CN1089641C - Regeneration process of hydrocarbon converting catalyst - Google Patents
Regeneration process of hydrocarbon converting catalyst Download PDFInfo
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- CN1089641C CN1089641C CN99106878A CN99106878A CN1089641C CN 1089641 C CN1089641 C CN 1089641C CN 99106878 A CN99106878 A CN 99106878A CN 99106878 A CN99106878 A CN 99106878A CN 1089641 C CN1089641 C CN 1089641C
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Abstract
The present invention relates to a regeneration technology for hydrocarbon conversion catalysts. After raw catalysts are lifted to a separation hopper at the top of a regenerator, the raw catalysts enter a low-pressure area of an isolation hopper after the raw catalysts are elutriated. The raw catalysts enter a buffer area of the regenerator under the pressure regulation of a variable pressure area of the isolation hopper and pass through a scorching area, a chlorine oxidation area and a calcining area of the regenerator by gravity. In the chlorine oxidation area, after a chloric gas which is in contact with the catalysts is withdrawn, the chloric gas is mixed with a regeneration cycle gas after heat exchange, and the chloric gas is circulated to the scorching area of the regenerator after the processing of dechlorination.
Description
The present invention relates to a kind of regeneration technology of hydrocarbon conversion catalyst, especially face the regeneration of H-H reaction catalyst.This catalyst contains a kind of carrier, the halogen of at least a catalytically-active metals and certain content, and the particle diameter of catalyst is between 0.5～5.0mm.
Catalyst surface is because of the carbon deposit inactivation in course of reaction for this class hydrocarbon conversion catalyst, and its regeneration technology generally needs following three steps:
(1) uses carbon deposit than the gas burning-off catalyst surface of low oxygen content.
(2) with the gas adding halide-containing of high oxygen content catalyst is handled, with the halogen on the make-up catalyst.
(3) with the gas of high oxygen content catalyst is calcined.
Generally realize above step with two kinds of regeneration technologies on the engineering: a kind of regeneration technology is to place fixed bed successively to cross bed with three kinds of required different air communication of above-mentioned three steps respectively catalyst; Second kind of regeneration technology is that catalyst is placed moving bed, makes it to pass through successively three different zones, and these three zones are from top to bottom respectively by three kinds of required different air-flows of above-mentioned three steps.Second kind of catalyst regeneration process wherein, because the catalyst charge weight is few, regeneration efficiency height, but advantages such as implement device long-term operation, and be widely used industrial, belong to second kind of catalyst regeneration process exactly as US4578370 and CN1045411A.
US4578370 adopts the movable bed catalyst regeneration technology, in this technology, reclaim equiment comprises one section radially moving-bed of catalyst scorch region, chlorine oxidation zone and calcining zone, after reclaimable catalyst separates through separating tank, regenerate by above-mentioned three districts in turn, in regenerative process, adopt the higher burning gases of a part of temperature as thermal current, remaining burning gases loops back scorch region after supercooling.In the method, catalyst directly enters the scorch region of regenerator by induction system, because the conveying of this type of catalyst can not be continuously strict, therefore burning also can not be continuously strict, causes the discontinuous of whole process, will cause like this that to burn efficient low.Also exist regeneration gas to adopt thermal cycle in this patent, water content is big in the gas phase, the shortcoming that specific surface area of catalyst decline is fast.In addition, chlorine oxidation zone and scorch region directly communicate, and the chlorine-containing gas in the chlorine oxidation zone can directly enter scorch region, has improved the requirement to the scorch region equipment material like this, has strengthened equipment investment.In the CN1045411A patent, reclaimable catalyst is risen to the separation hopper at regenerator top by reactor bottom, after elutriation, enter the potential device district, under allobar pressure is regulated, enter the buffering area at regenerator top, under the gravity effect, pass through two radially moving-bed of catalyst scorch regions then in succession, axial catalyst moving bed chlorine oxidation zone and axial catalyst moving bed calcining zone, from second moving-bed of catalyst combustion zone burning gases of discharging radially, after the gas that comes out with chlorine oxidation zone and calcining zone is pre-mixed, deliver to the washing loop again, in this method, because burning branch carries out for two sections, so the regenerator complex structure, the regenerator absolute altitude is too high.In addition, separate hopper except that elutriation, also serve as the low depressor in the catalyst transport process, because the pressure that separates hopper is subjected to the influence of various factors, pressure is easy to generate instability, particularly at the initial stage of going into operation, like this to the smooth operation generation considerable influence of catalyst transport.
The purpose of this invention is to provide a continuous reproducible, the simple catalyst regeneration process of flow process, and do not have the problem of high temperature chlorine-containing gas corrosion scorch region equipment.
In order to achieve the above object, the invention provides a kind of like this regeneration technology, contain a kind of carrier, the halogen of at least a catalytically-active metals and certain content, and the reclaimable catalyst of particle diameter between 0.5～5.0mm, rise to the separation hopper at regenerator top by reactor bottom, after elutriation, enter the low-pressure area of packing material bucket, under the pressure of isolating the hopper allobar is regulated, catalyst enters the buffering area at regenerator top through allobar from low-pressure area, enter radially moving-bed of catalyst scorch region by gravity by buffering area then, with contain the carbon deposit that the oxygen regeneration gas contacts the burning-off catalyst surface, regeneration gas recycles, catalyst after burning enters axial catalyst moving bed chlorine oxidation zone again under the gravity effect, contact with chlorine-containing gas and to carry out oxychloride, catalyst behind the oxychloride is under the gravity effect, enter axial catalyst moving bed calcining zone, under the oxygen-containing gas effect, calcine, catalyst after the calcining leaves regenerator by regenerator bottoms, through the degassing, after reduction is handled, enter reactor head and begin next circulation.In the described chlorine oxidation zone with chlorine-containing gas after catalyst contacts, isolate by dense catalyst bed and scorch region, and discharge, after the regeneration recycle gas of being extracted out by scorch region mixes by the chlorine-containing gas outlet of chlorine oxidation zone, carry out dechlorination and handle, be circulated to the scorch region of regenerator then.
Feature of the present invention also is, chlorine-containing gas by chlorine oxidation zone exports the chlorine-containing gas of discharging, after the cooler cooling, with mix through the cooled regeneration recycle gas of extracting out by scorch region, enter dechlorinator's dechlorination then, again drying device, filter, compressor and heat exchanger carry out drying, filter, boost and heat exchange after, divide two-way to enter the heater heating respectively, enter scorch region then, wherein one the tunnel is used to burn, and another road is used to regulate the temperature of scorch region bottom beds.
The remarkable result that the present invention produces is, compare with US4578370, because of having set up buffering area in the top of regenerator, isolate hopper place regenerator above, make catalyst enter scorch region continuously, thereby realized cyclic regeneration; Secondly, with chlorine-containing gas after catalyst contacts, isolate by dense catalyst bed and scorch region, in the chlorine oxidation zone so chlorine-containing gas can not enter scorch region, so, reduced requirement to the scorch region equipment material with regard to there not being the problem of high temperature chlorine-containing gas corrosion scorch region equipment; Compare with the CN1045411A technology, substituted former independent potential device, make the separation hopper only bear the function of elutriation, thereby reduced of the influence of the instability of separation hopper district pressure the regenerative system quiet run with the isolation hopper that has low-pressure area and allobar; Scorch region is one section moving-bed of catalyst, has simplified flow process, has reduced the absolute altitude of regenerator, has reduced equipment investment.
Use the present invention also can reach other effect, because regeneration recycle gas adopts cold circulation, use normal temperature compressed machine to promote, reduced investment, the regenerator operating pressure can change between 0.3～1.5Mpa, water content is few in the regeneration recycle gas, can slow down the minimizing speed of regenerated catalyst specific area, prolongs the service life of catalyst.
Describe the present invention in detail below in conjunction with accompanying drawing, but accompanying drawing does not limit the present invention.
Accompanying drawing and drawing explanation:
Accompanying drawing 1 is a kind of typical flowchart of the present invention.
As shown in Figure 1, the bottom lifter 22 of reclaimable catalyst by reactor 25 risen in the separation hopper 1 at regenerator 3 tops, dust in this catalyst is gone out by elutriation, the catalyst that settles down enters the low-pressure area 201 of isolating hopper 2, it is pressure minimum point in the catalyst circulation loop herein, under the pressure of the allobar 202 of isolating hopper 2 is regulated, catalyst enters the buffering area 4 at regenerator 3 tops through allobar 202 from low-pressure area 201, this place is a pressure peak in the catalyst circulation loop, under the gravity effect, catalyst enters radially moving-bed of catalyst scorch region 5 by buffering area 4, contact the carbon deposit of burning-off catalyst surface with oxygen-containing gas, the pressure of scorch region is between 0.35～1.5MPa, be generally 0.6～1.2MPa, the time of staying of catalyst was at 0.5～3.0 hour, catalyst coke content is in 0.01～10wt% scope, has a pressure balance mouth 39 herein at least, circulating air 36 inlets, cross hot gas 37 inlet and regeneration recycle gas 35 outlets for one, the inlet temperature of circulating air 36 is between 400～500 ℃, generally between 440～480 ℃, oxygen content is between 0.4～1.0mol%, generally between 0.5～0.7%.Reaction bed temperature is generally 400～550 ℃, in a word its maximum temperature be controlled at make local area and chlorine oxidation zone 6, calcining zone 7 bed temperature all under catalyst carrier maximum temperature allowed to bear, after burning, coke content on the catalyst drops to below the 0.02wt%, and the pressure depended on pressure balance port 39 of scorch region is regulated.Catalyst after burning enters axial catalyst moving bed chlorine oxidation zone 6 by many catalyst conduits 70 under the gravity effect, contact with chlorine-containing gas, carries out oxychloride.
Catalyst is piled naturally in catalyst conduit 70 bottoms and is ended, form dense catalyst bed, the bed temperature of chlorine oxidation zone 6 is higher 10～50 ℃ than the bed temperature of scorch region 5, general high 30 ℃, pressure equates with scorch region 5, catalyst is 1～3 hour in this time of staying, be generally 2 hours, local area has 34 and chlorine-containing gas of chlorine-containing gas outlet, 59 inlets at least, chlorine-containing gas 33 is mixed into chlorine-containing gas 59 with oxygen-containing gas 32 by calcining zone 7, enter chlorine oxidation zone 6 after these chlorine-containing gas 59 heater vias 15 heating, the inlet gas phase temperature of chlorine-containing gas 59 is between 510～550 ℃, be generally 530 ℃, chlorinity is between 0.1～1.0wt% in the gas phase, oxygen content is between 3～21mol%, isolate by pile the dense catalyst bed and the scorch region 5 that end naturally in catalyst conduit 70 bottoms through the chlorine-containing gas behind the beds, thereby can not enter scorch region 5, this chlorine-containing gas is discharged by the chlorine-containing gas outlet 34 of chlorine oxidation zone 6, chlorinity through the oxychloride rear catalyst reaches 0.5～1.5wt%, generally at 1wt%, catalyst behind the oxychloride enters axial catalyst moving bed calcining zone 7 under the gravity effect, calcine under the oxygen-containing gas effect.Export 34 chlorine-containing gas of discharging from the chlorine-containing gas of chlorine oxidation zone 6, after heat exchange cooler 19 heat exchange cooling, with mixed through the cooled regeneration recycle gas of heat exchanger 18 35, enter dechlorinator's 8 dechlorinations, the drying device 9 again, filter 10, compressor 11 and heat exchanger 18 carry out drying, filter, after boosting and heating, divide two-way to enter heater 17 respectively, 16 heat, by the circulating air 36 after heater 17 heating with by the scorch region 5 that hot gas 37 is introduced into regenerator 3 respectively of crossing after heater 16 heating, circulating air 36 is used to burn, and crosses the bed temperature that hot gas 37 is used to regulate scorch region 5 bottom catalyst.
At calcining zone 7, reaction bed temperature is higher 10～50 ℃ than the bed temperature of chlorine oxidation zone 6, general high 30 ℃, local area pressure is the self-balancing pressure of keeping calcining zone 7 dechlorination zoneofoxidations 6 oxygen-containing gas 32 flows, than chlorine oxidation zone 6 height, in local area, the time of staying of catalyst is 1～3 hour, is generally 2 hours.The oxygen content of the oxygen-containing gas 31 of introducing local area is between 5～21mol%, enter preceding first drying of local area and heating, oxygen-containing gas is through behind the beds, one oxygen-containing gas 32 is drawn out of back dechlorination zoneofoxidation 6, excessive part via pipeline 38 by emptying, catalyst after the calcining leaves regenerator by regenerator 3 bottoms, enter buffering area 20, after the degassing, rise to reactor 25 top buffering areas 23 by lifter 21, enter reducing zone 24 then, under the hydrogen environment, metal on the catalyst surface is reduced processing, make catalyst recover to enter the next circulation of reactor 25 beginnings after the activity.
In accompanying drawing 1, the lifting gas 54 in the lifter 22, the lifting gas 53 in the lifter 21, the elutriation gas 45 that separates in the hopper 1 all adopts nitrogen, and with compressor 12 circulations, the delivery air 57 of isolating in the hopper 2 also adopts nitrogen, this compares as medium with adopting hydrogen, and is both economical, again safety.
The present invention shown in the accompanying drawing 1 can realize purpose of the present invention well, reaches effect of the present invention.
Obviously, in accompanying drawing 1, reactor 25 also multistage reactor on vertical direction arranged superposed or horizontal direction, be arranged in juxtaposition, the catalyst that comes out from regenerator 3 also can outgas earlier, rises to reactor 25 tops after the reduction again.
Claims (3)
1. the regeneration technology of a hydrocarbon conversion catalyst, described catalyst contains a kind of carrier, the halogen of at least a catalytically-active metals and certain content, the catalyst granules diameter is between 0.5～5.0mm, in course of reaction, catalyst surface is because of the carbon deposit inactivation, and its regeneration technology comprises:
A) be promoted to reclaimable catalyst in the separation hopper (1) at regenerator (3) top by reactor bottom, after elutriation, enter the low-pressure area (201) of packing material bucket (2), under the pressure of the allobar (202) of isolating hopper (2) was regulated, catalyst entered the buffering area (4) at regenerator (3) top through allobar (202) from low-pressure area (201);
B) catalyst enters radially moving-bed of catalyst scorch region (5) by buffering area (4) under the gravity effect, and contains the carbon deposit that the oxygen regeneration gas contacts the burning-off catalyst surface, and regeneration gas recycles;
C) catalyst after burning enters axial catalyst moving bed chlorine oxidation zone (6) under the gravity effect, contacts with chlorine-containing gas, carries out oxychloride;
D) catalyst behind the oxychloride enters axial catalyst moving bed calcining zone (7) under the gravity effect, under the oxygen-containing gas effect, calcines;
E) catalyst after the calcining leaves regenerator by regenerator (3) bottom, after the degassing, reduction are handled, enters reactor head and begins next circulation;
In the described chlorine oxidation zone (6) with chlorine-containing gas after catalyst contacts, isolate by dense catalyst bed and scorch region (5), and discharge by the chlorine-containing gas of chlorine oxidation zone (6) outlet (34), with carry out the dechlorination processing after the regeneration recycle gas of being extracted out by scorch region (5) (35) mixes, be circulated to the scorch region (5) of regenerator then;
In described scorch region (5), the treatment conditions of catalyst are: pressure is between 0.35～1.5MPa, the time of staying of catalyst is 0.5～3.0 hour, circulating air (36) inlet temperature is between 400～500 ℃, oxygen content between 0.4～1.0mol%, the beds maximum temperature be controlled at make local area and chlorine oxidation zone (6), calcining zone (7) bed temperature all under catalyst carrier maximum temperature allowed to bear;
In described chlorine oxidation zone (6), the treatment conditions of catalyst are: bed temperature is higher 10～50 ℃ than the bed temperature of scorch region (5), pressure equates with scorch region, catalyst is 1～3 hour in this time of staying, chlorine-containing gas (33) is mixed into chlorine-containing gas (59) with the oxygen-containing gas (32) that is come by calcining zone (7) and enters chlorine oxidation zone (6), chlorine-containing gas (59) inlet gas phase temperature is between 510～550 ℃, chlorinity is between 0.1～1.0wt% in the gas phase, and oxygen content is between 3～21mol%;
In described calcining zone (7), the treatment conditions of catalyst are: the bed temperature of calcining zone (7) is higher 10～50 ℃ than the bed temperature of chlorine oxidation zone (6), local area pressure is the self-balancing pressure of keeping calcining zone (7) dechlorination zoneofoxidation (6) oxygen-containing gas (32) flow, the catalyst time of staying is 1～3 hour, the oxygen content of the oxygen-containing gas (31) of introducing local area is between 5～21mol%, enter preceding first drying of local area and heating, oxygen-containing gas is through behind the beds, one oxygen-containing gas (32) is drawn out of back dechlorination zoneofoxidation (6), excessive part emptying.
2. according to the regeneration technology of the described hydrocarbon conversion catalyst of claim 1, it is characterized in that: described chlorine-containing gas of discharging by the chlorine-containing gas outlet (34) of chlorine oxidation zone (6), after cooler (19) cooling, with mix through the cooled regeneration recycle gas of extracting out by scorch region (5) (35) of heat exchanger (18), enter dechlorinator (8) dechlorination then, drying device (9) again, filter (10), behind compressor (11) and the heat exchanger (18), divide two-way to enter heater (17) respectively, (16) heating, be introduced into scorch region (5) respectively by the circulating air (36) after heater (17) heating with by the hot gas (37) of crossing after heater (16) heating, circulating air (36) is used to burn, and crosses hot gas (37) and is used to regulate scorch region (5) bottom reaction bed temperature.
3. according to the regeneration technology of the described hydrocarbon conversion catalyst of claim 1, it is characterized in that: the lifting gas (54) in the lifter (22), lifting gas (53) in the lifter (21), the elutriation gas (45) that separates in the hopper (1) all adopts nitrogen, with compressor (12) circulation, the delivery air (57) of isolating in the hopper (2) also adopts nitrogen.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99106878A CN1089641C (en) | 1999-05-19 | 1999-05-19 | Regeneration process of hydrocarbon converting catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99106878A CN1089641C (en) | 1999-05-19 | 1999-05-19 | Regeneration process of hydrocarbon converting catalyst |
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| Publication Number | Publication Date |
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| CN1241454A CN1241454A (en) | 2000-01-19 |
| CN1089641C true CN1089641C (en) | 2002-08-28 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN99106878A Expired - Lifetime CN1089641C (en) | 1999-05-19 | 1999-05-19 | Regeneration process of hydrocarbon converting catalyst |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101658799B (en) * | 2009-09-14 | 2011-06-29 | 洛阳瑞泽石化工程有限公司 | Continuous catalyst regeneration method and device thereof |
| CN102259037A (en) * | 2010-05-24 | 2011-11-30 | 上海傲佳能源科技有限公司 | Process for continuously regenerating catalyst for liquefied gas aromatization and liquefied gas cracking |
| 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 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86108969A (en) * | 1985-12-27 | 1987-07-29 | 环球油品公司 | The method and apparatus of regeneration of hyolrocarbon conversion catalyst |
| CN1045411A (en) * | 1989-01-13 | 1990-09-19 | 法国石油公司 | The renovation process of aromatic hydrocarbon preparation or reforming catalyst |
| US4980325A (en) * | 1989-06-12 | 1990-12-25 | Uop | Method of controlling moisture in combustion section of moving bed regeneration process |
| US5776849A (en) * | 1983-11-10 | 1998-07-07 | Exxon Research & Engineering Company | Regeneration of severely deactivated reforming catalysts |
-
1999
- 1999-05-19 CN CN99106878A patent/CN1089641C/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5776849A (en) * | 1983-11-10 | 1998-07-07 | Exxon Research & Engineering Company | Regeneration of severely deactivated reforming catalysts |
| CN86108969A (en) * | 1985-12-27 | 1987-07-29 | 环球油品公司 | The method and apparatus of regeneration of hyolrocarbon conversion catalyst |
| CN1045411A (en) * | 1989-01-13 | 1990-09-19 | 法国石油公司 | The renovation process of aromatic hydrocarbon preparation or reforming catalyst |
| US4980325A (en) * | 1989-06-12 | 1990-12-25 | Uop | Method of controlling moisture in combustion section of moving bed regeneration process |
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| CN1241454A (en) | 2000-01-19 |
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Address after: 100029 Beijing City, Chaoyang District Hui Street No. 6 Patentee after: China Petrochemical Group Corp. Patentee after: Luoyang Petrochemical Engineering Corporation /SINOPEC Address before: 100029 Beijing City, Chaoyang District Hui Street No. 6 Patentee before: China Petrochemical Group Corp. Patentee before: Luoyang Petrochemical Engineering Co., China Petrochemical Group |
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Effective date of registration: 20130326 Address after: 471003 Zhongzhou West Road, Henan, China, No. 27, No. Patentee after: Luoyang Petrochemical Engineering Corporation /SINOPEC Address before: 100029 Beijing City, Chaoyang District Hui Street No. 6 Patentee before: China Petrochemical Group Corp. Patentee before: Luoyang Petrochemical Engineering Corporation /SINOPEC |
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