CN1089639C - Regeneration method of hydrocarbon converting catalyst - Google Patents
Regeneration method of hydrocarbon converting catalyst Download PDFInfo
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- CN1089639C CN1089639C CN98112916A CN98112916A CN1089639C CN 1089639 C CN1089639 C CN 1089639C CN 98112916 A CN98112916 A CN 98112916A CN 98112916 A CN98112916 A CN 98112916A CN 1089639 C CN1089639 C CN 1089639C
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Abstract
The present invention relates to a regeneration method 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 passes through a scorching area, a chlorine oxidation area and a calcining area of the regenerator by gravity. In the chlorine oxidation area, chloric gas is directly withdrawn after the chloric gas is in contact with the catalysts, washed by alkali, mixed with regeneration cycle gas after heat exchange and circulated to the scorching area of the regenerator.
Description
The present invention relates to a kind of renovation process of hydrocarbon conversion catalyst, especially face the regeneration of H-H reaction catalyzer.This catalyzer contains a kind of carrier, the halogen of at least a catalytically-active metals and certain content, and the particle diameter of catalyzer is at 0.5-5.0mm.
The regeneration of this class hydrocarbon conversion catalyst 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 catalyzer is handled, with the halogen on the make-up catalyst.
(3) with the gas of high oxygen content catalyzer is calcined.
Generally realize above step with two kinds of methods on the engineering: a kind of method is to place fixed bed successively to cross bed with three kinds of required different air communication of above-mentioned three steps respectively catalyzer; Second method is that catalyzer 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 catalyzer Intake Quantity is few, regeneration efficiency height, but advantages such as implement device long-term operation, and be widely used industrial, belong to second method exactly as US4578370 and CN1045411A.
US4578370 adopts the movable bed catalyst renovation process, in this method, reclaim equiment comprises one section radially moving-bed of catalyst scorch region, chlorine oxidation zone and calcining zone, after reclaimable catalyst separates through separator tank, regenerate by above-mentioned three districts in turn, in regenerative process, adopt the higher combustion gases of a part of temperature as hot gas flow, remaining combustion gases loops back scorch region after overcooling.In the method, catalyzer directly enters the scorch region of revivifier by delivery system, because the conveying of this type of catalyzer 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 cycling 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 facility investment.In the CN1045411A patent, reclaimable catalyst is risen to the separation hopper at revivifier top by reactor bottom, after elutriation, enter the potential device district, under allobar pressure is regulated, enter the buffer zone at revivifier top, under action of gravity, 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 combustion 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 revivifier complex structure, the regenerator column absolute altitude is too high, and it is too huge that next washs in the loop alkali cleaning equipment.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, the specification that also can dwindle alkali cleaning equipment simultaneously.
In order to achieve the above object, the invention provides a kind of like this renovation process, 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 revivifier 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, catalyzer enters the buffer zone at revivifier top through allobar from low pressure area, enter radially moving-bed of catalyst scorch region by gravity by buffer zone then, with contain the carbon deposit that the oxygen regeneration gas contacts the burning-off catalyst surface, resurgent gases recycles, catalyzer after burning enters axial catalyst moving-bed chlorine oxidation zone again under action of gravity, contact with chlorine-containing gas and to carry out oxychlorination, catalyzer behind the oxychlorination is under action of gravity, enter axial catalyst moving-bed calcining zone, under the oxygen-containing gas effect, calcine, catalyzer after the calcining leaves revivifier by regenerator bottoms, through the degassing, after reduction is handled, enter reactor head and begin next circulation.Have only the catalyzer conduit to communicate between described scorch region and the chlorine oxidation zone, with chlorine-containing gas after catalyzer contacts, discharge in the chlorine oxidation zone, after dechlorination is handled, enter the regeneration recycle gas loop, be circulated to scorch region by the chlorine-containing gas outlet of chlorine oxidation zone.
Feature of the present invention also is, the chlorine-containing gas of being discharged by chlorine oxidation zone exports out from chlorine-containing gas, after the water cooler cooling, enter the soda-wash tower dechlorination, with mix through cooled regeneration recycle gas, gas mixture drying device, strainer, compressor and interchanger carry out drying, filter, boost and heat exchange after, divide two-way to enter heater heats, 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 unusual effect that the present invention produces is, compare with US4578370, because of having set up buffer zone in the top of revivifier, isolate hopper place revivifier above, make catalyzer enter scorch region continuously, thereby realized cyclic regeneration; Secondly, have only the catalyzer conduit to communicate between scorch region and the chlorine oxidation zone, catalyzer in catalyzer conduit bottom naturally heap end, the prevention chlorine-containing gas enters 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 regeneration system rapidly quiet run with the isolation hopper that has low pressure area and allobar; Scorch region is one section moving-bed of catalyst, simplified the absolute altitude that flow process has reduced revivifier, reduced facility investment; Chlorine-containing gas is directly extracted out, alkali cleaning dechlorination separately, the specification of having dwindled alkali cleaning equipment.
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 revivifier working 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 surface area, prolongs the work-ing life of catalyzer.
Below in conjunction with accompanying drawing, describe the present invention in detail with specific embodiment, but accompanying drawing does not limit the present invention.
Accompanying drawing and drawing explanation:
Accompanying drawing 1 typical flowchart of the present invention.
Embodiment 1:
As shown in Figure 1, the bottom lifter 22 of reclaimable catalyst by reactor 25 risen in the separation hopper 1 at revivifier 3 tops, dust in this catalyzer is gone out by elutriation, the catalyzer that settles down enters the low pressure area 201 of isolating hopper 2, it is pressure lower-most point in the catalyst recirculation loop herein, under the pressure of the allobar 202 of isolating hopper 2 is regulated, catalyzer enters the buffer zone 4 at revivifier 3 tops through allobar 202 from low pressure area 201, this place is a pressure vertex in the catalyst recirculation loop, under action of gravity, catalyzer enters radially moving-bed of catalyst scorch region 5 by buffer zone 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 residence time of catalyzer was at 0.5-3.0 hour, catalyst coke content is in the 0.01-10wt% scope, has a pressure balance mouth 39 herein at least, circulation gas 36 inlets, cross hot gas 37 inlet and regeneration recycle gas 35 relief outlets for one, the temperature in of circulation gas 36 is between 400--500 ℃, generally between 440--480 ℃, oxygen level is between 0.4-1.0mol%, generally between 0.5-0.7%.Reaction bed temperature is generally 400--550 ℃, in a word its top temperature be controlled at make local area and chlorine oxidation zone 6, calcining zone 7 bed temperature all under support of the catalyst top temperature allowed to bear, after burning, coke content on the catalyzer drops to below the 0.02wt%, and the pressure depended on pressure balance port 39 of scorch region is regulated.Catalyzer after burning enters axial catalyst moving-bed chlorine oxidation zone 6 by many catalyzer conduits 70 under action of gravity, contact with chlorine-containing gas, carries out oxychlorination.
Catalyzer is piled naturally in catalyzer conduit 70 bottoms and is ended, stop the chlorine-containing gas in the chlorine oxidation zone 6 to enter scorch region 5, the bed temperature of chlorine oxidation zone 6 is than the high 10--50 of bed temperature ℃ of scorch region 5, general high 30 ℃, pressure equates with scorch region 5, catalyzer is 1-3 hour in this residence time, be generally about two hours, local area has 34 and chlorine-containing gas of chlorine-containing gas outlet, 59 inlets at least, chlorine 33 mixes with oxygen-containing gas 32 by calcining zone 7, enter chlorine oxidation zone 6 after these gas mixture heater via 15 heating, the inlet gas phase temperature of chlorine-containing gas 59 is between 510--550 ℃, be generally 530 ℃, cl content is between 0.1-1.0wt% in the gas phase, oxygen level is between 3-21mol%, through the chlorine-containing gas behind the beds, chlorine-containing gas outlet 34 by chlorine oxidation zone 6 is discharged, cl content through the oxychlorination rear catalyst reaches 0.5-1.5wt%, generally at 1wt%, catalyzer behind the oxychlorination is under action of gravity, enter axial catalyst moving-bed calcining zone 7, under the oxygen-containing gas effect, calcine.The chlorine-containing gas of discharging from chlorine oxidation zone 6 comes out from chlorine-containing gas outlet 34, after heat exchange water cooler 19 heat exchange cooling, enter soda-wash tower 8 dechlorinations, with mixed through the cooled regeneration recycle gas of interchanger 18 35, gas mixture is through moisture eliminator 9, strainer 10, compressor 11 and interchanger 18 carry out drying, filter, after boosting and heating, divide two-way to enter well heater 17,16 heat, by the circulation gas 36 after well heater 17 heating with by the scorch region 5 that hot gas 37 is introduced into revivifier 3 respectively of crossing after well heater 16 heating, circulation gas 36 is mainly used in and burns, cross hot gas 37 and be mainly used in the bed temperature of regulating scorch region 5 bottom catalyzer
At calcining zone 7, reaction bed temperature is than the high 10--50 of bed temperature ℃ of chlorine oxidation zone 6, general high 30 ℃, local area pressure is the self-balancing pressure of keeping calcining zone 7 dechlorination oxidation zones 6 oxygen-containing gass 32 flows, than chlorine oxidation zone 6 height, in local area, the residence time of catalyzer is 1-3 hour, is generally about two hours.Oxygen-containing gas 31 first drying and heating before introducing local area, oxygen-containing gas is through behind the beds, one oxygen-containing gas 32 is drawn out of back dechlorination oxidation zone 6, excessive part via pipeline 38 by emptying, catalyzer after the calcining leaves revivifier by revivifier 3 bottoms, enter buffer zone 20, after the degassing, rise to reactor 25 top buffer zones 23 by lifter 21, enter reduction zone 24 then, under the hydrogen environment, the metal on the catalyst surface is reduced processing, make catalyzer recover to enter the next circulation of reactor 25 beginnings after the activity.
In the present embodiment, 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.
Present embodiment can be realized purpose of the present invention well, reaches effect of the present invention.
Obviously, in the present embodiment, reactor 25 also staged reactor on vertical direction arranged superposed or horizontal direction, be arranged in juxtaposition, the catalyzer that comes out from revivifier 3 also can outgas earlier, rises to reactor 25 tops after the reduction again.
Claims (3)
1. the renovation process of a hydrocarbon conversion catalyst, described catalyzer contains a kind of carrier, the halogen of at least a catalytically-active metals and certain content, the granules of catalyst diameter is between 0.5～5.0mm, in reaction process, catalyst surface is because of the carbon deposit inactivation, and its renovation process comprises:
A) be promoted to reclaimable catalyst in the separation hopper (1) at revivifier (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, catalyzer entered the buffer zone (4) at revivifier (3) top through allobar (202) from low pressure area (201);
B) catalyzer enters radially moving-bed of catalyst scorch region (5) by buffer zone (4) under action of gravity, and contains the carbon deposit that the oxygen resurgent gases contacts the burning-off catalyst surface, and resurgent gases recycles;
C) catalyzer after burning enters axial catalyst moving-bed chlorine oxidation zone (6) under action of gravity, contacts with chlorine-containing gas, carries out oxychlorination;
D) catalyzer behind the oxychlorination enters axial catalyst moving-bed calcining zone (7) under action of gravity, under the oxygen-containing gas effect, calcines;
E) catalyzer after the calcining leaves revivifier by revivifier (3) bottom, after the degassing, reduction are handled, enters reactor head and begins next circulation;
Have only catalyzer conduit (70) to communicate between described scorch region (5) and the chlorine oxidation zone (6), in the chlorine oxidation zone (6) with chlorine-containing gas after catalyzer contacts, chlorine-containing gas outlet (34) by chlorine oxidation zone (6) is discharged, after dechlorination is handled, enter the regeneration recycle gas loop, be circulated to scorch region (5);
In described scorch region (5), the treatment condition of catalyzer are: pressure is between 0.35-1.5MPa, the residence time of catalyzer is 0.5-3.0 hour, circulation gas (36) temperature in is between 400-500 ℃, oxygen level between 0.4-1.0mol%, the beds top temperature be controlled at make local area and chlorine oxidation zone (6), calcining zone (7) bed temperature all under support of the catalyst top temperature allowed to bear;
In described chlorine oxidation zone (6), the treatment condition of catalyzer are: bed temperature is than the high 10-50 of bed temperature ℃ of scorch region (5), pressure equates with scorch region (5), catalyzer is 1-3 hour in this residence time, 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) temperature in is 510-550 ℃, and cl content is 0.1-1.0wt%, and oxygen level is 3-21mol%;
In described calcining zone (7), the treatment condition of catalyzer are: the bed temperature of calcining zone (7) is than high 10-50 ℃ of chlorine oxidation zone (6) bed temperature, local area pressure is the self-balancing pressure of keeping calcining zone (7) dechlorination oxidation zone (6) oxygen-containing gas (32) flow, the catalyzer residence time is 1-3 hour, the oxygen level of the oxygen-containing gas (31) of introducing local area is at 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 oxidation zone (6), excessive part emptying.
2. according to the renovation process of the described hydrocarbon conversion catalyst of claim 1, it is characterized in that: described chlorine-containing gas of being discharged by chlorine oxidation zone (6) comes out from chlorine-containing gas outlet (34), after water cooler (19) cooling, enter soda-wash tower (8) dechlorination, with mix through the cooled regeneration recycle gas of extracting out by scorch region (5) (35) of interchanger (18), gas mixture drying device (9), strainer (10), behind compressor (11) and the interchanger (18), divide two-way to enter well heater (17) respectively, (16) heating, be introduced into scorch region (5) respectively by the circulation gas (36) after well heater (17) heating with by the hot gas (37) of crossing after well heater (16) heating, circulation gas (36) is mainly used in and burns, and crosses hot gas (37) and is mainly used in adjusting scorch region (5) bottom reaction bed temperature.
3. according to the renovation process of claim 1 or 2 described hydrocarbon conversion catalysts, 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 |
|---|---|---|---|
| CN98112916A CN1089639C (en) | 1998-07-10 | 1998-07-10 | Regeneration method of hydrocarbon converting catalyst |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98112916A CN1089639C (en) | 1998-07-10 | 1998-07-10 | Regeneration method of hydrocarbon converting catalyst |
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| CN1241455A CN1241455A (en) | 2000-01-19 |
| CN1089639C true CN1089639C (en) | 2002-08-28 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN98112916A Expired - Lifetime CN1089639C (en) | 1998-07-10 | 1998-07-10 | Regeneration method of hydrocarbon converting catalyst |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101191080B (en) * | 2006-11-30 | 2012-02-29 | 中国石油化工股份有限公司 | Catalyst continuous reproducible low octane rating gasoline modifying method |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7803326B2 (en) * | 2007-08-01 | 2010-09-28 | Uop Llc | Hydrocarbon conversion unit including a reaction zone receiving transferred catalyst |
| CN104289257A (en) * | 2013-07-19 | 2015-01-21 | 中国石油天然气股份有限公司 | Regenerator for reducing dead zone catalyst |
Citations (2)
| 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 |
-
1998
- 1998-07-10 CN CN98112916A patent/CN1089639C/en not_active Expired - Lifetime
Patent Citations (2)
| 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 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101191080B (en) * | 2006-11-30 | 2012-02-29 | 中国石油化工股份有限公司 | Catalyst continuous reproducible low octane rating gasoline modifying method |
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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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