CN102040438A - Coaxial circular reaction-regeneration device with embedded riser - Google Patents
Coaxial circular reaction-regeneration device with embedded riser Download PDFInfo
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Abstract
The invention relates to a coaxial circular reaction-regeneration device with an embedded riser, mainly solving the problem of high temperature reaction difficulty in a traditional catalytic cracking process of light hydrocarbon and light oil by adopting a riser reactor for circular reaction regeneration. According to the technical scheme, the reaction-regeneration device comprises a settler, a regenerator and a riser reactor, wherein the main reaction area of the riser reactor is arranged in the regenerator, and the settler, the steam stripping segment and the riser reactor are arranged on the same axis. The invention favorably solves the problem and can be used in the industrial production for preparing ethylene and propylene through cracking light oil.
Description
Technical field
The present invention relates to the embedded riser tube circulating reaction-regenerating unit of a kind of coaxial-type.
Background technology
Ethene, propylene are important basic organic synthesis raw materials, in recent years, are subjected to the driving of downstream derivative demand, the market requirement sustainable growth of global ethene, propylene.At present, the production of ethene, propylene mainly relies on the steam heat cracking.About 90% ethene and 61% propylene are from the steam heat cracking process, though this technology is used widely in the world, but still there is unsatisfactory part, especially reaction needed high temperature (800～1000 ℃), energy consumption is big, low value-added dry gas yield height.If the introducing catalyzer adopts catalytic thermal cracking method, then can make temperature of reaction reduce by 50～200 ℃, reduce the generation of energy consumption and dry gas, and improve the propylene selectivity, so at present many investigators are devoted to the research of catalytic pyrolysis preparing ethylene, propylene.
The raw material of catalytic pyrolysis preparing ethylene, propylene can be divided into two big classes: heavy oil and lighter hydrocarbons/light oil.Lighter hydrocarbons, light oil are because hydrogen richness is higher than heavy oil, and the selectivity height of ethene, propylene is more suitable for the cracking stock as ethene, propylene.Yet the carbon number of lighter hydrocarbons, light oil is low, difficult cracking, and reaction needed generally is higher than 550 ℃ than higher temperature.This reaction process can adopt fixed-bed reactor and circulating fluid bed reactor.For fixed-bed reactor, technical process is fairly simple, but to catalyst stability and anti-coking performance demands height; And the carbochain of lighter hydrocarbons, light oil is short, and it is cracked into ethene, the required catalytic activity height of propylene, so there is the contradiction of difficulty mediation in catalyzer aspect raising activity and the inhibition coke, this also just becomes the bottleneck that restricts the fixed-bed process development.For circulating fluid bed reactor, can realize the successive reaction regeneration of catalyzer, needn't consider that catalyzer suppresses the performance of coking, catalyst activity can significantly improve, and is beneficial to the promotion catalyzed reaction, improves selectivity of light olefin, suppresses dry gas.This technology can be used for reference conventional heavy oils fluidized catalyst cracked technology pattern, and promptly reaction-regeneration system comprises riser reactor, revivifier and a settling vessel; The settling vessel bottom is a stripping stage; Settling vessel and riser reactor be coaxial arranging up and down, and the outlet of riser reactor top links to each other with the interior gas-solid quick disconnector of settling vessel; Settling vessel, riser reactor and revivifier are separate, are side by side and arrange; The revivifier bottom links to each other with the bottom of riser reactor by regenerator sloped tube; The settling vessel bottom links to each other with revivifier by inclined tube to be generated.Yet, because the hydrogen richness of lighter hydrocarbons, light oil is higher, though pyroreaction but the green coke amount is less, and the coke that generates when reaction institute heat requirement is by revivifier burning-off catalyst reaction in the ciculation fluidized bed process and providing, if the green coke amount is few, revivifier burns the shortage of heat of generation, is difficult to the high temperature that guarantees that cracking is required.Therefore, there is contradiction in the ciculation fluidized bed process of lighter hydrocarbons, naphtha catalytic cracking system ethene, propylene, heat undersupply this respect few in pyroreaction and green coke amount.For addressing this problem, some technology is coupled lighter hydrocarbons, naphtha catalytic cracking and heavy oil fluid catalytic cracking, adopt two riser reactors cracking light hydrocarbon/light oil and heavy oil respectively, a shared revivifier, relevant patent has WO99/57230, US2002/01899732002, ZL03126213.9 etc.Because the coke content height of heavy oil catalytic pyrolysis coking agent, the heat that heavy oil coking agent regeneration produces can be supplied with lighter hydrocarbons/naphtha catalytic cracking and the common institute of heavy oil fluid catalytic cracking heat requirement.Yet the shared a kind of catalyzer of these two reaction process, the requirement how this catalyzer takes into account two reaction process becomes a difficult problem again.In addition, existing fluid catalytic cracking of heavy oil riser arrangement, the heat radiation of riser reactor and regenerator sloped tube self is very important, if temperature of reaction is higher, for the then heat dissipation capacity increasing, this part heat lighter hydrocarbons that supply is difficult to guarantee for heat, naphtha catalytic cracking, more precious.
Summary of the invention
Technical problem to be solved by this invention is when adopting riser reactor to carry out circulating reaction regeneration in existing lighter hydrocarbons, the naphtha catalytic cracking process, is difficult to realize the problem of pyroreaction, provides a kind of new coaxial-type embedded riser tube reaction-regenerative device.When this reaction-regenerative device is used for lighter hydrocarbons, light oil high-temperature catalytic cracking ethylene preparation, propylene process, have that calorific loss is few, temperature of reaction is high, ethene and the high advantage of propene yield.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: the embedded riser tube circulating reaction-regenerating unit of a kind of coaxial-type mainly comprises at least one embedded riser reactor 1, revivifier 2, settling vessel 3; Settling vessel 3 inside are provided with gas-solid cyclone separator 8 and gas-solid quick disconnector 20, and top has products export 12, and the bottom is a stripping stage 4; The outside, stripping stage 4 bottoms has the reclaimable catalyst outlet, links to each other with the reclaimable catalyst inlet of revivifier 2 through inclined tube 18 to be generated; Stripping stage 4 is passed on embedded riser reactor 1 top, and outlet links to each other with gas-solid quick disconnector 20 in the settling vessel 3, and the middle part is a main reaction region, is positioned at revivifier 2 inside, and the bottom is positioned at revivifier and be provided with at least one feed nozzle 10 outward; Revivifier 2 is positioned at stripping stage 4 belows, and inside is provided with gas-solid cyclone separator 19, and top has exhanst gas outlet 16, and the bottom has the regenerated catalyst outlet, links to each other with riser reactor 1 bottom through regenerator sloped tube 5; Settling vessel 3 and embedded riser reactor 1 are on same axis.
In the technique scheme, feed nozzle 10 preferred versions advance the unreacted lighter hydrocarbons of lighter hydrocarbons of different nature, light oil or freshening, light oil respectively for being provided with at least 2.The emulsion zone of revivifier 2 is provided with fuel oil gas nozzle 15, can spray fuel oil gas and improve regenerator temperature.Gas-solid cyclone separator 19 in gas-solid cyclone separator 8 in the settling vessel 3 and the revivifier 2 is 1～3 grade.Main reaction region can reducing, the caliber that is positioned at the intensive emulsion zone part of revivifier 2 lower catalytic agent is little, the caliber that is positioned at the low freeboard of fluidized bed part of revivifier 2 top density of catalyst is big, thereby form two reaction zones, be fit to revivifier emulsion zone and the bigger situation of the freeboard of fluidized bed temperature difference, to reduce the excessive and distortion that causes of riser tube different sites temperature contrast, caliber is 0.5～0.9 than preferable range.
The average reaction temperature of embedded riser reactor 1 is 570～680 ℃, and reaction pressure is 0.1～0.35MPa, and agent-oil ratio is 6～40 (weight ratios), and catalyst in reactor density is 50～400 kilograms/meter
3, it is 0.5～13 meter per second that oil gas enters reactor place linear velocity.Temperature is 650～750 ℃ in the revivifier 2.Lighter hydrocarbons, the preferred hybrid C 4 gas of light oil raw material, petroleum naphtha, FCC gasoline, solar oil or hydrogenation tail oil.Catalyzer is selected from sial, aluminium phosphorus, aluminium silicophosphate molecular sieve or the composite molecular screen that at least a aperture is 0.4～0.65 nanometer, carrier is suitable porousness body material mixture, porous matrix material comprises kaolin, aluminum oxide, silicon oxide, magnesium oxide, zirconium white, Thorotrast, beryllium oxide etc., itself has acidity, certain catalytic performance is arranged, and matrix also can be cogelled form.
Product yield of the present invention is defined as ethene that the unit time generates, propylene quality divided by material quantity, and transformation efficiency is defined as (the unconverted raw material of 100-)/100 * 100%.The residence time be the riser reactor volume divided by oil gas logarithmic mean volumetric flow rate, wherein oil gas logarithmic mean volumetric flow rate is the logarithm of the difference of riser tube outlet and inlet oil gas volumetric flow rate divided by the merchant of oil gas vent and inlet average-volume flow.Agent-oil ratio (C/O) is the ratio of catalyst recirculation amount (ton/hour) and total feed (ton/hour).
The present invention is from providing the angle of additional heat and minimizing thermosteresis, riser reactor is placed internal regenerator, and introducing fuel oil gas line, both utilized the high temperature atmosphere of internal regenerator that reaction institute heat requirement is provided, reduce the calorific loss of riser reactor again, thereby realize lighter hydrocarbons, light oil high-temperature catalytic cracking ethylene preparation, propylene.Adopt technical scheme of the present invention can guarantee that average reaction temperature reaches 570～680 ℃ in the riser tube.Be raw material with the FCC petroleum naphtha, adopting the ZSM-5 molecular sieve catalyst, temperature of reaction is 630 ℃, and agent-oil ratio is 32 o'clock, and once through ethylene yield is 15.13%, and propene yield is 26.61%, has obtained better technical effect.
Description of drawings
Fig. 1 is the structural representation of reaction-regenerative device of the present invention.
Among Fig. 1,1 is embedded riser reactor, and 2 is revivifier, and 3 is settling vessel, 4 is stripping stage, and 5 is regenerator sloped tube, and 6 are the regeneration guiding valve, and 8 is the settling vessel internal cyclone separators, 9 is air-distributor, and 10 is nozzle, and 11 is lighter hydrocarbons, light oil raw material, 12 is splitting gas, and 13 for promoting medium, and 14 is regeneration air, 15 is the fuel oil gas nozzle, and 16 is exhanst gas outlet, and 17 is guiding valve to be generated, 8 is inclined tube to be generated, and 19 is the revivifier internal cyclone separators, and 20 are the gas-solid quick disconnector.
Lighter hydrocarbons, light oil raw material 11 enter in the embedded riser reactor 2 through feed nozzle 10, contact with regenerated catalyst, and reaction generates the product that contains low-carbon alkene, carry reclaimable catalyst and enter settler 3 through gas-solid quick disconnector 20; Most of catalyst that cyclone separator 8 is separated enters settler 3, and gaseous products and the catalyst that do not separated by cyclone separator 8 of part enter the next stage cyclone separator and carry out Re-isolation, and gaseous products 12 enters follow-up centrifugal station through outlet line; Settler 3 interior reclaimable catalysts process stripping section 4 strippings are by inclined tube 18 to be generated and guiding valve to be generated 17, enter coke-burning regeneration in the regenerator 2, the flue gas that the coke burning generates enters follow-up energy-recuperation system through regenerator internal cyclone separators 19 from exhanst gas outlet 16; The catalyst that regeneration is finished enters in the embedded riser 1 by regenerated catalyst circulation inclined tube 5; Promoting medium 13 moves upward and raw material 11 haptoreactions the regenerated catalyst in the embedded riser reactor 1.
The invention will be further elaborated below by embodiment.
Embodiment
[embodiment 1]
Carried out 5 groups of experiments on device shown in Figure 1, reaction raw materials, reaction conditions, catalyzer and reaction result are as shown in table 1.Riser reactor is nested in internal regenerator, and a feed nozzle is equipped with in the place that the bottom is positioned at the revivifier outside, and the riser reactor specification is 40 millimeters * 4 millimeters * 4.5 meters of Φ, does not have reducing.The settling vessel specification is 80 millimeters * 6 millimeters * 1.5 meters of Φ, and cyclonic separator wherein is an one-level.The revivifier specification is 273 millimeters * 6 millimeters * 4 meters of Φ, and cyclonic separator wherein is an one-level.2 meters plane is provided with three fuel oil gas nozzles apart from the bottom in the revivifier, and five equilibrium is arranged, and feeds methane gas and burns, and methane flow is 80 ml/min.Temperature in the revivifier is 680～730 ℃.
The quality percentage composition of butylene is that 73.8% (the quality percentage composition of wherein suitable-2-butylene is 23.48% in the hybrid C 4, instead-the quality percentage composition of 2-butylene is 48.86%, the quality percentage composition of 1-butylene is 1.46%), the quality percentage composition of normal butane is 26.2%; The FCC petroleum naphtha is mainly amylene, hexene, and the quality percentage composition is respectively 36.4% and 34.1%.
The preparation method of experiment catalyst system therefor:, add suitable quantity of water, HCl and H with molecular sieve, carrier and binding agent mechanically mixing
3PO
4(preparation SAPO-34 does not add during catalyzer), the control pH value is not less than 3, and slurries stir the back in 500 ℃ of following spray shapings.In the ZSM-5 catalyzer of gained, P
2O
5Content is 2%, and the mass ratio of HZSM-5 molecular sieve and matrix is 3: 6.8; The silica alumina ratio SiO of HZSM-5 molecular sieve
2/ Al
2O
3Be 38; Matrix is the mixture of kaolin and aluminium sesquioxide, and both mass ratioes are 2: 8.In the SAPO-34 catalyzer of gained, the mass ratio of HSAPO-34 molecular sieve and matrix is 3.5: 6.5; The phosphorus al mole ratio P of HSAPO-34 molecular sieve
2O
5/ Al
2O
3Be 0.9, silica alumina ratio SiO
2/ Al
2O
3Be 1.2; Matrix is the mixture of kaolin and aluminium sesquioxide, and both mass ratioes are 1: 9.
Table 1
[comparative example 1]
Do not use embedded riser tube shown in Figure 1, and adopt the external riser tube of conventional flow fluidized catalytic cracking unit to carry out 2 groups of contrast experiments, wherein riser reactor is in the revivifier outside, specification is 25 millimeters * 2.5 millimeters * 6 meters of Φ, do not have reducing, other main structure parameters are with the used experimental installation of embodiment 1.Reaction raw materials, catalyzer, reaction conditions and result are as shown in table 2.Raw materials used composition is seen embodiment 1.Temperature in the revivifier is 680～730 ℃.
[embodiment 2]
Adopt embedded riser arrangement substantially the same manner as Example 1, two feed nozzles are set on the wherein embedded riser tube, two nozzles advance hybrid C 4 and FCC petroleum naphtha from bottom to top respectively at a distance of 0.2 meter, and reaction raw materials, reaction conditions, catalyzer and reaction result are as shown in table 3.Raw materials used composition is seen embodiment 1.Temperature in the revivifier is 680～730 ℃.
Table 2
Table 3
Claims (5)
1. the embedded riser tube circulating reaction-regenerating unit of coaxial-type mainly comprises embedded riser reactor (1), revivifier (2), settling vessel (3); Settling vessel (3) inside is provided with gas-solid cyclone separator (8) and gas-solid quick disconnector (20), and the top has products export (12), and the bottom is stripping stage (4), and stripping stage (4) bottom links to each other with revivifier (2) bottom through inclined tube to be generated (18); Revivifier (2) is positioned at stripping stage (4) below, and inside is provided with gas-solid cyclone separator (19), and top has exhanst gas outlet (16), and bottom regenerator sloped tube (5) links to each other with riser reactor (1) bottom; Stripping stage (4) is passed on embedded riser reactor (1) top, the interior gas-solid quick disconnector (20) of outlet and settling vessel (3) links to each other, its middle part is a main reaction region, is positioned at revivifier (2) inside, and the bottom is positioned at outside the revivifier and is provided with at least one feed nozzle (10); Settling vessel (3), stripping stage (4) and embedded riser reactor (1) are on same axis.
2. the embedded riser tube circulating reaction-regenerating unit of coaxial-type according to claim 1 is characterized in that feed nozzle (10) is at least 2.
3. the embedded riser tube circulating reaction-regenerating unit of coaxial-type according to claim 1 is characterized in that the emulsion zone of revivifier (2) is provided with fuel oil gas nozzle (15).
4. the embedded riser tube circulating reaction-regenerating unit of coaxial-type according to claim 1 is characterized in that gas-solid cyclone separator (8) and the interior gas-solid cyclone separator (19) of revivifier (2) in the settling vessel (3) is 1～3 grade.
5. the embedded riser tube circulating reaction-regenerating unit of coaxial-type according to claim 1, the part caliber that the main reaction region that it is characterized in that embedded riser reactor (1) is arranged in the revivifier emulsion zone is little, the part caliber that is arranged in the revivifier freeboard of fluidized bed is big, and the caliber ratio is 0.5～0.9.
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Cited By (4)
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|---|---|---|---|---|
| CN102559240A (en) * | 2012-01-17 | 2012-07-11 | 马俊杰 | Dual-cycle mode catalytic cracking reaction regenerative system production technology and device |
| CN103725320A (en) * | 2012-10-10 | 2014-04-16 | 中国石油化工股份有限公司 | Catalytic cracking apparatus and method for increasing yield of ethene and/or propylene |
| CN103725321B (en) * | 2012-10-10 | 2015-10-28 | 中国石油化工股份有限公司 | The petroleum hydrocarbon catalytic cracking process of a kind of high output of ethylene and/or propylene and device thereof |
| CN105585408A (en) * | 2014-10-20 | 2016-05-18 | 中国石油化工股份有限公司 | Method for preparing light olefin from small molecular hydrocarbon mixture |
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Application publication date: 20110504 |