of catalyzer in fluidized-bed reactor, and then the weight hourly space velocity of reaction in control fluidized-bed reactor, can increase thus the technique flexibility ratio of catalytic conversion reaction.Catalyzer after revivifier 6 regeneration is introduced riser reaction zone 1 by catalyst transport 11.
In Fig. 1, stripper 4 is positioned at the below of fluidized bed reaction zone 3, and be communicated with the bottom of fluidized bed reaction zone 3, to the water vapour of supplying in stripper, can be upwards by fluidized bed reaction zone, as the dilution water steam of the catalytic conversion reaction wherein occurring, obtain second stage employ, be conducive to reduce the overall energy consumption of reaction.
The present invention another for catalytic convention design of the present invention, as shown in Figure 2.Also to comprise catalyst transport pipeline 7 from installing different described in Fig. 1, for a part of regenerated catalyst is delivered to fluidized bed reaction zone 3,3 to provide second strand of regenerated catalyst to fluidized bed reaction zone.A catalyzer part after revivifier 6 regeneration is introduced riser reaction zone 1 as first strand of catalyzer by catalyst transport 11, and a part is introduced fluidized bed reaction zone 3 as second strand of catalyzer by catalyst transport 7.
Embodiment 1～4
Effect when embodiment 1～4 explanation adopts refining shale heavy oil feedstock catalysis conversion method provided by the invention.
Embodiment 1～4 used catalyst, take total catalyst weight as benchmark, containing 20 % by weight Y zeolite, 10 % by weight ZRP-1 zeolites, 45 % by weight kaolin, in the al binder of aluminum oxide 25 % by weight.Described method for preparing catalyst is as follows: DASY zeolite (is contained to RE
2o
32 % by weight, catalyzer asphalt in Shenli Refinery of China Petrochemical Industry product) (catalyzer asphalt in Shenli Refinery of China Petrochemical Industry product, containing 1.1 % by weight RE with ZRP-1
2o
31.2 % by weight P) water making beating, make the slurries that solid content is 30 % by weight, kaolin (Suzhou China Kaolin Co., Ltd product), pseudo-boehmite (Shandong Aluminium Industrial Corp's product) and water are mixed to making beating and prepare solid content 30 % by weight slurries, above-mentioned two kinds of slurries are mixed, at 50 ℃, stir and within 30 minutes, obtain catalyst slurry, by the dry catalyzer that obtains of catalyst slurry spraying.Catalyzer is at 800 ℃, with 100% water vapour aging 10 hours.Use medium-sized tester, in device, the loading amount of catalyzer is 60 kilograms, the diameter ratio of riser tube 1 and fast bed 21: 1.5, the length ratio of riser tube 1 and fast bed 22: 1, the diameter of riser reaction zone 1 is 18mm, be highly 6m, the diameter of fluidized bed reaction zone (reactor) 3 is 64mm, is highly 0.5m.
In each embodiment, dilution water steam from the middle part of riser reactor 1 (height 1/2) introduce, the weight ratio of water stripping steam and shale oil raw material is 3: 100, and stripping oil gas is introduced fluidized bed reaction zone 3, and the pressure in settling vessel (settling vessel top) is 0.2MPa.
Embodiment 1
As shown in Figure 1, shale oil raw material Y1 (character is in Table 1) enters fast bed reaction zone 2 to flow process; Unconverted oil (initial boiling point of unconverted oil is 300 ℃, and final boiling point is 550 ℃, lower same) is entered riser reaction zone 1 and enter fast bed reaction zone 2 after regenerated catalyst (the first strand of catalyzer) contact reacts of transfer lime 11 introducings; The reacted oil gas in fast bed reaction zone 2 and catalyzer cause the bottom of fluidized-bed reactor 3, and react in fluidized bed reaction zone 3, reacted catalyzer 3 bottom leaves fluidized bed reaction zone and enters stripper from fluidized bed reaction zone, oil gas 3 top leaves from fluidized bed reaction zone, enter settling vessel, enter fractionating system after isolating the catalyzer carrying; Reaction conditions and reaction result are in Table 2.
Embodiment 2
Flow process as shown in Figure 1, shale heavy oil feedstock Y1 (character is in Table 1) enters fast bed reaction zone 2, after regenerated catalyst (the first strand of catalyzer) contact reacts that unconverted oil (300～550 ℃ of boiling ranges) is entered riser reaction zone 1 and entered riser reaction zone 1 through transfer lime 11, enter fast bed reaction zone 2, it is separated that reacted oil gas and catalyzer enter settling vessel, after separation, catalyzer enters stripper, and oil gas is introduced fractionating system; Fluidized-bed reactor 3 zero material level operations (not comprising the 3rd reaction zone).Reaction conditions and the results are shown in Table 2.
Embodiment 3
As shown in Figure 1, shale oil raw material Y2 (character is in Table 1) enters fast bed reactor 2 to flow process; Unconverted oil is entered riser reactor 1 and enter fast bed reaction zone 2 after the regenerated catalyst contact reacts of transfer lime 11 introducings; The bottom of the reacted oil gas of fast bed reactor 2 and catalyzer influent stream fluidized bed reactor 3, reaction in fluidized-bed reactor 3, reacted catalyzer enters stripper from the bottom of fluidized-bed reactor 3, reacted oil gas leaves at 3 tops from fluidized bed reaction zone, through settling vessel, introduces product fractionating system.Reaction conditions and the results are shown in Table 2.
Comparative example 1
Comparative example 1 explanation adopts riser tube to add the effect that fluidized-bed reactor carries out shale oil catalytic conversion.Shale oil raw material (shale heavy oil Y1) in riser reactor with catalyzer contact reacts after, oil gas is introduced fluidized-bed reactor with catalyzer and is continued to react, catalyzer enters stripper from the bottom of fluidized-bed reactor, oil gas leaves from the top of fluidized-bed reactor 3, through settling vessel, introduce fractionating system, reaction conditions and the results are shown in Table 2.
Comparative example 2
According to the method for embodiment 2, difference is that shale heavy oil feedstock and unconverted oil are mixed laggard riser reactor (riser reactor 1), fluidized-bed reactor 3 zero material level operations (can regulate the material level of fluidized-bed reactor 3 by valve 42)
According to the method for embodiment 1, different is by catalyst transport 7, regenerated catalyst to be caused to the top (charge level place, bed top) of fluidized bed reaction zone 3, to introduce second strand of catalyzer in fluidized bed reaction zone, the ratio of second strand of catalyzer and first strand of catalyzer (introducing the regenerated catalyst of riser reactor 1) is 30: 100.Flow process as shown in Figure 2.
The character of raw material is in Table 1, and test-results is in Table 2.In table 2: reaction zone A refers to that riser reaction zone, B refer to that fast bed reaction zone, C refer to fluidized bed reaction zone.In table 2, recycle ratio is the unconverted oil and the weight ratio of introducing the shale heavy oil feedstock of fast bed reaction zone 2 of introducing riser reaction zone 1; Water injection rate is the water vapor amount and the weight percent of introducing the shale heavy oil feedstock (fresh feed) of reactor 2 of introducing riser reactor 1; The water stripping steam consumption of stripper is 3 % by weight with the ratio of shale heavy oil feedstock; Agent-oil ratio is the catalyzer and the weight ratio of introducing the shale heavy oil feedstock of reactor 2 of introducing this reaction zone the unit time.
From table 2, catalysis conversion method provided by the invention, has higher transformation efficiency and light-end products productive rate, and cracking masout productive rate is low, and liquefied gas and gasoline yield are high, and dry gas yied is low, can obtain compared with high productivity of propylene in addition.
Table 1
Claims (12)
1. a shale oil catalytic method for transformation, comprise shale oil raw material and unconverted oil are carried out to the step of catalytic cracking reaction in catalyst cracker, described catalyst cracker comprises at least two reaction zones, unconverted oil contacts and carries out catalytic cracking reaction with first strand of catalyzer in the first reaction zone, then introduce the second reaction zone of connecting with the first reaction zone and react, shale oil raw material is introduced in second reaction zone and is reacted; The first described reaction zone is riser reaction zone; Second reaction zone is fast bed reaction zone; The reaction conditions of the first reaction zone: temperature of reaction is 480～650 ℃, the weight ratio of first strand of catalyzer and shale oil raw material is 4～30, the reaction times is 0.5～4s; The reaction conditions of second reaction zone: temperature of reaction is 450～620 ℃, the weight ratio of catalyzer and shale oil raw material is 4～30, the reaction times is 0.5～6s.
2. in accordance with the method for claim 1, it is characterized in that, the first described reaction zone is riser reaction zone; Second reaction zone is fast bed reaction zone; The reaction conditions of the first reaction zone: temperature of reaction is 490～600 ℃, the weight ratio of first strand of catalyzer and shale oil raw material is 4～30, the reaction times is 0.8～3s; The reaction conditions of second reaction zone: temperature of reaction is 480～580 ℃, the weight ratio of catalyzer and shale oil raw material is 4～30, the reaction times is 1～4s.
3. in accordance with the method for claim 2, it is characterized in that, also comprise the 3rd reaction zone of connecting with second reaction zone, the reacted oil gas in second reaction zone and catalyzer are introduced the 3rd reaction zone; Described the 3rd reaction zone is riser reaction zone or fluidized bed reaction zone.
4. in accordance with the method for claim 3, it is characterized in that, in the 3rd reaction zone, also introduce second strand of catalyzer; The weight ratio of second strand of catalyzer and first strand of catalyzer is 5～70:100.
5. in accordance with the method for claim 4, it is characterized in that, the 3rd described reaction zone is fluidized bed reaction zone, introducing fluidized bed reaction zone, bottom from the oil gas of second reaction zone and catalyzer from fluidized bed reaction zone, leaving the catalyzer of fluidized bed reaction zone draws from the bottom of fluidized bed reaction zone, leave the oil gas of fluidized bed reaction zone from its Base top contact, second strand of catalyzer is from the first half or the introducing fluidized bed reaction zone, top of fluidized bed reaction zone.
6. according to the method described in claim 3,4 or 5, it is characterized in that the reaction conditions of described the 3rd reaction zone: temperature of reaction is 480～650 ℃, weight hourly space velocity 0.5～30h
-1.
7. in accordance with the method for claim 1, it is characterized in that the reaction conditions of the first reaction zone: temperature of reaction is 490～600 ℃, the reaction times is 0.8～3s.
8. in accordance with the method for claim 7, it is characterized in that, the reaction conditions of second reaction zone is: temperature of reaction is 480～580 ℃, and the reaction times is 1～4s.
9. in accordance with the method for claim 1, it is characterized in that, described shale oil raw material is shale oil, shale heavy oil or one or more in hydrorefined shale heavy oil.
10. the catalytic cracking reaction device for method described in claim 1, comprise riser reaction zone (1), the fast bed reaction zone (2) of connecting with riser reaction zone (1), the diameter ratio of the diameter of fast bed reaction zone (2) reaction tubes and riser reaction zone (1) reaction tubes is 1.05～1.7:1.
11. according to device claimed in claim 10, it is characterized in that, the ratio of fast bed reaction zone (2) tube length of reaction tube and riser reaction zone (1) tube length of reaction tube is 0.2～1:1.
12. according to the device described in claim 10 or 11, it is characterized in that, also comprise fluidized bed reaction zone (3), stripper (4), settling vessel (5) and revivifier (6), described stripper (4) is positioned at the below of described fluidized bed reaction zone (3), and described stripper (4) is directly communicated with the bottom of described fluidized bed reaction zone (3), the optional position, bottom of the outlet of described fast bed reaction zone (2) and described fluidized bed reaction zone (3) is communicated with, and the entrance of the gas-solid separation equipment that the top exit of described fluidized bed reaction zone (3) is interior with settling vessel (5) is communicated with.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010202781.4A CN102286291B (en) | 2010-06-18 | 2010-06-18 | Catalytic conversion method of shale oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010202781.4A CN102286291B (en) | 2010-06-18 | 2010-06-18 | Catalytic conversion method of shale oil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102286291A CN102286291A (en) | 2011-12-21 |
| CN102286291B true CN102286291B (en) | 2014-04-30 |
Family
ID=45333055
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010202781.4A Active CN102286291B (en) | 2010-06-18 | 2010-06-18 | Catalytic conversion method of shale oil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102286291B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR3088072B1 (en) | 2018-11-05 | 2021-08-27 | Ifp Energies Now | FLUIDIZED BED CATALYTIC CRACKING PROCESS OF SHALE OIL IN CO-TREATMENT WITH A CONVENTIONAL FCC LOAD |
| CN113583705B (en) * | 2020-04-30 | 2023-03-10 | 中国石油化工股份有限公司 | Catalytic cracking method and apparatus for carrying out the method |
| CN115282901A (en) * | 2022-10-08 | 2022-11-04 | 南通市中京机械有限公司 | Oil shale reacting furnace |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4579070A (en) * | 1985-03-01 | 1986-04-01 | The M. W. Kellogg Company | Reducing mode circulating fluid bed combustion |
| CN101045881A (en) * | 2006-03-31 | 2007-10-03 | 中国石油化工股份有限公司 | Catalytic converter |
| CN101591562A (en) * | 2009-06-25 | 2009-12-02 | 中国石油化工集团公司 | A kind of fluidized catalytic cracking method and device thereof |
-
2010
- 2010-06-18 CN CN201010202781.4A patent/CN102286291B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4579070A (en) * | 1985-03-01 | 1986-04-01 | The M. W. Kellogg Company | Reducing mode circulating fluid bed combustion |
| CN101045881A (en) * | 2006-03-31 | 2007-10-03 | 中国石油化工股份有限公司 | Catalytic converter |
| CN101591562A (en) * | 2009-06-25 | 2009-12-02 | 中国石油化工集团公司 | A kind of fluidized catalytic cracking method and device thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102286291A (en) | 2011-12-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102071054B (en) | Catalytic cracking method | |
| CN102051213B (en) | Catalytic cracking method | |
| CN102899078B (en) | Catalytic cracking method for producing propylene | |
| CN102206509B (en) | Hydrocarbon catalytic conversion method for producing propylene and light aromatic hydrocarbon | |
| CN107663462B (en) | A kind of method and system of catalyzed conversion | |
| CN102690679B (en) | Catalytic cracking method for producing propylene | |
| CN102286294B (en) | Method for producing propylene and light arenes by catalytic conversion of hydrocarbons | |
| CN103627434B (en) | A kind of catalyst cracking method with hydrotreatment combinations produce propylene | |
| CN102690682B (en) | Catalytic cracking method and catalytic cracking device for producing propylene | |
| CN102373084A (en) | Method producing light fuel oil and propylene from poor residual oil | |
| CN102286291B (en) | Catalytic conversion method of shale oil | |
| CN107557066B (en) | A kind of catalysis conversion method and system of inferior feedstock oil | |
| CN110964559B (en) | Catalytic cracking method and device for producing low-carbon olefins | |
| CN110540861B (en) | Catalytic cracking process and system | |
| CN109666505B (en) | Catalytic cracking process and system | |
| CN102086413B (en) | Hydrocarbon oil catalytic conversion method | |
| CN111423905B (en) | Catalytic cracking process and system | |
| CN1690174A (en) | Catalytic conversion process for petroleum hydrocarbons | |
| CN102465036B (en) | Shale oil processing method for producing propylene | |
| CN110540860B (en) | Process and system for catalytic cracking by adopting double descending pipes | |
| CN101987964B (en) | Catalytic conversion method of hydrocarbon oil | |
| CN101928589B (en) | Catalytic cracking method of hydrocarbon oil | |
| CN111423904B (en) | Catalytic cracking process and system | |
| CN102086414B (en) | Method for catalyzing and conversing hydrocarbon oil | |
| CN113897216A (en) | Catalytic cracking method and system |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |