CN101850276A - Catalyst regeneration method for improving selectivity of catalyst - Google Patents
Catalyst regeneration method for improving selectivity of catalyst Download PDFInfo
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- CN101850276A CN101850276A CN 200910131985 CN200910131985A CN101850276A CN 101850276 A CN101850276 A CN 101850276A CN 200910131985 CN200910131985 CN 200910131985 CN 200910131985 A CN200910131985 A CN 200910131985A CN 101850276 A CN101850276 A CN 101850276A
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Abstract
The invention relates to a catalyst regeneration method for improving the selectivity of a catalyst. A catalyst to be regenerated is contacted with oxygen-containing gas in a first fluidized bed and generates a coke combustion reaction, the mixture of the obtained semi-regenerated catalyst and flue gas enters a second fluidized bed regenerator, is contacted with the optional oxygen-containing gas and generates the coke combustion reaction continuously, the regenerated catalyst enters a reactor, and the flue gas enters an energy recovery system of the flue gas by a cyclone separator. The distribution of the activity of the regenerated catalyst obtained by the method is more uniform, the activity of the regenerated catalyst obtained by the method more approaches to the equilibrium activity of a catalyst, part of heavy metal on the surface of the regenerated catalyst is buried by a substrate under the conditions of low temperature and long-time operation, and the rest part of the heavy metal is passivated. When hydrocarbon carries out a catalytic cracking reaction on the regenerated catalyst, the yields of dry gas and coke are obviously lowered.
Description
Technical field
The present invention relates to contain in the poor oil catalytic cracking process coke burning regeneration method of Pd/carbon catalyst.More particularly, the present invention relates in the poor oil catalytic cracking process, cause catalyst activity and selectivity seriously to reduce because of depositing a large amount of coke and metal on the catalyst, must be through high-temperature oxydation regeneration, carry out passivation with most of coke burning-off on the catalyst and to metal active on the catalyst, to recover activity of such catalysts and selectivity.
Background technology
Poor oil owing to there is condensation reaction, except that generating light hydrocarbons, also generates a part of coke when carrying out catalytic cracking reaction, thereby be deposited on activity of such catalysts and selectivity are reduced.Therefore, adopt the high-temperature oxydation renovation process, the burning of the coke on the catalyst is removed to recover the serviceability of catalyst, this process is called the regeneration of catalyst, usually claim that the catalyst of deposit coke is a reclaimable catalyst, the catalyst behind the oxidation regeneration is a regenerated catalyst.Early stage catalyst recovery process is to feed oxygen-containing gas and adopt the single hop regeneration in low speed circulating fluidized bed, in the fluid bed of this low linear speed, the full back-mixing of gas-solid, gas and solid contacting efficiency are low, catalyst regeneration speed is slow, caused the regenerator catalyst inventory excessive, the regeneration effect of catalyst is poor, and the regenerated catalyst carbon content is 0.2 heavy %, it is low to burn intensity, is about 100kg (amount of coke)/[h (unit interval) T (catalyst inventory)].Along with molecular sieve catalyst uses on catalytic cracking unit widely, the especially use of the molecular sieve catalyst of USY type, the carbon content of the remnants on the regenerated catalyst and regeneration are very big to recovering the influence of activity of such catalysts and selectivity.Therefore, reduce catalyst inventory in the regenerative process and improve the direction that the catalyst regeneration effect becomes the regeneration techniques exploitation effectively.This is because in service at catalytic cracking unit, catalyst constantly is subjected to the effect of high temperature and water vapour, the heavy metal deposition that carries in the feedstock oil is on catalyst surface, activity of such catalysts constantly reduces, need fresh makeup catalyst to keep the equilibrium activity of catalyst in reaction-regeneration system, when one timing of fresh catalyst magnitude of recruitment, the catalyst general reserve is low more in the reaction-regeneration system, the catalyst replacement rate is just high more, and the equilibrium activity of reaction-regeneration system catalyst is also just high more so.
USP3,563,911 disclose a kind of two-stage regeneration, and reclaimable catalyst is in proper order by first dense-phase fluidized bed and second dense-phase fluidized bed, contact with oxygen containing gas and to make that coke carries out combustion reaction on the catalyst surface, the flue gas that is produced mixes and entrained catalyst enters the dilute phase settling section.The first dense-phase fluidized bed regeneration temperature is greater than 1050 °F (promptly 565.5 ℃); The gas superficial linear velocity of second dense-phase fluidized bed is 1.25 feet per seconds~6 feet per seconds (i.e. 0.381 meter per second~1.83 meter per seconds), and regeneration temperature is 1125~1350 °F (promptly 607.2~732.2 ℃).This method is compared with catalyst single hop renovation process, and under the not high condition of regenerative process carbon-burning load, it is nearly 40% that the reserve of regenerator inner catalyst can reduce, and the carbon content of regenerated catalyst can be lower than 0.1% weight.
CN1052688A discloses a kind of two-stage oxidizing regenerative method of fluid catalyst, reclaimable catalyst contacts the combustion reaction of concurrent green coke charcoal with oxygen containing gas in first dense-phase fluidized bed, the gas superficial linear velocity of first dense-phase fluidized bed is 0.8~2.5 meter per second, the catalyst mean residence time is 0.6~1.0 minute, and regeneration temperature is 650~750 ℃; Catalyst is removed most of coke in the first fluidized bed after, the catalyst of partial regeneration and gas pass distributor together and on flowing to, enter second fluid bed, contact the combustion reaction of concurrent green coke charcoal again with oxygen containing gas, the gas superficial linear velocity of second dense-phase fluidized bed is 1.2~3.0 meter per seconds, the catalyst mean residence time is 1.0~2.2 minutes, regeneration temperature is 700~800 ℃, after catalyst is fully regenerated, regenerated catalyst separates with flue gas, part regenerated catalyst enters reactor, and another part regenerated catalyst turns back to the first fluidized bed.This method has been simplified the structure and the regeneration technology flow process of regenerator.
CN1221022A discloses a kind of lapping type two-stage regeneration technology of heavy oil fluidized catalystic cracking, this method comprises two regenerators of arranged superposed, one section regeneration is last, the temperature of first section regenerator is 650~720 ℃, two sections regeneration are following, the temperature of second section regenerator is 650~780 ℃, be connected as a single entity with the low pressure drop distribution grid between two regenerators, make full use of contain certain excess oxygen content two sections regenerated flue gas as one section regenerative combustion gas, to save the oxygen-containing gas consumption is energy savings and producing cost, and two regenerators only need be with a flue and double slide valve or butterfly valve, simple in structure, be convenient to control, because minimizing equipment, thereby the compact construction investment that reduced arranged.
After adopting highly active zeolite catalyst, regenerator superficial gas flow velocity increases to more than 0.6 meter per second, burns intensity and brings up to more than the 100kg/ (th), and regeneration temperature is about about 700 ℃, and the catalyst time of staying is below 4 minutes.Develop from regeneration techniques, the development goal of regeneration techniques is under the deactivation environment of catalyst and abrasive conditions relatively relax always, the regenerated catalyst carbon content is controlled at below 0.10% weight, be preferably lower than 0.05% weight, burning intensity brings up to more than the 100kg/ (th), reach the highest with realization regenerated catalyst activation recovering, thereby realize the conversion capability maximum of hydro carbons.
But when pursuing the selectivity of purpose product, too high catalyst activity is unfavorable for that the selectivity of purpose product improves, especially fresh catalyst self has higher catalyst activity, how fresh catalyst activity is reduced to the equilibrium catalyst activity level as soon as possible.In addition, when the heavier feedstock oil of processing, the more metal of deposition on the catalyst, and regeneration temperature up to 700 ℃ about, cause the influence that is deposited on these metal pair catalyst self structure on the catalyst to increase the weight of, thereby reduced selection of catalysts.
CN101362959A discloses a kind of catalysis conversion method of producing propylene and high-knock rating gasoline, and the raw material of difficult cracking contacts with hot regenerated catalyst earlier, at 600~750 ℃ of temperature, weight (hourly) space velocity (WHSV) 100~800h
-1, pressure 0.10~1.0MPa, catalyst and raw material weight ratio 30~150, the weight ratio of water vapour and raw material is to carry out cracking reaction under 0.05~1.0 the condition, the reaction logistics mixes with the feedstock oil of easily cracking, at 450~620 ℃ of temperature, weight (hourly) space velocity (WHSV) 0.1~100h
-1, pressure 0.10~1.0MPa, catalyst and raw material weight ratio 1.0~30, the weight ratio of water vapour and raw material is to carry out cracking reaction under 0.05~1.0 the condition; Reclaimable catalyst is with after reaction oil gas separates, reclaimable catalyst enters stripper, Returning reactor behind stripping, coke burning regeneration, reaction oil gas obtains purpose product propylene and high-knock rating gasoline and the raw material of cracking again through separation, and it is that 180~260 ℃ cut, heavy aromatics raffinated oil that the raw material of described cracking again comprises boiling range.The productive rate and the selectivity of this method propylene significantly increase, and the productive rate and the octane number of gasoline improve significantly, and dry gas yied reduces amplitude up to more than the 80 heavy %.This method is based on reaction space-time restriction effect theory, adopt Reaction Separation technology separating with alkane building stone in the feedstock oil and aromatic hydrocarbons building stone, saturated branch in the alkane building stone and light aromatic hydrocarbons are converted into fluid product through relaxing catalytic cracking process, part asphalitine in the aromatic hydrocarbons building stone is adsorbed by the catalyst outer surface, polycyclic aromatic hydrocarbon and colloid are retained in the distillate behind the upgrading as far as possible, thereby realize alkane and this notion of alkane building stone selective cracking.The distillate that contains more polycyclic aromatic hydrocarbon and colloid carries out hydrogenation in the hydrotreatment unit saturated or carry out extracting in heavy aromatics extracting unit, the saturated distillate of hydrogenation or to raffinate oil be the catalytically cracked stock of high-quality, improve the selectivity of catalytic cracking unit production purpose product, thereby realize that petroleum resources rationally and efficiently utilize.The employed catalyst of this method preferably activity of such catalysts is more even with other property distribution, thereby helps the control of response parameter.
Summary of the invention
The objective of the invention is to provide on the basis of existing technology a kind of catalyst recovery process that improves catalyst selectivity, to improve selection of catalysts.
The catalyst recovery process that improves catalyst selectivity provided by the invention comprises:
Reclaimable catalyst is earlier in first fluidized bed regenerator, contact with oxygen-containing gas, in temperature is 550~750 ℃, the catalyst mean residence time is 0.5~2 minute condition regeneration, the coke combustion reaction takes place, the mixture of gained half regenerated catalyst and flue gas enters in second fluid bed regenerator, contact with optional oxygen-containing gas, in temperature is 550~700 ℃, the catalyst mean residence time is that 3~30 minutes condition continues regeneration, the coke combustion reaction takes place, catalyst after the regeneration enters reactor, and flue gas enters smoke energy recovering system through cyclone separator.
In first fluidized bed regenerator, described catalyst mean residence time is preferably 0.6~1.0 minute; Described temperature is preferably 600~700 ℃; The gas superficial linear velocity of first fluidized bed regenerator is 0.5~3.0 meter per second, is preferably 0.6~1.5 meter per second.
In second fluid bed regenerator, described catalyst mean residence time is preferably 4~25 minutes; Described temperature is preferably 580~680 ℃; The gas superficial linear velocity of the close phase section of second fluid bed regenerator is 0.1~0.6 meter per second, is preferably 0.2~0.5 meter per second.
The regeneration temperature of second fluid bed regenerator preferably is lower than the regeneration temperature of first fluidized bed regenerator, and the regeneration temperature of second fluid bed regenerator is more preferably less than 10~50 ℃ of the regeneration temperatures of first fluidized bed regenerator.
Described oxygen-containing gas is selected from one or more in air, oxygen, the oxygen-enriched air.
Catalyst after the described regeneration can be divided into two parts, and wherein a part of regenerated catalyst enters reactor, and another part regenerated catalyst turns back in the first fluidized bed, mixes with reclaimable catalyst to improve the temperature of catalyst.
When heat in the regenerator was superfluous, or/and interior heat collector heat-obtaining promptly can be delivered to outside heat removing with the internal regenerator divided catalyst and cool off, cooled catalyst turned back to regenerator to described internal regenerator divided catalyst again through external warmer.
Described catalyst comprises zeolite, inorganic oxide and optional clay, and each component accounts for total catalyst weight respectively: the heavy % in zeolite 1 heavy %~50, the heavy % in the heavy % in inorganic oxide 5 heavy %~99, clay 0 heavy %~70.Its mesolite is as active component, be selected from mesopore zeolite and/or optional large pore zeolite, mesopore zeolite accounts for the heavy % in 0 heavy %~100 of zeolite gross weight, the heavy % in preferred 20 heavy %~80, large pore zeolite accounts for the heavy % in 0 heavy %~100 of zeolite gross weight, the heavy % in preferred 20 heavy %~80.Mesopore zeolite is selected from ZSM series zeolite and/or ZRP zeolite, also can carry out modification with transition metals such as nonmetalloids such as phosphorus and/or iron, cobalt, nickel to above-mentioned mesopore zeolite, the more detailed description of relevant ZRP is referring to US5,232,675, the ZSM series zeolite is selected from one or more the mixture among the zeolite of ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38, ZSM-48 and other similar structures, the more detailed description of relevant ZSM-5 is referring to US3,702,886.Large pore zeolite is selected from one or more the mixture in this group zeolite that the super steady Y that is obtained by Rare Earth Y (REY), rare earth hydrogen Y (REHY), distinct methods, high silicon Y constitute.
Inorganic oxide is selected from silica (SiO as bonding agent
2) and/or alundum (Al (Al
2O
3).
Clay is as bonding agent, is selected from kaolin, halloysite, imvite, diatomite, galapectite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite, the bentonite one or more.
Compare with existing renovation process, major advantage of the present invention is following three aspects:
1, the regenerated catalyst activity distribution is more even, and more near the equilibrium activity of catalyst, when hydro carbons carries out catalytic cracking reaction on this regenerated catalyst, dry gas and coke yield will reduce significantly.
2, the lip-deep heavy metal of regenerated catalyst is under low temperature and long-time operation condition, and the part heavy metal is buried by matrix, and remaining part heavy metal is passivated, thereby influence reduces to molecular sieve, and dry gas yied and coke yield influence are reduced.
3, intensity is burnt in regeneration increases significantly.
Description of drawings
Accompanying drawing is the basic procedure schematic diagram that improves the catalyst recovery process of catalyst selectivity provided by the invention.
The specific embodiment
Further specify method provided by the present invention below in conjunction with accompanying drawing, but therefore the present invention is not subjected to any restriction.
Accompanying drawing is the basic procedure schematic diagram that improves the catalyst recovery process of catalyst selectivity provided by the invention.
As shown in drawings, reclaimable catalyst enters first fluidized bed regenerator 2 through inclined tube 1 to be generated, oxygen-containing gas is entered the bottom of first fluidized bed regenerator 2 by main air distribution grid 4 through pipeline 3, contact the combustion reaction of concurrent green coke charcoal with reclaimable catalyst, half regenerated catalyst and flue gas enter the bottom of second fluid bed regenerator 7 through distribution grid 5, optional oxygen-containing gas enters the bottom of second fluid bed regenerator 7 through pipeline 6, half regenerated catalyst is fully regenerated in second fluid bed regenerator 7, and flue gas is successively through regenerator dilute phase section 8, cyclone separator 9 and flue gas pipeline 10 enter smoke energy recovering system 11.Partial regeneration catalyst after the regeneration enters the bottom of first fluidized bed regenerator 2 through circulation inclined tube 12, mix with reclaimable catalyst, the partial regeneration catalyst enters riser reactor 16 bottoms through regenerator sloped tube 13 in addition, it is up that pre-lifting medium enters riser reactor bottom lifting regenerated catalyst through pipeline 14, feedstock oil enters riser reactor 16 through pipeline 15 and contacts with regenerated catalyst and carry out catalytic cracking reaction, and reaction oil gas enters piece-rate system 21 through settler 18, cyclone separator 19 and oil-gas pipeline 20 successively and obtains the purpose product.Reclaimable catalyst enters inclined tube 1 to be generated through settler 18 and stripper 17 and turns back to dense-phase fluidized bed regenerator 2 and carry out next round regeneration.
The following examples will be further specified the present invention, but not thereby limiting the invention.Employed feedstock oil is decompression residuum in embodiment and the Comparative Examples, and its character is listed in table 1.Catalyst is produced by catalyst branch company of Sinopec Group Shandong catalyst plant, and goods number is MLC-500, and its character is listed in table 2.
Embodiment
Embodiment carries out on kitty cracker, as shown in drawings.According to renovation process proposed by the invention catalyst is regenerated, oxygen-containing gas is an air, and first fluidized bed regenerator gases superficial linear vilocity is 1.0 meter per seconds, and the catalyst mean residence time is 1.5 minutes, and regeneration temperature is 680 ℃; The second fluid bed regenerator gas superficial linear velocity is 0.3 meter per second, and the catalyst mean residence time is 15 minutes, and regeneration temperature is 650 ℃.Nickel content on the regenerated catalyst is 10000 μ g/g, and the catalyst after the regeneration enters reactor, and the feedstock oil listed with table 1 contacts, and carries out catalytic cracking reaction, and regeneration condition, reaction condition, regeneration result and reaction result are listed in table 3.
Comparative Examples
Comparative Examples also is to carry out on identical kitty cracker, pair reclaimable catalyst identical with embodiment of renovation process routinely regenerated, catalyst property is listed in table 2, first fluidized bed regenerator gases superficial linear vilocity is 1.2 meter per seconds, the catalyst mean residence time is 1.0 minutes, and regeneration temperature is 700 ℃; The second fluid bed regenerator gas superficial linear velocity is 1.2 meter per seconds, and the catalyst mean residence time is 2.0 minutes, and regeneration temperature is 720 ℃.Nickel content on the regenerated catalyst also is 10000 μ g/g, and the catalyst after the regeneration enters reactor, and the feedstock oil listed with table 1 contacts, and carries out catalytic cracking reaction, and regeneration condition, reaction condition, regeneration result and reaction result are listed in table 3.
As can be seen from Table 3, compare with Comparative Examples, adopt renovation process proposed by the invention, under close conversion ratio and identical regenerated catalyst nickel content, dry gas and coke yield reduce significantly, and resulting regenerated catalyst improves significantly to the selectivity of dry gas and coke.
Table 1
The feedstock oil title | Decompression residuum |
Density (20 ℃), kilogram/rice 3 | ??920.9 |
Kinematic viscosity, millimeter 2/ second | |
??80℃ | ??/ |
??100℃ | ??114.4 |
Carbon residue, heavy % | ??8.2 |
Condensation point, ℃ | ??25 |
Acid number, mgKOH/g | ??/ |
Total nitrogen, heavy % | ??0.33 |
Sulphur, heavy % | ??0.21 |
Carbon, heavy % | ??86.91 |
Hydrogen, heavy % | ??12.55 |
Tenor, ppm | |
Nickel | ??8.8 |
Vanadium | ??0.1 |
Iron | ??1.8 |
Copper | ??<0.1 |
Sodium | ??3.0 |
Calcium | |
Boiling range, ℃ | |
Initial boiling point | ??415 |
??10% | ??545 |
??30% | ??/ |
Table 2
The catalyst goods number | ??MLC-500 |
Chemical composition, heavy % | |
Aluminium oxide | ??50.2 |
Sodium oxide molybdena | ??0.321 |
Iron oxide | ??/ |
Rare earth | |
Apparent density, kilogram/rice 3 | ??700 |
Pore volume, milliliter/gram | ??0.38 |
Specific area, rice 2/ gram | ??229 |
Abrasion index is when weighing % -1 | ??1.9 |
Size consist, heavy % | |
0~40 micron | ??17.3 |
40~80 microns | ??49.3 |
>80 microns | ??33.4 |
Table 3
Embodiment | Comparative Examples | |
Regeneration unit | ||
First fluidized bed regenerator | ||
Gas superficial velocity, meter per second | ??1.0 | ??1.2 |
The catalyst time of staying, minute | ??1.5 | ??1.0 |
Embodiment | Comparative Examples | |
Regeneration temperature, ℃ | ??680 | ??700 |
Second fluid bed regenerator | ||
Gas superficial velocity, meter per second | ??0.3 | ??1.2 |
The catalyst time of staying, minute | ??15 | ??2.0 |
Regeneration temperature, ℃ | ??650 | ??720 |
Carbon content on the regenerated catalyst, heavy % | ??0.09 | ??0.05 |
Regenerated catalyst nickel content, μ g/g | ??10000 | ??10000 |
The cracking hydrocarbon reaction member | ||
The riser outlet temperature, ℃ | ??500 | ??510 |
The weight ratio of catalyst/feed | ??6 | ??4 |
Reaction time, second | ??3 | ??3 |
The weight ratio of water vapour/raw material | ??0.05 | ??0.05 |
Product distributes, heavy % | ||
Dry gas | ??2.75 | ??3.21 |
Liquefied gas | ??12.95 | ??13.10 |
Gasoline | ??44.68 | ??43.30 |
Diesel oil | ??21.50 | ??20.78 |
Slurry oil | ??9.11 | ??9.86 |
Coke | ??9.01 | ??9.75 |
Add up to | ??100.0 | ??100.0 |
Embodiment | Comparative Examples | |
Total liquid yield, heavy % | ??79.13 | ??77.18 |
Octane number | ||
??RON | ??91.4 | ??91.2 |
??MON | ??79.4 | ??78.6 |
Claims (9)
1. catalyst recovery process that improves catalyst selectivity, it is characterized in that reclaimable catalyst is earlier in first fluidized bed regenerator, contact with oxygen-containing gas, in temperature is 550~750 ℃, the catalyst mean residence time is 0.5~2 minute condition regeneration, the coke combustion reaction takes place, the mixture of gained half regenerated catalyst and flue gas enters in second fluid bed regenerator, contact with optional oxygen-containing gas, in temperature is 550~700 ℃, the catalyst mean residence time is that 3~30 minutes condition continues regeneration, the coke combustion reaction takes place, catalyst after the regeneration enters reactor, and flue gas enters smoke energy recovering system through cyclone separator.
2. according to the method for claim 1, it is characterized in that in first fluidized bed regenerator that described catalyst mean residence time is 0.6~1.0 minute; Described temperature is 600~700 ℃; The gas superficial linear velocity of first fluidized bed regenerator is 0.5~3.0 meter per second.
3. according to the method for claim 1, it is characterized in that in second fluid bed regenerator that described catalyst mean residence time is 4~25 minutes; Described temperature is 580~680 ℃; The gas superficial linear velocity of the close phase section of second fluid bed regenerator is 0.1~0.6 meter per second.
4. according to the method for claim 1, it is characterized in that described oxygen-containing gas is selected from one or more in air, oxygen, the oxygen-enriched air.
5. according to the method for claim 1, it is characterized in that the catalyst after the described regeneration is divided into two parts, wherein a part of regenerated catalyst enters reactor, and another part regenerated catalyst turns back in the first fluidized bed and mixes with reclaimable catalyst.
6. according to the method for claim 1, it is characterized in that described internal regenerator divided catalyst through external warmer or/and interior heat collector heat-obtaining.
7. according to the method for claim 1, it is characterized in that described catalyst comprises zeolite, inorganic oxide and optional clay, each component accounts for total catalyst weight respectively: the heavy % in zeolite 1 heavy %~50, the heavy % in the heavy % in inorganic oxide 5 heavy %~99, clay 0 heavy %~70.
8. according to the method for claim 1, it is characterized in that the regeneration temperature of second fluid bed regenerator is lower than the regeneration temperature of first fluidized bed regenerator.
9. according to the method for claim 8, the regeneration temperature that it is characterized in that second fluid bed regenerator is lower than 10~50 ℃ of the regeneration temperatures of first fluidized bed regenerator.
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CN2009101319850A CN101850276B (en) | 2009-03-31 | 2009-03-31 | Catalyst regeneration method for improving selectivity of catalyst |
RU2010111850/04A RU2529021C2 (en) | 2009-03-31 | 2010-03-29 | Method of catalyst regeneration |
GB201005341A GB2469195B (en) | 2009-03-31 | 2010-03-30 | A catalyst regeneration process for improving catalyst selectivity |
JP2010077451A JP5537220B2 (en) | 2009-03-31 | 2010-03-30 | Catalyst regeneration method for improving catalyst selectivity |
US12/749,996 US8791038B2 (en) | 2009-03-31 | 2010-03-30 | Catalyst regeneration process for improving catalyst selectivity |
KR1020100028479A KR101654598B1 (en) | 2009-03-31 | 2010-03-30 | A catalyst regeneration process for improving catalyst selectivity |
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