CN1136994C - Continuous catalyst-regenerating process - Google Patents
Continuous catalyst-regenerating process Download PDFInfo
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- CN1136994C CN1136994C CNB011184248A CN01118424A CN1136994C CN 1136994 C CN1136994 C CN 1136994C CN B011184248 A CNB011184248 A CN B011184248A CN 01118424 A CN01118424 A CN 01118424A CN 1136994 C CN1136994 C CN 1136994C
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- regeneration gas
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Abstract
The present invention relates to a continuous catalyst regenerating method. Catalysts to be regenerated orderly and downwards pass through a buffer zone, a chark zone, an oxychlorination zone and a calcining zone of a regenerator; regeneration gas firstly enters the upper space in the chark zone, which is surrounded by an inner screen, and passes through an upper catalyst bed layer in the radial direction; the mixed gas passes through a lower catalyst bed layer along the radial direction after the regeneration gas is mixed with replenished normal-temperature inert gas and dry air in the space surrounded by an outer screen and the inner wall of the regenerator; the mixed gas is led out of the regenerator after entering a lower space surrounded by the inner screen, and then the led-out gas returns to the chark zone of the regenerator for cyclic use through the steps of purification, drying, etc. The method can make the catalyst regenerated under the environment of lower temperature and low water content.
Description
Technical field
The present invention relates to a kind of renovation process of hydrocarbon conversion catalyst, more particularly, is a kind of continuous Catalyst-regenerating process.
Background technology
Catalytic reforming is a kind of hydrocarbon conversion process, it is a main products with stop bracket gasoline and aromatic hydrocarbons, and the cheap hydrogen of by-product, the main chemical reactions that takes place has dehydrogenation reaction, dehydrocyclization reaction, isomerization reaction, cracking reaction and green coke reaction etc., wherein the sedimentation of coke of green coke reaction generation is on the surface of catalyzer, activity of such catalysts is descended, need activity of such catalysts to be recovered through regenerative process.Processes such as regenerative process generally comprises and makes charcoal, chlorination renewal, roasting and reduction.The process of making charcoal is with oxygen-containing gas burn off coke deposited on catalyst charcoal, takes away the burning liberated heat simultaneously.The chlorination renewal process is the chlorine constituent element that runs off on the make-up catalyst, makes active metal component on the catalyzer oxidized and be evenly distributed on the carrier surface of catalyzer simultaneously.Roasting process is removed moisture contained in the catalyzer.Reduction process is the metal active constituent element reduction that makes oxidation state in the atmosphere of hydrogen.
Moving bed technique is applied to after the hydrocarbon conversion process, has realized the circulation of catalyzer between reactor and revivifier, thereby has reached the purpose of continuous catalyst regenerating, and activity of such catalysts is maintained on the higher level all the time.The revivifier of the cyclic regeneration system of hydrocarbon conversion catalyst generally is made up of make charcoal district and roast area, and the revivifier of continuous reforming catalyst often will increase the oxychlorination district, with the chlorine constituent element that runs off on the make-up catalyst and make active metal component obtain redispersion.The agent structure in district of making charcoal is a bed radially, and catalyzer relies on gravity to move down with speed slowly in the ring structure bed, contains the oxygen regeneration gas radially by beds, the process thereby realization is made charcoal continuously.There are radially bed and axially two kinds of structures of bed in the oxychlorination district, and roast area is generally the axial arrangement bed.
Depending primarily on the speed that its specific surface area descends the work-ing life of hydrocarbon conversion catalyst, is humidity, regeneration temperature and the catalyzer of the regeneration gas residence time in the high-temperature zone and influence the principal element that its specific surface area descends.Process is carried out under hot conditions because make charcoal, and the coke deposited on catalyst charcoal can generate aqueous vapor in combustion processes, make charcoal and under aqueous environment, finish, so the regeneration process of making charcoal of hydrocarbon conversion catalyst is the main process that influences catalyst life.
For the bed of radially making charcoal, because in the bed ingress, catalyzer has higher carbon content, when with the time radially by the containing the oxygen regeneration gas and contact of beds, make charcoal and emit a large amount of heats, and gradually inwardly the screen cloth place assemble, cause in bed top near the temperature drift of the bed screen cloth, and lower owing to the carbon content on the catalyzer in the bottom of bed, the liberated heat of making charcoal is less, and the temperature rise of bed is less.So for whole bed; the high-temperature zone on bed top brings adverse influence easily for the performance of catalyzer; and the bottom bed temperature is lower; also have the potentiality that further improve the ability of making charcoal; therefore suitably regulate the performance of the interior temperature distribution of bed to guard catalyst, will have positive effect the work-ing life that prolongs catalyzer.
USP4,578,370 and the reclaiming process that provides of CN86102807A in, the district that makes charcoal of revivifier is one section radially bed structure, catalyzer relies on gravity slowly to move down in annular space, make charcoal and distinguish the gas space separated into two parts at outer screen cloth place, corresponding upper catalyst bed layer mainly works the effect of making charcoal, the lower catalyst bed layer plays heatable catalyst, so that catalyzer enters the oxychlorination district with higher temperature, regeneration gas is drawn revivifier after pipe core converges, after a small amount of emptying through the regeneration blower fan, and be divided into two strands, a stock-traders' know-how air cooler wherein, enter the upper catalyst bed layer behind the well heater, another thigh directly enters the lower catalyst bed layer.Do not establish dehumidification system in the circulation loop of regeneration gas, water-content in the regeneration gas is to regulate by the emptying that replenishes air and regeneration gas, finally be stabilized to an equilibrium value, the water-content in the regeneration gas maintains a higher level all the time, and the performance of catalyzer is had adverse influence.
USP4,859,643 and USP5, in 277,880 reclaiming procesies that provide, the district that makes charcoal of revivifier is pyramidal structure, different axial positions, bed have different thickness, can improve along the gas distribution of bed axial location, the top bed is thinner, the tolerance of distributing is bigger, and the bottom bed is thicker, and the tolerance of distribution is less, satisfy the needs of different axial locations to oxygen preferably, catalyzer reduced in the residence time of high-temperature zone, bed top simultaneously.But do not establish dehumidification system in the circulation loop of regeneration gas, have higher water-content in the regeneration gas.
USP4,880,604 and USP4,977, in 119 reclaiming procesies that provide, the district that makes charcoal of revivifier is one section strip structure, and catalyzer relies on gravity slowly to move down in the bar shaped space, and the upper and lower of outer screen cloth has different percentage of open area, thereby make regeneration gas that different distributions be arranged vertically, the tolerance that the top bed distributes is bigger, and the tolerance that the bottom bed distributes is less, helps satisfying the needs of different axial locations to oxygen.But do not establish dehumidification system in the circulation loop of regeneration gas, have higher water-content in the regeneration gas.
In the reclaiming process that above-mentioned patent is introduced,, has higher water-content in the reprocessing cycle gas owing in the regeneration gas loop dehumidification system is not set.Though USP4,578,370 and CN86102807A in mentioned the regeneration gas segmentation and entered the district that makes charcoal, but concerning total regeneration gas, still be equivalent to whole cross section by the outer screen cloth in district of making charcoal, the flux of gas is less than normal on the cross section, and there is the high-temperature zone in the screen cloth place in the bed top, and the regeneration of the catalyzer process of making charcoal is finished under high temperature, high water content environment, this high temperature, high water content environment cause the loss of specific surface area of catalyst easily, thereby shorten the work-ing life of catalyzer.USP4,859,643, USP5,277,880, USP4,880,604 and USP4,977,119 have proposed the bed structure of pyramidal structure bed and different percentage of open area, increased the required amount of oxygen of top bed, to adapt to the high Special Circumstances of district's ingress catalyzer carbon content of making charcoal, although the gas volume that bed top is passed through has had increase, but owing to increased the required amount of oxygen of making charcoal simultaneously, the liberated heat of making charcoal has also had increase, thereby the high-temperature condition on bed top is not eased, and just makes catalyzer in the residence time on bed top reducing to a certain degree arranged.Simultaneously, owing in the regeneration gas loop dehumidification system is not set, there is the water-content problem of higher in the reprocessing cycle gas too.
USP5,034,117 and the reclaiming process that provides of CN1045411A in, revivifier make charcoal the district beds be divided into two sections, catalyzer is transported to the bottom charcoal burning step by dipleg from the top charcoal burning step, every section bed has identical scantlings of the structure, the entry condition of two sections bed regeneration gass is different, the temperature in of bottom bed regeneration gas is higher than the top bed, by replenishing air in the space between two sections beds, makes two sections beds have desired separately oxygen level.Regeneration gas is successively through drawing revivifier behind top charcoal burning step, the bottom charcoal burning step, and enters washing, dehumidification system after oxychlorination district exit gas mixes, and returns the top charcoal burning step of revivifier through recycle compressor.Because be provided with dehumidification system in the reprocessing cycle loop, the water-content in the reprocessing cycle gas is lower, and owing to adopted segmentation pressurization regeneration, the mass flux of regeneration gas is bigger in the bed, thus the temperature rise of bed more not the sectional situation tangible reduction has been arranged.
Summary of the invention
The objective of the invention is to provide on the basis of existing technology a kind of hydrocarbon conversion catalyst at lesser temps, than the continuous regeneration method under the low water content environment.
Method provided by the invention is:
Reclaimable catalyst from moving-burden bed reactor passes through buffer zone, make charcoal district, oxychlorination district and roast area downwards successively in revivifier, the catalyzer after the regeneration leaves revivifier.
In the district that makes charcoal, the space that is surrounded by interior screen cloth is divided into upper and lower two portions, the upper space that screen cloth surrounded in regeneration gas entered, with centrifugation radially by behind the upper catalyst bed layer, outside in the space that screen cloth and inwall surround, after carrying out thorough mixing with normal temperature rare gas element that replenishes and dry air, again in mode entad radially by the lower catalyst bed layer, the lower space that screen cloth surrounds in entering, then draw revivifier, recycle through returning revivifier after the processes such as heat exchange, alkali cleaning washing, drying, filtration, supercharging and heating.
This method can make catalyzer regenerate under at lesser temps, than the low water content environment, helps prolonging the work-ing life of catalyzer.
Description of drawings
Accompanying drawing is the schematic flow sheet of continuous Catalyst-regenerating process provided by the invention.
Embodiment
Method provided by the invention is so concrete enforcement:
Revivifier is followed successively by buffer zone from top to bottom, make charcoal district, oxychlorination district and roast area.
Reclaimable catalyst from moving-burden bed reactor enters revivifier, in buffer zone by the hot regeneration gas of its underpart suitably after the heating, enter the district that makes charcoal along many diplegs downwards by gravity, in the annular space in district of making charcoal, rely on gravity slowly to move down, contact with regeneration gas and burn whole coke, then enter the oxychlorination district and mend chlorine and dispersed metal constituent element again, go out revivifier after entering the moisture that removes in the roast area on the catalyzer again.
Drying contains the oxygen regeneration gas and is introduced by the top, district of making charcoal, the upper space that screen cloth surrounds in entering, temperature in is 400～480 ℃, the inlet oxygen level is 0.2～1.0v%, the water-content of regeneration gas is 50～200ppmv, radially pass through the upper catalyst bed layer with centrifugation, outside in the space that screen cloth and inwall surround, after carrying out thorough mixing with normal temperature rare gas element that replenishes and dry air, the temperature that makes regeneration gas is 480～520 ℃, the inlet oxygen level is 0.2～1.0v%, again in mode entad radially by the lower catalyst bed layer, the lower space that screen cloth surrounds in entering, then draw revivifier, after oxychlorination district exit gas mixes, enter the alkali cleaning water wash column, wash HCl and CO in the regeneration gas off
2, after the portion gas emptying, after residual gas drying, filtration and the supercharging, wherein small part gas returns chlorine oxidation zone, return after the overwhelming majority is heated to 400～480 ℃ revivifier make charcoal the district recycle.Operation absolute pressure in the above-mentioned revivifier is 0.3～1.0 MPa.
Renovation process of the present invention is applicable to all types of hydrocarbon conversion catalysts, is particularly useful for continuous reforming catalyst.
Specify renovation process provided by the present invention below in conjunction with accompanying drawing, but not thereby limiting the invention.The shape of equipment and pipeline and size are not subjected to the restriction of accompanying drawing, but come as the case may be to determine.
Accompanying drawing is the schematic flow sheet of continuous Catalyst-regenerating process provided by the invention.
Reclaimable catalyst enters buffer zone 2 in the revivifier through pipeline 1, by many diplegs 3 enter ring-type make charcoal the district 5, finish the catalyzer of making charcoal and enter oxychlorination district 9 through dipleg 8, catalyzer behind benefit chlorine and the metal redispersion enters roast area 11 through dipleg 10, after removing the moisture on the catalyzer, catalyzer is drawn revivifier by pipeline 12.
Be divided into 4 and 6 two portions by the make charcoal space that surrounds of interior screen cloth in district of revivifier.Reprocessing cycle gas is introduced revivifier through pipeline 33, enter upper space 4, temperature in is 440 ℃, oxygen level is 0.5v%, water-content is 100ppmv, radially pass through the upper catalyst bed layer with centrifugation, sedimentary most of coke on the while burn off catalyzer, then entering the space 7 that make charcoal district outer screen cloth and revivifier inwall surround, carry out thorough mixing with normal temperature rare gas element that replenishes into through pipeline 36 and dry air herein, the mixed regeneration gas temperature reaches 480 ℃, oxygen level reaches 0.6v%, and in mode entad radially by the lower catalyst bed layer, remaining coke on the burn off catalyzer simultaneously, and enter lower space 6, draw revivifier by pipeline 13.
In the reprocessing cycle gas return path, regeneration gas from pipeline 13 enters interchanger 14, and heat exchange is after pipeline 15 with after gas from the oxychlorination district of pipeline 16 mixes, enters water cooler 17, further cooled regeneration gas enters alkali cleaning water wash column 19 through pipeline 18, removes HCl and CO
2Regeneration gas draw by pipeline 20, after pipeline 21 part emptying, enter moisture eliminator 23 through pipeline 22, the regeneration gas that removes moisture enters strainer 25 through pipeline 24, regeneration gas after the purification enters recycle compressor 27 through pipeline 26, regeneration gas after the supercharging is drawn by pipeline 28, wherein a part of regeneration gas returns the oxychlorination district through pipeline 29, mainstream gas enters pipeline 30, small part gas is drawn by pipeline 34, after converging with dry air from pipeline 35, in pipeline 36 added to space 7, the main flow of gases entered interchanger 14 in the pipeline 30, after regeneration gas heat exchange in the pipeline 13, enter well heater 32 through pipeline 31, the regeneration gas after the intensification is introduced revivifier and is entered space 4 by pipeline 33, finishes the circulation of regeneration gas.
Respectively number among the figure and be described as follows: 2 are buffering area, and 4 is to make charcoal to distinguish the top sky that interior screen cloth surrounds Between, 6 is to make charcoal to distinguish the lower space that interior screen cloth surrounds, and 5 for making charcoal district's beds, and 7 for burning The space that screen cloth and inwall surround outside the charcoal district, 9 are the oxychlorination district, and 11 is roast area, and 14 are heat exchange Device, 17 is water cooler, and 19 are the alkali cleaning water scrubber, and 23 is drier, and 25 is filter, 27 are Recycle compressor, 32 is heater, 3,8,10 are dipleg under the catalyst, 1,12,13, 15,16,18,20,21,22,24,26,28,29,30,31,33,34,35,36 Be pipeline.
The invention has the advantages that:
1, make charcoal in the district after the space that surrounds of screen cloth is divided into up and down two parts, with USP4,578,370, USP4,859,643, USP5,277,880, USP4,880,604 and USP4,977,119 compare, regeneration The flow area of gas has reduced one times, thereby the quality that has increased regeneration gas on the bed cross section is logical Coke burning liberated heat is certain in the amount, bed, and regeneration gas is entering second one Divide before the bed, can regulate inlet temperature by normal temperature inert gas and dry air, therefore The temperature rise of bed has had obvious reduction, has reduced simultaneously the peak temperature in the bed, is conducive to protection and urges Change the performance of agent, the service life of extending catalyst. Owing to adopted pressurization regeneration, although regeneration The flow area of gas has reduced one times, but regeneration gas also can be kept by the superficial gas velocity of bed In lower level, be unlikely in bed, to occur the adherent phenomenon of catalyst.
2, the space that directly screen cloth in the district that makes charcoal is surrounded is divided into two parts, except reducing bed The peak temperature outside, also than USP5,034,117 and the handle that proposes of the CN1045411A district's bed of making charcoal be divided into Two sections renovation process saves two sections catalyst blanking diplegs between the bed, the reduction regenerator Highly, simplify the structure that regenerator is made charcoal and distinguished, save equipment investment.
3, because the top of regenerator is provided with buffering area, the reclaimable catalyst in the buffering area and its are down The hot regeneration gas of section carries out heat exchange, and the temperature of catalyst improves, thus catalyst with Higher temperature enters the district that makes charcoal, and has improved the efficient of making charcoal on bed top.
4, be provided with the process such as dry processing in the regeneration gas loop, the water content in the regeneration gas very Low, thus coke combustion is finished under the environment of low water content, and catalyst compares in coke combustion Surface area losses is very little, is conducive to the service life of extending catalyst.
5, be provided with caustic washing system in the regeneration cycle gas return path, removed in the regeneration gas HCl, the directly emptying of a part of regeneration gas has reduced simultaneously to respectively establishing in the regeneration gas loop The requirement of standby material.
Claims (5)
1, a kind of continuous Catalyst-regenerating process, reclaimable catalyst from moving-burden bed reactor passes through buffer zone downwards successively in revivifier, the district makes charcoal, oxychlorination district and roast area, catalyzer after the regeneration leaves revivifier, it is characterized in that regeneration gas is introduced into the upper space that is surrounded by screen cloth in the district that makes charcoal, with centrifugation by behind the upper catalyst bed layer, in the space that surrounds by outer screen cloth and revivifier inwall, after normal temperature rare gas element that replenishes and dry air mix, again radially in mode entad by the lower catalyst bed layer, and enter the lower space that surrounds by interior screen cloth, draw revivifier subsequently, pass through heat exchange successively, the alkali cleaning washing, dry, filter, supercharging and the heating after return revivifier make charcoal the district recycle.
2, according to the method for claim 1, the regeneration gas temperature that it is characterized in that entering the upper catalyst bed layer is 400～480 ℃.
3, according to the method for claim 1, the regeneration gas temperature that it is characterized in that entering the lower catalyst bed layer is 480～520 ℃.
4, according to the method for claim 1, the inlet oxygen level that it is characterized in that entering the regeneration gas of upper catalyst bed layer and lower catalyst bed layer is 0.2～1.0v%.
5, according to the method for claim 1, the regeneration gas water-content that it is characterized in that entering the upper catalyst bed layer is 50～200ppmv.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011184248A CN1136994C (en) | 2001-05-30 | 2001-05-30 | Continuous catalyst-regenerating process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011184248A CN1136994C (en) | 2001-05-30 | 2001-05-30 | Continuous catalyst-regenerating process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1387951A CN1387951A (en) | 2003-01-01 |
| CN1136994C true CN1136994C (en) | 2004-02-04 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011184248A Expired - Lifetime CN1136994C (en) | 2001-05-30 | 2001-05-30 | Continuous catalyst-regenerating process |
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| CN (1) | CN1136994C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4989771B1 (en) * | 2011-04-15 | 2012-08-01 | 田中貴金属工業株式会社 | Regeneration method of exhaust gas purification catalyst |
| CN103028450B (en) * | 2011-09-30 | 2016-03-02 | 中国石油化工股份有限公司 | catalytic conversion catalyst regeneration method |
| CN110639598A (en) * | 2018-06-27 | 2020-01-03 | 中国石化工程建设有限公司 | Catalyst oxychlorination and drying method for catalyst regeneration process and catalyst regeneration process |
| CN113578398B (en) * | 2020-04-30 | 2023-10-27 | 中国石油天然气集团有限公司 | Catalyst regenerator |
| CN113578399B (en) * | 2020-04-30 | 2023-11-28 | 中国石油天然气集团有限公司 | Catalyst regeneration and burn method and device |
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2001
- 2001-05-30 CN CNB011184248A patent/CN1136994C/en not_active Expired - Lifetime
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| CN1387951A (en) | 2003-01-01 |
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Granted publication date: 20040204 |