CN1345911A - Method for regulating heat balance of catalytic conversion technological reaction-regeneration system - Google Patents
Method for regulating heat balance of catalytic conversion technological reaction-regeneration system Download PDFInfo
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- CN1345911A CN1345911A CN 00124665 CN00124665A CN1345911A CN 1345911 A CN1345911 A CN 1345911A CN 00124665 CN00124665 CN 00124665 CN 00124665 A CN00124665 A CN 00124665A CN 1345911 A CN1345911 A CN 1345911A
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Abstract
The method for regulating thermal equilibrium of reaction-regeneration system of catalytic conversion process includes the following steps: feeding raw material and aqueous vapour into reactor from lower portion of lift pipe, making then contact with hot regenerated catalyst, feeding the material stream produced after reaction into the setting vessel, and feeding the oil vapour separated out into fractionation system, feeding the catalyst to be regenerated into the stripper zone, injecting heavy fractino into proper position of stripper zone, and making the regenerated catalyst circulate to lift pipe reactor for use. Said invention method can combust poor slurry oil produced in catalyst conversion process to increase the heat quantity of reaction regeneration system so as to avoid non-uniform combustion produced by directly spraying combustion oil to regenerator and can prevent catalyst from locally-overheating and deactivating.
Description
The invention belongs to the thermally equilibrated method of reaction-regeneration system in a kind of adjusting catalysis conversion method.
Catalytic pyrolysis is to be that raw material production is the method for main purpose product with light olefins such as ethene, propylene with the heavy petroleum hydrocarbon.The main process of this method is: the heavy crude hydrocarbon feed is in riser tube or downstriker transfer limes reactor, in the presence of high-temperature steam, contact with solid acid catalyst, weight ratio (hereinafter to be referred as agent-oil ratio) at 650～750 ℃ of temperature of reaction, reaction pressure 0.15～0.4MPa, 0.2～5 second reaction times, catalyzer and stock oil is 15～40: 1, the weight ratio of water vapor and stock oil is under 0.3～1: 1 the condition, carries out the catalytic pyrolysis reaction.Reaction product, water vapor and reclaimable catalyst are after quick gas solid separation, and reaction product isolated obtains main purpose product ethene, propylene; Reclaimable catalyst enters revivifier behind the water vapor stripping, contact with oxygen-containing gas to carry out coke burning regeneration, and the regenerated catalyst Returning reactor of heat recycles.
Since the cracking reaction transformation efficiency height of catalytic pyrolysis technology, the temperature of reaction height, cracking reaction heat is big, and therefore the more conventional catalytic cracking of heat that needs aspect reaction or other catalysis conversion method want many.The coke that self cracking generates often can not satisfy the thermally equilibrated demand of reaction-regeneration system self.The measure that increases the reaction-regeneration system heat at present on technology mainly contains following 5 kinds:
1, add heavier feedstocks, mix residual oil more.But after mixing residual oil, can cause the gas olefins yield to descend more, require employed catalyzer that enough heavy oil conversion performances and preventing from heavy metal pollution ability must be arranged simultaneously;
2, the CO perfect combustion technology that adopts is burnt in regeneration.Can make among Jiao the carbon burning liberated heat double above and avoid secondary combustion, this is the method that at first adopts usually;
3, adopt reprocessed oil slurry or/and the operating method of recycle stock, to improve coke yield.But recycle stock or/and reprocessed oil slurry injects conversion zone, might be influenced the cracking reaction of fresh feed;
4, improve raw material preheating temperature, set up raw materials furnace and heating.This also is usually the method for the increase reactor-regenerator system thermal of employing.But the temperature to stock oil heating is restricted, and the highest feeding temperature of vacuum gas oil is not more than 400 ℃, is not more than 350 ℃ usually for the vacuum gas oil raw material of mixing residual oil, otherwise can cause heat cracking reaction takes place in the boiler tube, and further causes coking;
5, to revivifier spray combustion oil.When revivifier sprayed combustion oil, generally in order to be uniformly dispersed, the spray light cycle oil cuts that adopt owing to having only a nozzle, easily caused dispersion inhomogeneous more, and it is inhomogeneous to cause burning, and causes catalyzer local superheating inactivation, or secondary combustion takes place.
The objective of the invention is to provide on the basis of existing technology a kind of method of regulating heat balance of catalytic conversion technological reaction-regeneration system, to solve the problem of catalytic pyrolysis technology and other catalysis conversion method reaction-regeneration system shortage of heat.
Method provided by the invention is: raw material and water vapor enter from the riser tube bottom, contact with the regenerated catalyst of heat, use the pre-lifting medium that enters from the riser tube bottom to promote, and carry out scission reaction after raw material and the catalyst mix.Reacted logistics enters the settling vessel with or without the dense fluidized bed bioreactor, the reaction oil gas that carries catalyzer separates through cyclonic separator, wherein oil gas enters fractionating system, and reclaimable catalyst enters stripping stage, heavy ends is injected the appropriate location of stripping stage.Catalyst recirculation after the regeneration to riser reactor uses.
After heavy ends being injected the appropriate location of stripping stage, the colloid, the bituminous matter that are rich in polycyclic aromatic hydrocarbons in the heavy ends are attracted on the reclaimable catalyst, and bring revivifier into and burn, to increase green coke amount and burning heat release, lighter component is carried out the light product of cracking reaction generation in the heavy ends, and is stripped in the logistics of cracked reaction product.
Being used for the thermally equilibrated heavy ends of conditioned reaction-regeneration system rapidly can be the middle runnings of the self-produced slurry oil of catalytic conversion process, boiling range＞200 ℃, it also can be the cut more than boiling range＞200 that obtain of conventional catalytic cracking unit ℃, can also be the heavy ends that coking, thermally splitting, viscosity breaking generate, or straight run vacuum residuum, straight-run pitch.Described heavy ends accounts for 0.1～10 heavy % of raw material.
Above-mentioned heavy ends injects from the stripping stage bottom, and decanting point is the appropriate location above the stripped vapor inlet, as stripping stage baffle plate is arranged, and is preferably in the below of basecoat baffle plate.Nozzle opening down, axial angle α is 30 °～60 °.
The catalytic pyrolysis of raw materials used and reaction conditions in this method, regeneration and reaction-regeneration system shortage of heat and other catalytic conversion process are identical as the catalysis conversion method of voluminous liquefied gas and gasoline simultaneously, technologies such as catalysis conversion method that deep catalytic cracking is producing more propylene.
Below in conjunction with accompanying drawing method provided by the present invention is given further instruction.
Accompanying drawing illustrates a kind of method flow of regulating heat balance of catalytic conversion technological reaction-regeneration system, and the shape and size of equipment and pipeline are not subjected to the restriction of accompanying drawing, but determines as the case may be.
Raw material delivers to that process furnace 2 carries out preheating or without process furnace through pipeline 1, enter riser reactor 5 with water vapor through pipeline 3, the pre-medium that promotes enters through the bottom of pipeline 4 from riser tube 5, the catalyzer of heat enters the bottom of riser tube 5 through regenerated catalyst inclined tube 14, promotes with pre-lifting medium.Carry out scission reaction after raw material and the catalyst mix.
Reacted logistics enters the settling vessel 9 with or without the dense fluidized bed bioreactor, the reaction oil gas that carries catalyzer separates through cyclonic separator 10, wherein oil gas enters fractionating system through pipeline 11, reclaimable catalyst enters settling vessel stripping stage 8 by cyclonic separator 10, use stripped vapor to carry out stripping, remove the oil gas of catalyst entrainment from pipeline 6.Being used for conditioned reaction-regenerative heat equilibrated heavy ends enters the appropriate location of stripping stage 8 through pipeline 7, its overwhelming majority is attracted on the reclaimable catalyst, and bring revivifier into and burn, small part is carried out cracking reaction and is generated light product, and is stripped in the logistics of cracked reaction product.
The reclaimable catalyst that is adsorbed with above-mentioned heavy ends enters through reclaimable catalyst inclined tube 13 and burns jar 15, with of the high temperature catalyst contact of revivifier two close sections mutually 17 by outer circulating tube 16, use the air-lift unit that provides from pipeline 12 also to burn rapidly, catalyzer after burning exports thick cyclonic separator 19 by dilute phase pipe 18 and dilute phase pipe and enters revivifier settling vessel 20, in the dilute phase of revivifier settling vessel 20, not settled catalyzer and regenerated flue gas enter revivifier cyclonic separator 21 in the lump and carry out gas solid separation, and flue gas enters smoke energy recovering system by pipeline 22.
The slurry oil inferior that method provided by the invention can be produced catalytic pyrolysis technology burns, to increase the heat of reaction-regeneration system.Avoided directly spraying combustion oil to revivifier and caused that burning is inhomogeneous, caused catalyzer local superheating inactivation and secondary combustion, the slurry oil productive rate inferior that also will contain granules of catalyst simultaneously reduces to lower level.
The present invention is applicable to catalytic pyrolysis technology, also is applicable to catalytic conversion process that other reactive moieties the needs more heats situation as the catalytic conversion process of voluminous liquefied gas and gasoline simultaneously, technological reaction-regeneration system shortages of heat such as catalytic conversion process that deep catalytic cracking is producing more propylene.
Accompanying drawing is a kind of schematic flow sheet of regulating the method for heat balance of catalytic conversion technological reaction-regeneration system.
Each numbering is described as follows in the accompanying drawing:
1,3,4,6,7,11,12,22 all represent pipeline, 2 is process furnace, and 5 is riser reactor, 8 is stripping stage, and 9 is the settling vessel of reactor, and 10 is the cyclonic separator of reacting-settler, 13 is the reclaimable catalyst inclined tube, and 14 is the regenerated catalyst inclined tube, and 15 for burning jar, 16 is the outer circulating tube of revivifier, 17 is two close phase sections of revivifier, and 18 is the dilute phase pipe, the 19 thick cyclonic separators for the outlet of dilute phase pipe, 20 is the settling vessel of revivifier, and 21 is the cyclonic separator of revivifier.
The following examples will give further instruction to method provided by the invention, but not thereby limiting the invention.
Comparative Examples
This Comparative Examples is not injected any heavy ends at the stripping stage of catalytic pyrolysis device.
The vacuum residuum of mixing 30 heavy % with vacuum gas oil is raw material, and raw material and water vapor enter from the riser tube bottom, contact with the regenerated catalyst of heat, uses the pre-lifting medium that enters from the riser tube bottom to promote, and carries out scission reaction after raw material and the catalyst mix.Reacted logistics enters the settling vessel with or without the dense fluidized bed bioreactor, and the reaction oil gas that carries catalyzer separates through cyclonic separator, and wherein oil gas enters fractionating system, and reclaimable catalyst enters stripping stage.Catalyst recirculation after the regeneration to riser reactor uses.
Operational condition and test-results are as shown in table 1, as can be seen from Table 1, coke yield only is 8.7 heavy %, can not satisfy the demand of reaction-regeneration system heats such as raw material, water vapor, atmosphere temperature rising, cracking reaction heat, thermosteresis, raw material must be heated to 528 ℃ at process furnace, just can remedy the deficiency of reaction-reactivation heat, but in actually operating, for heavy oil or mix residual oil raw material, so high process furnace preheating temperature can cause thermally splitting and tube coking, and this scheme is infeasible.
Embodiment
This embodiment injects the self-produced slurry oil of this catalytic pyrolysis device at stripping stage, and the slurry oil that injects stripping stage accounts for 2.3 heavy % of raw material, and used raw material is identical with reaction conditions and Comparative Examples.
Raw material and water vapor enter from the riser tube bottom, contact with the regenerated catalyst of heat, use the pre-lifting medium that enters from the riser tube bottom to promote, and carry out scission reaction after raw material and the catalyst mix.Reacted logistics enters the settling vessel with or without the dense fluidized bed bioreactor, the reaction oil gas that carries catalyzer separates through cyclonic separator, wherein oil gas enters fractionating system, reclaimable catalyst enters stripping stage, the slurry oil that accounts for raw material 2.3 heavy % is injected above the stripped vapor inlet, nozzle opening down, axial angle α is 45 °.Catalyst recirculation after the regeneration to riser reactor uses.
Operational condition and test-results are as shown in table 1, as can be seen from Table 1, coke yield is 11.0 heavy %, when coke yield is 11 weight %, its required raw material preheating temperature only is 349 ℃, can satisfy the requirement of reaction-regeneration system thermal equilibrium, this is feasible in the full scale plant operation, and can obtain effect preferably.Table 1
| Scheme | Comparative Examples | Embodiment |
| The raw material treatment capacity, ton/time | ????50 | ????50 |
| Temperature of reaction, ℃ | ????640 | ????640 |
| Reaction water filling quantity of steam, heavy % | ????55 | ????55 |
| Agent-oil ratio | ????23.0 | ????23.0 |
| Operating method | One way | One way |
| Regeneration | CO perfect combustion | CO perfect combustion |
| Regeneration temperature, ℃ | ????750 | ????750 |
| CO in the flue gas 2/CO | ????297.8 | ????297.8 |
| O in the flue gas 2, heavy % | ????3.0 | ????3.0 |
| Hydrogen richness among Jiao, heavy % | ????8.0 | ????8.0 |
| Product distributes, heavy % | ||
| ????H 2～C 2 | ????40.2 | ????40.2 |
| ????C 3～C 4 | ????26.4 | ????26.4 |
| Gasoline | ????11.7 | ????11.7 |
| Solar oil | ????8.5 | ????8.5 |
| Slurry oil | ????4.0 | ????1.7 |
| Coke | ????8.7 | ????11.0 |
| Loss | ????0.5 | ????0.5 |
| Add up to | ????100.0 | ????100.0 |
| The desired raw material preheating temperature, ℃ | ????528 | ????349 |
| Explanation | Preheating temperature＞350 ℃, infeasible | Preheating temperature＜350 ℃, feasible |
Claims (5)
1, a kind of method of regulating heat balance of catalytic conversion technological reaction-regeneration system, raw material and water vapor enter from the riser tube bottom, contact with the regenerated catalyst of heat, promote with the pre-lifting medium that enters from the riser tube bottom, reacted logistics enters the settling vessel with or without the dense fluidized bed bioreactor, the reaction oil gas that carries catalyzer separates through cyclonic separator, wherein oil gas enters fractionating system, reclaimable catalyst enters stripping stage, catalyst recirculation after the regeneration to riser reactor uses, and it is characterized in that heavy ends is injected the appropriate location of stripping stage.
2, according to the method for claim 1, it is characterized in that described heavy ends can be the middle runnings of the self-produced slurry oil of catalytic conversion process, boiling range＞200 ℃, it also can be the cut more than boiling range＞200 that obtain of conventional catalytic cracking unit ℃, can also be the heavy ends that coking, thermally splitting, viscosity breaking generate, or straight run vacuum residuum, straight-run pitch.
3,, it is characterized in that described heavy ends accounts for 0.1～10 heavy % of raw material according to the method for claim 1 or 2.
4, according to the method for claim 1, it is characterized in that described heavy ends injects from the stripping stage bottom, decanting point above the stripped vapor inlet, nozzle opening down, axial angle α is 30 °～60 °.
5, according to the method for claim 1 or 2, it is characterized in that described catalytic conversion process regeneration system rapidly shortage of heat, this technology comprises the catalytic conversion process or the deep catalytic cracking technology of catalytic pyrolysis technology, voluminous liquefied gas of while and gasoline.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001246658A CN1151232C (en) | 2000-09-28 | 2000-09-28 | Method for regulating heat balance of catalytic conversion technological reaction-regeneration system |
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| CNB001246658A CN1151232C (en) | 2000-09-28 | 2000-09-28 | Method for regulating heat balance of catalytic conversion technological reaction-regeneration system |
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| CN1345911A true CN1345911A (en) | 2002-04-24 |
| CN1151232C CN1151232C (en) | 2004-05-26 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101164684B (en) * | 2006-10-20 | 2010-10-06 | 中国石油化工股份有限公司 | Combined fluidized bed reactor |
| CN101164685B (en) * | 2006-10-20 | 2010-10-06 | 中国石油化工股份有限公司 | Combined quickly fluidized bed reactor |
| CN101063041B (en) * | 2006-04-28 | 2011-04-20 | 中国石油化工股份有限公司 | Method for regulating heat balance |
| CN105622316A (en) * | 2014-10-29 | 2016-06-01 | 中国石油化工股份有限公司 | Conversion method of Fischer-Tropsch synthesis oil raw material |
| CN106609151A (en) * | 2015-10-21 | 2017-05-03 | 中国石油化工股份有限公司 | Method for producing low-carbon olefin |
| CN116212973A (en) * | 2021-12-03 | 2023-06-06 | 中国石油化工股份有限公司 | Catalytic cracking regeneration equipment and regeneration method suitable for maintaining heat balance |
| WO2023122477A1 (en) * | 2021-12-20 | 2023-06-29 | Uop Llc | Process and apparatus for contacting feed and catalyst with improved fluid dynamics |
-
2000
- 2000-09-28 CN CNB001246658A patent/CN1151232C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101063041B (en) * | 2006-04-28 | 2011-04-20 | 中国石油化工股份有限公司 | Method for regulating heat balance |
| CN101164684B (en) * | 2006-10-20 | 2010-10-06 | 中国石油化工股份有限公司 | Combined fluidized bed reactor |
| CN101164685B (en) * | 2006-10-20 | 2010-10-06 | 中国石油化工股份有限公司 | Combined quickly fluidized bed reactor |
| CN105622316A (en) * | 2014-10-29 | 2016-06-01 | 中国石油化工股份有限公司 | Conversion method of Fischer-Tropsch synthesis oil raw material |
| CN105622316B (en) * | 2014-10-29 | 2017-12-22 | 中国石油化工股份有限公司 | A kind of method for transformation of Fischer-Tropsch synthesis oil raw material |
| CN106609151A (en) * | 2015-10-21 | 2017-05-03 | 中国石油化工股份有限公司 | Method for producing low-carbon olefin |
| CN106609151B (en) * | 2015-10-21 | 2018-05-18 | 中国石油化工股份有限公司 | A kind of method for producing low-carbon alkene |
| CN116212973A (en) * | 2021-12-03 | 2023-06-06 | 中国石油化工股份有限公司 | Catalytic cracking regeneration equipment and regeneration method suitable for maintaining heat balance |
| WO2023122477A1 (en) * | 2021-12-20 | 2023-06-29 | Uop Llc | Process and apparatus for contacting feed and catalyst with improved fluid dynamics |
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| CN1151232C (en) | 2004-05-26 |
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Granted publication date: 20040526 Termination date: 20180928 |