CN1184283C - Catalytic cracking method using double tube reactor - Google Patents
Catalytic cracking method using double tube reactor Download PDFInfo
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- CN1184283C CN1184283C CNB011414774A CN01141477A CN1184283C CN 1184283 C CN1184283 C CN 1184283C CN B011414774 A CNB011414774 A CN B011414774A CN 01141477 A CN01141477 A CN 01141477A CN 1184283 C CN1184283 C CN 1184283C
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Abstract
The present invention relates to a catalytic cracking method in which a sleeve pipe type reactor is adopted, which comprises: (1) a catalyst is supplied into the bottom of the sleeve pipe type reactor through a catalyst inlet pipe to flow upwards under the action of a prelifting medium, part of the catalyst flows into an inner pipe, and the rest catalyst is supplied into an annular reaction space formed between the inner pipe and an outer pipe to continue to flow upwards under the action of the prelifting medium; (2) hydrocarbon oil as a raw material is injected into the inner pipe of the reactor and into the annular space between the inner pipe and the outer pipe to contact the catalyst and react with the catalyst, and reaction material flows continue to flow upwards along the wall of the reactor; (3) the reaction material flows in the inner pipe and in the annular space between the inner pipe and the outer pipe are converged at an inlet of a converging pipe and supplied into gas-solid quick separation equipment through the converging pipe so that reaction oil gas and the catalyst with deposited carbon after the reaction are separated from each other; (4) the reaction oil gas is conveyed into a subsequent separation system and further divided into various products, and the catalyst after the reaction is returned to the reactor and circularly used after being stripped and regenerated.
Description
Technical field
The invention belongs to the catalyst cracking method of petroleum hydrocarbon under the situation that does not have hydrogen, more particularly, is a kind of method that adopts double tube reactor to carry out hydrocarbon oil catalytic cracking.
Background technology
Though the catalytic cracking process process has experienced the development of many decades, formed the more complete technical system of a cover, but the oil refining worker is still carrying out unremitting research and exploration, wish that this technological process not only can satisfy the requirement of the environmental regulation of increasingly stringent, and variation that can meeting the market requirement, be that enterprise creates good economic benefit.
USP5043522 and USP5846403 are the improvement to conventional catalytic cracking process.They make the upstream injecting lift pipe reactor of part catalytic gasoline by the stock oil feed nozzle, contact, react with high temperature, highly active regenerated catalyst, with light olefins such as propylene enhancing, butylene, the octane value of gasoline are improved.
CN1279270A has disclosed the method for a kind of while increasing production of liquid gas and diesel oil.This method also is with the upstream injecting lift pipe reactor of catalytic gasoline by the stock oil feed nozzle, makes it contact, react with regenerated catalyst earlier.The catalytic gasoline of this part freshening is fully cracking under high temperature, high agent-oil ratio, generates a large amount of liquefied gas, and the coke of deposition trace on catalyzer has suitably reduced activity of such catalysts simultaneously, helps high-yield diesel oil.
USP3894933 has introduced a kind of catalyst cracking method of duo-lift tube reactor of a shared settling vessel.This method is to make light cycle oil inject a riser reactor, contacts, reacts with regenerated catalyst, and make its transformation efficiency less than 30%; Reacted catalyzer enters another root riser tube, contacts, reacts with heavy cycle oil with fresh feed.
CN1069054A has proposed a kind of hydrocarbon cracking method of adaptable multieffect.This method relate to two independently riser reactor and link to each other with riser tube two the cover settling separation systems.In first riser reactor, light hydrocarbons and regenerated catalyst be at 600～700 ℃, agent-oil ratio 10～40, and the reaction times is to react under 2～20 seconds the condition, and the control catalyst carbon content is 0.1～0.4 heavy %; Reacted catalyzer enters in another root riser tube, contacts with heavy hydrocarbon, and reacts under the catalytic cracking reaction condition of routine.
In sum, the disclosed catalysis conversion method of processing lightweight oil and mink cell focus simultaneously of background technology can be divided into following two classes basically: (1) is adopted single riser reactor and the lightweight oil inlet is arranged on the upstream of mink cell focus inlet; (2) adopt duo-lift tube reactor, make different riser tubes handle different raw materials.The equipment of first kind method is changed little, but the reaction conditions of lightweight oil is relatively-stationary basically, is difficult to by the optimization of operating parameters product distribution and product property be improved.Second class methods have overcome the deficiency of first kind method, and the operational condition of every riser tube all is to regulate separately, and different stock oil is reacted under suitable separately condition.But for second class methods, no matter be the construction cost or all therefore and significantly increases of the improvement expenses of equipment of device.In addition, in the actual industrial production process,, can make the operation easier of device increase many because flow process is complicated.
Summary of the invention
The objective of the invention is to: a kind of catalyst cracking method that adopts double tube reactor is provided, and this method can be hydrocarbon oil crude material of different nature and builds suitable reaction conditions, and the product distribution and the product property of catalytic cracking process are improved.
Method provided by the invention may further comprise the steps:
(1) catalyzer enters the bottom of double tube reactor through the catalyst inlet pipe, and under the effect of pre-lifting medium, upwards flow, pipe in the part catalyzer flows into, and the catalyzer of rest part enter in annular reaction space between pipe and the outer tube, and under the pre-effect that promotes medium, continue upwards to flow;
(2) hydrocarbon oil crude material injects the interior pipe of this reactor and the annular space between interior pipe and the outer tube, contacts, reacts with catalyzer, and reactant flow continues upwards to flow along wall;
(3) reactant flow in the annular space between pipe and interior pipe and the outer tube is converged in the ingress of convergence tube, and enters in the gas-solid sharp separation equipment through convergence tube, and the reaction oil gas and the catalyzer of reaction back carbon deposit are separated;
(4) reaction oil gas is sent into subsequent separation system, and reacted catalyzer through stripping, regeneration after, Returning reactor recycles.
Compared with prior art, beneficial effect of the present invention is mainly reflected in following aspect:
Method equipment provided by the invention is simple, flexible operation.Not only mink cell focus and lightweight oil can react in same reactor, and can adjust reaction conditions flexibly according to physico-chemical property, the mass rate of raw material, have created favourable condition thereby distribute, improve product quality for improving product.
Method provided by the invention can realize the flexible adjustment of multiple production decision, for example, and gasoline scheme, diesel oil scheme, liquefied gas scheme etc.Oil refining enterprise adopts this method in time to adjust the product mix according to the variation of the market requirement, obtains remarkable economic efficiency more.
In addition, utilize method provided by the invention to improve the quality of products, alleviate petroleum products pollution that environment caused.By evidence: this method can reduce content of olefin in gasoline, improve gasoline octane rating; Reduce condensation point of diesel oil, improve the susceptibility of diesel oil, improve diesel oil stability flow ability modifying agent; Simultaneously, this method has certain effect to the content that reduces impurity such as sulphur, nitrogen in vapour, the diesel oil.
Description of drawings
Fig. 1 is the structural representation of telescoping catalyst cracker of the present invention.
Fig. 2 is the principle flow chart that the invention provides method.
Fig. 3 is the principle flow chart that the invention provides method.
Embodiment
The structure of double tube reactor of the present invention as shown in Figure 1.This reactor mainly comprises with lower member: regenerator inlet tube 1, interior pipe 2, outer tube 3, convergence tube 4, promote distribution rings 5,6 and 7 and feed nozzle 8 and 9 in advance; Wherein, interior pipe 2 is coaxial with outer tube 3, and the ratio of interior pipe cross sectional area of tube core and inner and outer pipes annular space cross-sectional area is 1: 0.1～10; The lower end of interior pipe 2 is positioned at regenerator inlet top, and interior length of tube accounts for 10～70% of this total reactor length; One end of convergence tube 4 links to each other with outer tube 3 upper ends, and the other end links to each other with gas-solid separation equipment, and convergence tube 4 is 1: 0.2～0.8 with the ratio of the cross-sectional area of interior pipe 2; Pre-lifting distribution rings 5,6 and 7 lays respectively at the bottom of this reactor, interior pipe and outer tube.This reactor has been applied for utility model patent, and application number is 01258820.2.
In method provided by the invention, the catalyzer that enters double tube reactor through the catalyst inlet pipe can be the high temperature regeneration agent from revivifier, also can be the mixture of regenerator and spent agent and/or half regenerator.The catalyzer that enters double tube reactor through the catalyst inlet pipe can be lowered the temperature through catalyst cooler, also can utilize the catalyst mix jar to make regenerator and spent agent and/or half regenerator thorough mixing after, enter double tube reactor through the catalyst inlet pipe again.
The catalyzer that the present invention uses can be any catalyzer that is applicable to catalytic cracking process, its active ingredient can be selected from Y type or HY type zeolite, the ultrastable Y that contains or do not contain rare earth and/or phosphorus, the ZSM-5 series zeolite that contains or do not contain rare earth and/or phosphorus or supersiliceous zeolite, β zeolite, the ferrierite with five-membered ring structure a kind of, two or three, also can be the amorphous silicon aluminium catalyzer.
In method provided by the invention, the annular reaction spatial bottom between the bottom of double tube reactor, interior pipe bottom and interior pipe and the outer tube is equipped with pre-lifting medium.The pre-medium that promotes adopts steam, dry gas or their mixture all can.Interior pipe gas superficial linear speed is 0.3～6.0m/s, and the gas superficial linear speed of the annular space between the inner and outer pipe is 0.2～8.0m/s.
The hydrocarbon oil crude material of the annular space in injecting between pipe and interior pipe and the outer tube is selected from: the mixture of one or more of time processing gasoline fraction, secondary processing of gasoline cut, time processing diesel oil distillate, secondary processing diesel oil cut, straight-run gas oil, wax tailings, deasphalted oil, hydrofined oil, hydrocracking tail oil, vacuum residuum or long residuum.The hydrocarbon oil crude material of pipe is preferred in injecting: the mixture of one or more of straight-run gas oil, wax tailings, deasphalted oil, hydrofined oil, hydrocracking tail oil, vacuum residuum or long residuum.The hydrocarbon oil crude material of the annular space in injecting between pipe and the outer tube is preferred: the mixture of one or more of time processing gasoline fraction, secondary processing of gasoline cut, time processing diesel oil distillate, secondary processing diesel oil cut.
Hydrocarbon oil crude material is as follows at the reaction conditions of interior pipe: 460～580 ℃ of temperature of reaction, preferred 480～550 ℃; Reaction pressure 0.1～0.6MPa, preferred 0.2～0.4MPa; Agent-oil ratio 3～15, preferred 4～10; Oil gas is 1.0～10 seconds in the residence time of interior pipe, preferred 1.5～5.0 seconds; Temperature before catalyzer contacts with hydrocarbon ils is 620～720 ℃, preferred 650～700 ℃; Atomizing steam 1～15 heavy % (accounting for raw material), preferred 2～10 heavy %.
Reaction conditions in the annular space of hydrocarbon oil crude material between interior pipe and outer tube is as follows: 300～680 ℃ of temperature of reaction, preferred 400～600 ℃; Reaction pressure 0.1～0.6MPa, preferred 0.2～0.4MPa; Agent-oil ratio 2～30, preferred 4～20; The residence time of oil gas is 0.5～20 second, preferred 1～15 second; Atomizing steam 1～15 heavy % (accounting for raw material), preferred 1～10 heavy %.Reaction conditions in the annular space of hydrocarbon oil crude material between interior pipe and outer tube can further be optimized according to the character of hydrocarbon oil crude material and the requirement of purpose product.When during as the main purpose product, adopting comparatively harsh reaction conditions with liquefied gas or low-carbon alkene, for example, 530～680 ℃ of temperature of reaction, agent-oil ratio 8～30,5～20 seconds oil gas residence time etc.; When during as the main purpose product, then taking relative demulcent operational condition with gasoline and/or diesel oil, for example, 300～540 ℃ of temperature of reaction, agent-oil ratio 2～8,1～5 second oil gas residence time etc.
In finish mixture in the annular space between pipe and interior pipe and the outer tube mix mutually in the convergence tube ingress, reaction oil gas continues reaction in convergence tube, reaction times is 0.1～3.0 second, reaction pressure, temperature, agent-oil ratio etc. are decided on the reaction conditions of interior pipe and annular space, be generally, the weight ratio of 450～600 ℃ of temperature of reaction, agent-oil ratio 4～12, reaction pressure 0.1～0.6MPa, water vapour and hydrocarbon oil crude material is 0.01～0.10: 1.
As shown in Figure 2, catalyzer enters the bottom of double tube reactor through catalyst inlet pipe 1, and under the effect of pre-lifting medium, upwards flow, pipe 2 in the part catalyzer flows into, and the catalyzer of rest part enter in annular reaction space between pipe 2 and the outer tube 3, and under the pre-effect that promotes medium, continue upwards mobile; Hydrocarbon oil crude material injects the interior pipe of this reactor and the annular space between interior pipe and the outer tube through nozzle 8 and 9 respectively, contacts, reacts with catalyzer, and reactant flow continues upwards to flow along wall; Reactant flow in the annular space between interior pipe and interior pipe and the outer tube is converged in the ingress of convergence tube 4, and enters in the settling vessel 12 through convergence tube, gas-solid sharp separation equipment, and reaction oil gas is separated with the catalyzer of reaction back carbon deposit; Reaction oil gas enters subsequent separation system 14, further be separated into various products, and reacted catalyzer falls into stripper 13, the entrained reaction oil gas of stripping catalyst under the effect of water vapour; Catalyzer behind the stripping is sent into revivifier 15 coke burning regenerations, and the catalyzer Returning reactor after the regeneration recycles.
As shown in Figure 3, catalyzer enters the bottom of double tube reactor through catalyst inlet pipe 1, and under the effect of pre-lifting medium, upwards flow, pipe 2 in the part catalyzer flows into, and the catalyzer of rest part enter in annular reaction space between pipe 2 and the outer tube 3, and under the pre-effect that promotes medium, continue upwards mobile; Hydrocarbon oil crude material injects the interior pipe of this reactor and the annular space between interior pipe and the outer tube through nozzle 8 and 9 respectively, contacts, reacts with catalyzer, and reactant flow continues upwards to flow along wall; Reactant flow in the annular space between interior pipe and interior pipe and the outer tube is converged in the ingress of convergence tube 4, and enters in the settling vessel 12 through convergence tube, gas-solid sharp separation equipment, and reaction oil gas is separated with the catalyzer of reaction back carbon deposit; Reaction oil gas enters subsequent separation system 14, further be separated into various products, and reacted catalyzer falls into stripper 13, the entrained reaction oil gas of stripping catalyst under the effect of water vapour; Catalyzer behind the stripping is sent into revivifier 15 coke burning regenerations, and the catalyzer after the regeneration enters catalyst mix jar 16, mixes with reclaimable catalyst and/or half regenerated catalyst, and mixed catalyzer Returning reactor recycles.
Except that above-mentioned Fig. 2 and shown in Figure 3, in method provided by the invention, the mixture that enters the regenerated catalyst of reactor or regenerated catalyst and reclaimable catalyst and/or half regenerated catalyst can enter the bottom of double tube reactor again after the catalyst cooler cooling.
The following examples will give further instruction to method provided by the invention, but therefore the present invention is not subjected to any restriction.
Used catalyzer is that trade names are LV-23 by Lanzhou oil-refining chemical head factory catalyst plant industrial production among the embodiment, and its main character is referring to table 1.Used hydrocarbon oil crude material is mixed 30 heavy %VR for grand celebration VGO among the embodiment, and its character sees Table 2.The testing apparatus that is adopted among the embodiment is the multifunctional small-size riser fluid catalytic cracking.
Present embodiment explanation: adopt method provided by the invention, and with lightweight oil during as the main purpose product, resulting test-results.
Main testing sequence is as follows: the recycle stock of the stock oil shown in the table 1 and this device mixes, in the interior pipe of preheating oven heating back sprue bushing formula reactor, with from regenerator sloped tube, and contact, react through the pre-regenerated catalyst that promotes the medium lifting.Annular reaction space in reacted gas that this device is produced injects between pipe and the outer tube contacts, reacts with therebetween regenerator.Finish mixture and the finish mixture in the annular reaction space in the interior pipe are up along wall respectively, mix, continue reaction in the ingress of convergence tube mutually, and enter in the settling vessel.In settling vessel internal reaction oil gas and reacted catalyst separating, oil gas enters follow-up fractionating system through gas pipeline, further is separated into various products.The product that is generated is measured respectively and analyzes.Reclaimable catalyst is sent into the revivifier coke burning regeneration behind the water vapor stripping, the catalyzer Returning reactor after the regeneration recycles.
Main operational condition is referring to table 3, and product distributes and sees Table 4, and main products character sees Table 5.By table 4 and table 5 as can be seen, when with lightweight oil during as the main purpose product, the present invention can make the yield of gasoline+diesel oil reach 77.80 heavy % under lower dry gas and coke yield, and total liquid is received and reached 89.96 heavy %.
Present embodiment explanation: adopt method provided by the invention, and with liquefied gas during as the main purpose product, resulting test-results.
Main testing sequence is as follows: the stock oil shown in the table 1 in the interior pipe of preheating oven heating back sprue bushing formula reactor, with from regenerator sloped tube, and contact, react through the pre-regenerated catalyst that promotes the medium lifting.This device is produced inject less than 350 ℃ lightweight oil (gasoline+diesel oil) in annular reaction space between pipe and the outer tube, contact, react with therebetween regenerator.Finish mixture and the finish mixture in the annular reaction space in the interior pipe are up along wall respectively, mix, continue reaction in the ingress of convergence tube mutually, and enter in the settling vessel.In settling vessel internal reaction oil gas and reacted catalyst separating, oil gas enters follow-up fractionating system through gas pipeline, further is separated into various products.The product that is generated is measured respectively and analyzes.Reclaimable catalyst is sent into the revivifier coke burning regeneration behind the water vapor stripping, the catalyzer Returning reactor after the regeneration recycles.
Main operational condition is referring to table 3, and product distributes and sees Table 4, and main products character sees Table 5.By table 4 and table 5 as can be seen, when with liquefied gas during as the main purpose product, the present invention can make liquefied gas yield reach 29.46 heavy % under lower dry gas and coke yield, and total liquid is received and reached 86.65 heavy %.
Present embodiment explanation: adopt method provided by the invention, and with gasoline during as the main purpose product, resulting test-results.
Main testing sequence is as follows: the recycle stock of the stock oil shown in the table 1 and this device mixes, in the interior pipe of preheating oven heating back sprue bushing formula reactor, with from regenerator sloped tube, and contact, react through the pre-regenerated catalyst that promotes the medium lifting.(density is 0.7316g/cm to the coker gasoline raw material
3, RON=58.8, MON=65.4, olefin(e) centent be 37.49 heavy %) inject in annular reaction space between pipe and the outer tube, contact, react with therebetween regenerator.Finish mixture and the finish mixture in the annular reaction space in the interior pipe are up along wall respectively, mix, continue reaction in the ingress of convergence tube mutually, and enter in the settling vessel.In settling vessel internal reaction oil gas and reacted catalyst separating, oil gas enters follow-up fractionating system through gas pipeline, further is separated into various products.The product that is generated is measured respectively and analyzes.Reclaimable catalyst is sent into the revivifier coke burning regeneration behind the water vapor stripping, the catalyzer Returning reactor after the regeneration recycles.
Main operational condition is referring to table 3, and product distributes and sees Table 4, and main products character sees Table 5.By table 4 and table 5 as can be seen, when with gasoline during as the main purpose product, the present invention can be under lower dry gas and coke yield, make gasoline yield can reach 59.49 heavy %, yield of light oil is 78.14 heavy %, and total liquid is received and reached 90.00 heavy %, and gasoline products has quality preferably.
Embodiment 4
Present embodiment explanation: adopt method provided by the invention, and with diesel oil during as the main purpose product, resulting test-results.
Main testing sequence is as follows: as shown in Figure 3, the recycle stock of the stock oil shown in the table 1 and this device mixes, after the preheating oven heating in the interior pipe of sprue bushing formula reactor, contact, react with the mixture of spent agent with regenerator from catalyst mix jar 16.(density is 0.8520g/cm to the coker gas oil raw material
3, sulphur content 8225ppm, nitrogen content 5018ppm, cetane value be 47) inject in annular reaction space between pipe and the outer tube, contact, react with therebetween catalyzer.Finish mixture and the finish mixture in the annular reaction space in the interior pipe are up along wall respectively, mix, continue reaction in the ingress of convergence tube mutually, and enter in the settling vessel.In settling vessel internal reaction oil gas and reacted catalyst separating, oil gas enters follow-up fractionating system through gas pipeline, further is separated into various products.The product that is generated is measured respectively and analyzes.Reclaimable catalyst is behind the water vapor stripping, the part catalyzer is sent into the revivifier coke burning regeneration, and the reclaimable catalyst of rest part directly enters catalyst mix jar 16, with the catalyst mix after the regeneration, the blending ratio of regenerated catalyst and reclaimable catalyst is 2: 1, and the mixture Returning reactor recycles.
Main operational condition is referring to table 3, and product distributes and sees Table 4, and main products character sees Table 5.By table 4 and table 5 as can be seen, when with diesel oil during as the main purpose product, the present invention can make diesel yield reach 35.13 heavy % under lower dry gas and coke yield, and total liquid is received and reached 89.93 heavy %.
Embodiment 5
Present embodiment explanation: adopt method provided by the invention, and with liquefied gas and diesel oil during as the main purpose product, resulting test-results.
Main testing sequence is as follows: the recycle stock of the stock oil shown in the table 1 and this device mixes, in the interior pipe of preheating oven heating back sprue bushing formula reactor, with from regenerator sloped tube, and contact, react through the pre-regenerated catalyst that promotes the medium lifting.Annular reaction space in gasoline fraction that this device is produced injects between pipe and the outer tube contacts, reacts with therebetween regenerator.Finish mixture and the finish mixture in the annular reaction space in the interior pipe are up along wall respectively, mix, continue reaction in the ingress of convergence tube mutually, and enter in the settling vessel.In settling vessel internal reaction oil gas and reacted catalyst separating, oil gas enters follow-up fractionating system through gas pipeline, further is separated into various products.The product that is generated is measured respectively and analyzes.Reclaimable catalyst is sent into the revivifier coke burning regeneration behind the water vapor stripping, the catalyzer Returning reactor after the regeneration recycles.
Main operational condition is referring to table 3, and product distributes and sees Table 4, and main products character sees Table 5.By table 4 and table 5 as can be seen, when with liquefied gas and diesel oil during as the main purpose product, the present invention can make liquefied gas yield reach 19.08 heavy % under lower dry gas and coke yield, and diesel yield reaches 31.46 heavy %, and total liquid is received and reached 88.80 heavy %.
Table 1
| The stock oil title | Grand celebration VGO mixes 30%VR |
| Density (20 ℃), g/cm 3Refractive index (70 ℃) kinematic viscosity, mm 2/ s, 80 ℃ of 100 ℃ of condensation points, ℃ aniline point, ℃ carbon residue, heavy % | 0.8881 1.4784 31.88 18.09 ＞50 112.9 2.7 |
| Four components, heavy % stable hydrocarbon aromatic hydrocarbons gum asphalt | 62.1 25.2 12.6 0.1 |
| Elementary composition, heavy % C H S N Br, gBr/100g | 85.74 13.01 0.13 0.20 2.8 |
| Metal content, ppm Fe Ni Cu V Na | 2.3 3.0 ＜0.1 0.1 2.6 |
| Boiling range, ℃ initial boiling point 5% 10% 30% 50% | 339 388 421 473 526 |
| Characterization factor | 12.7 |
Table 2
| Catalyzer | LV-23 |
| Chemical constitution, heavy % Al 2O 3 Na 2O RE 2O 3 | 51.2 0.32 2.0 |
| The physical properties specific surface, m 2/ g pore volume, ml/g tap density, g/cm 3Abrasion index, %h -1Size composition, V% 0～20 μ m 0～40 μ m 0～80 μ m 0～110 μ m 0～149 μ m median size, μ m | 228 0.39 0.70 1.7 3.2 19.2 68.5 81.8 96.3 66.8 |
| Medium-sized aging condition | 800 ℃/15h/100% water vapor |
| The aging little work of agent | 61 |
Table 3
| Test number purpose product | Embodiment | 1 gasoline+diesel oil freshening operation | The operation of | The operation of | The operation of embodiment 4 diesel oil freshenings | Embodiment 5 liquefied gas+diesel oil freshening operation |
| Interior pipe: stock oil fresh feed amount, the g/h temperature of reaction, ℃ agent-oil ratio reaction times, the s atomized water, heavy % heavy oil recycle ratio | Fresh material+recycle stock 936 510 5.1 1.62 5.7 0.28 | Fresh material 1,190 550 8.0 1.58 6.1 0 | Fresh material+recycle stock 1,047 515 6.2 1.60 5.8 0.15 | Fresh material+recycle stock 873 530 4.5 1.50 5.9 0.39 | Fresh material+recycle stock 944 520 5.0 1.55 5.7 0.26 | |
| Annular reaction space: stock oil light oil amount, g/h hydrogen-oil ratio (accounting for fresh feed), heavy % temperature of reaction, ℃ agent-oil ratio reaction times, the s atomized water, heavy % | 56 liters/hour 7.8 570 6.1 2.46 3.5 of reacted gases | Catalysis＜350 ℃ distillate 143 12.0 620 12.2 1.67 8.8 | Coker gasoline 157 15.0 610 8.0 1.32 8.6 | Coker gas oil 137 15.7 540 4.9 1.47 8.6 | Catalytic gasoline 236 25.0 580 7.9 0.91 8.7 | |
| The convergence tube temperature of reaction, ℃ agent-oil ratio reaction times, the s water-oil ratio, heavy % | 490 5.5 0.60 4.9 | 530 9.4 0.64 8.1 | 510 7.2 0.51 6.2 | 475 5.0 0.53 6.3 | 500 6.6 0.41 6.3 |
Table 4
| | Embodiment | 1 | | | Embodiment 4 | Embodiment 5 |
| Scheme | Gasoline+diesel oil | Liquefied gas | Gasoline | Diesel oil | Liquefied gas+diesel oil | |
| Material balance, heavy % | ||||||
| Dry gas | 2.89 | 3.26 | 2.79 | 2.49 | 3.23 | |
| Liquefied gas | 12.16 | 29.46 | 11.86 | 10.72 | 19.08 | |
| Gasoline | 49.28 | 40.70 | 59.49 | 44.08 | 38.26 | |
| Diesel oil | 28.52 | 16.49 | 18.65 | 35.13 | 31.46 | |
| Heavy oil | 0.00 | 3.03 | 0.00 | 0.00 | 0.00 | |
| Coke | 7.15 | 7.06 | 7.21 | 7.53 | 7.97 | |
| Amount to | 100.00 | 100.00 | 100.00 | 100.00 | 100.00 | |
| Transformation efficiency, heavy % | 73.48 | 80.48 | 81.35 | 64.87 | 68.54 | |
| Yield of light oil *, heavy % | 77.80 | 57.19 | 78.14 | 79.21 | 69.72 | |
| Total lighter hydrocarbons liquid is received *, heavy % | 89.96 | 86.65 | 90.00 | 89.93 | 88.80 |
* yield of light oil=yield of gasoline+diesel yield
Total lighter hydrocarbons liquid receipts=yield of liquefied gas+yield of gasoline+diesel yield
Table 5
| Gasoline property density (20 ℃) g/cm
3Existent gum, mg/100ml mercaptan sulfur, ppm maleic value, gI
2/ 100g inductive phase, min S, ppm N, ppm octane value (actual measurement) RON MON alkane content, the v% olefin(e) centent, the v% aromaticity content, | Embodiment | 1 0.7268 3 34 1.2 583 134 43 90.1 78.4 35.1 52.3 12.6 | | | Embodiment 4 0.7255 2 53 0.8 623 158 53 89.2 78.1 35.7 50.7 13.6 | Embodiment 5 0.7341 3 35 1.1 489 152 41 91.3 79.5 42.0 37.8 20.2 |
| Diesel oil character density, g/cm 3Condensation point, ℃ cetane value S, m% N, the m% initial boiling point, ℃ 90% distillates, ℃ | 0.8718 -3 42.4 0.22 0.01 209 325 | 0.8805 -10 38.4 0.27 0.03 212 329 | 0.8732 -4 41.0 0.30 0.06 211 331 | 0.8679 -3 40.2 0.31 0.02 203 333 | 0.8709 -10 42.6 0.23 0.02 204 324 |
Claims (7)
1, a kind of catalyst cracking method that adopts double tube reactor may further comprise the steps:
(1) catalyzer enters the bottom of double tube reactor through the catalyst inlet pipe, and under the effect of pre-lifting medium, upwards flow, pipe in the part catalyzer flows into, and the catalyzer of rest part enter in annular reaction space between pipe and the outer tube, and under the pre-effect that promotes medium, continue upwards to flow;
(2) hydrocarbon oil crude material injects the interior pipe of this reactor and the annular space between interior pipe and the outer tube, contacts, reacts with catalyzer, and reactant flow continues upwards to flow along wall;
(3) reactant flow in the annular space between pipe and interior pipe and the outer tube is converged in the ingress of convergence tube, and enters in the gas-solid sharp separation equipment through convergence tube, and the oil gas and the catalyzer of reaction back carbon deposit are separated;
(4) oil gas is sent into subsequent separation system, and reacted catalyzer through stripping, regeneration after, Returning reactor recycles;
Wherein, the hydrocarbon oil crude material of pipe is selected from the described injection: the mixture of one or more of straight-run gas oil, wax tailings, deasphalted oil, hydrofined oil, hydrocracking tail oil, vacuum residuum or long residuum; And the hydrocarbon oil crude material of the annular space between pipe and the outer tube is selected from injecting: the mixture of one or more of time processing gasoline fraction, secondary processing of gasoline cut, time processing diesel oil distillate, secondary processing diesel oil cut; Described hydrocarbon oil crude material is as follows at the reaction conditions of interior pipe: 460～580 ℃ of temperature of reaction, reaction pressure 0.1～0.6MPa, agent-oil ratio 3～15, oil gas are 1.0～10 seconds, catalyzer with temperature before hydrocarbon ils contacts in the residence time of interior pipe is 620～720 ℃, atomizing steam 1～15 heavy %; Reaction conditions in the annular space of described hydrocarbon oil crude material between interior pipe and outer tube is as follows: the residence time of 300～680 ℃ of temperature of reaction, reaction pressure 0.1～0.6MPa, agent-oil ratio 2～30, oil gas is 0.5～20 second, atomizing steam 1～15 heavy %;
Described reactor mainly comprises with lower member: catalyst inlet pipe (1), interior pipe (2), outer tube (3), convergence tube (4), promote distribution rings (5,6,7) and feed nozzle (8,9) in advance; Wherein, interior pipe (2) is coaxial with outer tube (3), and the ratio of the cross-sectional area of the die of interior pipe (2) and inner and outer pipes annular space cross-sectional area is 1: 0.1～10; The lower end of interior pipe (2) is positioned at the catalyst inlet top, and interior length of tube accounts for 10～70% of this total reactor length; One end of convergence tube (4) links to each other with outer tube (3) upper end, and the other end links to each other with gas-solid separation equipment, and convergence tube (4) is 1: 0.2～0.8 with the ratio of the cross-sectional area of the die of interior pipe (2); Pre-lifting distribution rings (5,6,7) lays respectively at the annular reaction spatial bottom between this reactor, interior pipe and interior pipe and the outer tube;
The gas superficial linear speed of pipe is 0.3～6.0m/s in described, and the gas superficial linear speed of the annular space between the inner and outer pipe is 0.2～8.0m/s.
2, according to the method for claim 1, it is characterized in that the described catalyzer that enters double tube reactor through the catalyst inlet pipe is selected from: a kind of in the mixture of regenerator, regenerator and spent agent and/or half regenerator.
3,, it is characterized in that the described catalyzer that enters double tube reactor through the catalyst inlet pipe lowers the temperature through catalyst cooler according to the method for claim 1.
4, according to the method for claim 1, it is characterized in that described activity of such catalysts component be selected from Y type or HY type zeolite, the ultrastable Y that contains or do not contain rare earth and/or phosphorus, the ZSM-5 zeolite that contains or do not contain rare earth and/or phosphorus or supersiliceous zeolite, β zeolite, the ferrierite with five-membered ring structure a kind of, two or three.
5, according to the method for claim 1, it is characterized in that described hydrocarbon oil crude material is as follows at the reaction conditions of interior pipe: 480～550 ℃ of temperature of reaction, reaction pressure 0.2～0.4MPa, agent-oil ratio 4～10, oil gas are 1.5～5.0 seconds, catalyzer with temperature before hydrocarbon ils contacts in the residence time of interior pipe is 650～700 ℃, atomizing steam 2～10 heavy %.
6, according to the method for claim 1, it is characterized in that the reaction conditions in the annular space of described hydrocarbon oil crude material between interior pipe and outer tube is as follows: the residence time of 400～600 ℃ of temperature of reaction, reaction pressure 0.2～0.4MPa, agent-oil ratio 4～20, oil gas is 1～15 second, atomizing steam 1～10 heavy %.
7,, it is characterized in that the reaction conditions of reactant flow in convergence tube is in the described step (3): 450～600 ℃ of temperature of reaction, reaction pressure 0.1～0.6MPa, 0.1～3.0 second reaction times according to the method for claim 1.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011414774A CN1184283C (en) | 2001-09-27 | 2001-09-27 | Catalytic cracking method using double tube reactor |
| JP2002249000A JP4412886B2 (en) | 2001-08-29 | 2002-08-28 | Catalytic cracking of petroleum hydrocarbons |
| US10/229,155 US20030116471A1 (en) | 2001-08-29 | 2002-08-28 | Catalytic cracking process of petroleum hydrocarbons |
| FR0210720A FR2829143B1 (en) | 2001-08-29 | 2002-08-29 | PROCESS FOR CATALYTIC CRACKING OF PETROLEUM HYDROCARBONS |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011414774A CN1184283C (en) | 2001-09-27 | 2001-09-27 | Catalytic cracking method using double tube reactor |
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| CN1410513A CN1410513A (en) | 2003-04-16 |
| CN1184283C true CN1184283C (en) | 2005-01-12 |
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| CNB011414774A Expired - Lifetime CN1184283C (en) | 2001-08-29 | 2001-09-27 | Catalytic cracking method using double tube reactor |
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| CN101993710A (en) * | 2009-08-25 | 2011-03-30 | 中国石油大学(北京) | Method and device for carrying out partitioning catalytic cracking on coking waxen oil |
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