CN103721762B - A kind of reduction CO2 emission also improves optionally catalyst recovery process - Google Patents
A kind of reduction CO2 emission also improves optionally catalyst recovery process Download PDFInfo
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Abstract
A kind of reduction CO2 emission also improves optionally catalyst recovery process, band Pd/carbon catalyst first in burning tank after pure oxygen partial regeneration, enter through dilute phase pipe in the dense-phase bed of regenerating unit and burn residual coke, dense-phase bed arranges heat collector to control the temperature of dense-phase bed, flue gas traps enter smoke energy recovering system, carbon dioxide separating system separating carbon dioxide successively after cyclonic separation after, and regenerated catalyst enters reactor cycles and uses after catalyst cooling, activation.The method not only can make catalyst holomorphosis, and catalyst activity is more evenly distributed, thus reduces catalytic cracking by-product coke and dry gas yied; And significantly can reduce carbon emission, even reach zero carbon emission.
Description
Technical field
The present invention relates to the renovation process containing Pd/carbon catalyst in a kind of hydrocarbon process.More particularly, the present invention relates in mink cell focus catalytic cracking process and realize carbon dioxide discharge-reduction and the catalyst recovery process improving catalyst choice.
Background technology
Now, lot of challenges that the development of whole world petroleum refining industry faces oil price volatility, the aggravation of crude oil in poor quality trend, oil quality specification improves, energy-saving and emission-reduction requirement becomes sternly, bio-fuel develops rapidly etc., minimizing CO2 emission, mitigation of climate change have become petroleum refining industry and to have transformed mode of economic growth, kept the only way of sustainable development.In October, 2009, national publication controls the action target of greenhouse gas emission, namely arrives the year two thousand twenty nationwide units GDP CO
2discharge declined 40% to 45% than 2005, and during clearly proposing " 12 ", per GDP CO2 emission reduces by 17%, and country is in the likely collection " carbon tax " in good time of " 12 " period simultaneously.Therefore effectively reduce carbon emission in petroleum refining and chemical process to seem and be even more important, trap, seal up for safekeeping and manage CO
2the vital task in refinery's future will be become.Carbon emission in processing of heavy oil process is the carbon emission of catalytic cracking burning, hydrogen production process and the energy consumption of technical process mainly.Catalytic cracking unit is the core process units of refinery, becomes CO because catalyst burns
2one of main source of discharge.
US2011/0155642 A1 discloses a kind of catalytic cracking process process reducing CO2 emission, adopt coke-burning riser series connection dense bed regenerating unit, pure oxygen and the regeneration techniques in coke-burning riser multiple spot delivery of supplemental oxygen, this technology Special attention will be given to adds a tank in regeneration and circuit to be generated respectively, wherein the tank employing nitrogen of regenerative circuit carries out degassed to regenerated catalyst, and the tank of circuit to be generated burns efficiency to improve the front temperature of reclaimable catalyst regeneration to improve by introducing reclaimable catalyst and regenerated catalyst mixing.But the introducing of regenerative circuit nitrogen finally inevitably makes nitrogen play a reversed role in flue gas by regenerator, obviously lose the advantage of pure oxygen regeneration, only burn efficiency and increase, but the recovery of carbon dioxide adds difficulty.
US4542114 discloses a kind of integral process process reclaiming the flue gas compositions such as carbon dioxide, can be implemented in burning process and go back hydrogen manufacturing and carbon dioxide product, eliminate sulphur, the aerial discharge of nitrogen oxide completely, the pure oxygen mist that it adopts carbon dioxide to dilute carries out catalyst and burns to produce rich carbonated flue gas simultaneously.But this technique not increasing interior heat collecting device for realizing in regenerator, emphasize the wherein preferred 30-24% of oxygen concentration 60-21% in mist, thus part losing the advantage adopting purity oxygen regeneration, burns efficiency as increased substantially, reducing regenerator size etc.
US5565089 discloses a kind of catalytic cracking catalyst process of regenerating, first enter regenerator with air to carry out catalyst and burn, then the carbon dioxide in reclaiming flue gas, recycled carbon dioxide and be incorporated to oxygen-containing gas stream gradually until in regenerator temperature normal, finally only inject oxygen and carbon dioxide carries out burning of catalyst.This process of regenerating only pays close attention to the improvement of regenerative process gas handling system aspect and the process of flue gas, does not consider the problem of regenerator configuration or the concrete aspect such as regeneration technology process and catalytic cracking catalyst circulation.
CN1600431A discloses a kind of incomplete regen-eration smoke combustion technology, adopt the way of supplementing air in the incomplete regen-eration flue gas between catalyst regenerator and flue gas turbine inlet, CO in incomplete regen-eration flue gas is burnt away, thus make flue-gas temperature be increased to 660-760 DEG C, flue gas turbine inlet temperature is finally made to reach 640-700 DEG C, improve cigarette machine organic efficiency, reduce plant energy consumption with recovered flue gas pressure energy to greatest extent.Adopt the present invention, the concentration according to unit scale and CO and/or entraining hydrocarbon supplements air capacity 20-300Nm
3/ min, effectively can improve flue-gas temperature 20-80 DEG C, improves cigarette engine efficiency.For single hop incomplete regen-eration, in flue, supplement air flue gas also can be made to carry hydro carbons Thorough combustion secretly, eliminate its impact on cigarette machine, but effectively can not reduce CO2 emissions.
Catalyst coke burning regeneration method due to routine in fluid bed, passes into air or oxygen-containing gas regenerates, and air is primarily of O
2and N
2composition, containing a large amount of N in the regenerated flue gas therefore produced after catalyst coke burning regeneration
2, CO
2with a small amount of O
2and CO.And the flue gas of this composition is due to CO
2concentration is low, therefore CO
2separating difficulty is large, cost is high, cannot be isolated collection, directly can only discharge, thus cause greenhouse effects after entering energy-recuperation system.
In addition, from the development of regenerator, pursue the at utmost recovery realizing regenerated catalyst activity, to realize the maximum conversion ability of hydro carbons always.But the activity of catalyst is the concept statement of a macroscopical conversion ratio, does not embody the pursuit of object product selectivity.For example can realize regenerated catalyst activation recovering during regeneration the highest, but this regenerated catalyst may cause high coke and dry gas yied due to its high activity when participating in reaction, this does not wish to see.Therefore need a kind of uniformity pursuing catalyst activity recovery during regeneration, realize one acid on regenerated catalyst in other words and be uniformly distributed, thus realize low coke and dry gas yied, high object product selectivity.Therefore, be necessary develop a kind of reduction CO2 emission and improve optionally catalyst recovery process.
Summary of the invention
The object of the invention is to provide a kind of on the basis of existing technology reduce CO2 emission and improve optionally catalyst recovery process.
Reduction CO2 emission provided by the invention also improves the regenerating unit pattern that optionally catalyst recovery process adopts burning tank, dilute phase pipe series connection dense bed, and burning tank is fast bed operation, and dense bed is bubbling bed operation, and the method comprises:
(1) the band Pd/carbon catalyst from catalytic cracking unit stripping section first adopts pure oxygen gas to regenerate in burning tank, and coke combustion reaction occurs, and the ratio of burning in burning tank is 40-50%;
(2) from burning tank, catalyst out and flue gas enter dense-phase bed through dilute phase pipe, pure oxygen gas is supplemented further bottom dense-phase bed, make that the catalyst of incomplete regen-eration burns further in dense-phase bed, holomorphosis, the ratio of burning of dense-phase bed is 50-60%;
(3) dense-phase bed arranges heat collector and carries out heat-obtaining to catalyst, is no more than 750 DEG C preferably more than 720 DEG C with the temperature controlling dense-phase bed;
(4) supplement or not replenishment cycles flue gas bottom burning tank, when replenishment cycles flue gas, keep being not less than 30% from the oxygen concentration regenerator cyclone separation system flue gas out and be preferably not less than 40%;
(5) flue gas enters smoke energy recovering system after cyclone separator is separated, and enters carbon dioxide separating system subsequently, traps after separating carbon dioxide;
(6) regenerator sloped tube arranges catalyst activation system, and this system comprises catalyst cooler and activator, enters reactor cycles again use from regenerator regenerated catalyst out after catalyst activation system.
The operating condition of described burning tank is: temperature 550-720 DEG C, and catalyst mean residence time is preferred 30.0-80.0 second 20.0-90.0 second, and the gas superficial linear velocity of burning tank is that 1.0-3.0m/s is preferably 1.2-2.0m/s.In burning tank, can interior heat collector be set, also can not arranges, depend on that whether the temperature of burning tank is more than 750 DEG C.
The operating condition of described dense-phase bed is: temperature 600 ~ 750 DEG C, and catalyst mean residence time is 1.0-4.0 minute preferred 1.0-3.0 minute, and gas superficial linear velocity is that 0.4-0.8m/s is preferably 0.4-0.6m/s.Dense-phase bed arrange heat collector be interior heat collector or/and external warmer, heat collector is one or more.
The operating condition of described catalyst activation system is: the catalyst cooler similar in activation system is in external warmer, and wherein catalyst is close operates mutually, and density is 300-700kg/m
3, cooling medium can be water or other medium.Cooler needs to ensure that regenerated catalyst temperature after cooling is 550-640 DEG C, and optimum is 560-630 DEG C.Activator is a fluidized bed plant, and fluidizing agent presses through hot water and steam in being, its pressure is 3.0-3.5MPa, and temperature is 400-450 DEG C.Catalyst is close in activator to be operated mutually, and density is 300-500kg/m
3, the catalyst time of staying is wherein 2-8 minute, preferred 3-6 minute.
Described catalyst comprises zeolite, inorganic oxide and optional clay, and each component accounts for total catalyst weight respectively and is: the heavy % of the heavy %-70 of the heavy % of the heavy %-50 of zeolite 1, the heavy % of the heavy %-99 of inorganic oxide 5, clay 0.Its mesolite is active component, be selected from mesopore zeolite and/or optional large pore zeolite, mesopore zeolite accounts for the heavy % of 10 heavy %-100 of zeolite gross weight, preferably the heavy % of 20 heavy %-80, large pore zeolite accounts for the heavy % of 0 heavy %-90 of zeolite gross weight, preferably the heavy % of 20 heavy %-80.Mesopore zeolite is selected from one or more mixtures in ZSM series zeolite and/or ZRP zeolite, also can carry out modification to transition metals such as the nonmetalloids such as above-mentioned mesopore zeolite phosphorus and/or iron, cobalt, nickel.One or more mixture in this group zeolite that large pore zeolite is selected from the super steady Y obtained by Rare Earth Y (REY), rare earth hydrogen Y (REHY), distinct methods, high silicon Y is formed.
Inorganic oxide, as catalyst carrier, is selected from silica and/or alundum (Al2O3) or both mixtures.
Clay, as bonding agent, is selected from one or more in kaolin, imvite, diatomite, saponite, rectorite, sepiolite, hydrotalcite and bentonite.
Compared with existing renovation process, major advantage of the present invention is following two aspects:
1, the method not only can make catalyst holomorphosis, significantly can reduce carbon emission, even zero carbon emission simultaneously, reduces greenhouse effects.
2, the method significantly can reduce device catalyst inventory especially regenerator reserve, greatly reduces the size of static equipment and dynamic equipment, reduces investment, reduces floor space.
3, because purity oxygen concentration in regenerative system is high, thus make to burn efficiency and increase substantially, the recovery time shortens, and reduces the fragmentation of catalyst, wearing and tearing, improves the service efficiency of catalyst.
4, the activity that the method can realize regenerated catalyst is uniformly distributed, thus coke and dry gas yied in the product of catalytic cracking are reduced.
Accompanying drawing explanation
Accompanying drawing is reduction CO2 emission provided by the invention and improves optionally catalyst recovery process schematic flow sheet.
Detailed description of the invention
Further illustrate method provided by the present invention below in conjunction with accompanying drawing, but the present invention is not therefore subject to any restriction.
Accompanying drawing is reduction CO2 emission provided by the invention and improves optionally catalyst recovery process schematic flow sheet.
In accompanying drawing, each numbering is described as follows:
1,10,11,12,13,18,20,21,27,28,29 all pipeline is represented; 2 is burning tank; 3 is dilute phase pipe; 4 is dense-phase bed; 5 is dilute-phase zone; 6 is regenerator; 7 and 17 are cyclone separation system; 8 is smoke energy recovering system; 9 is carbon dioxide separating system; 14 is riser reactor; 15 is stripping section; 16 is settler; 19 is oil and gas separating system; 22 is external warmer; 30 is catalyst cooler; 31 is activator.
As shown in drawings, reclaimable catalyst enters burning tank 2 through inclined tube 1 to be generated, pure oxygen gas enters burning tank 2 through pipeline 20, concurrent green coke charcoal combustion reaction, up is contacted with reclaimable catalyst, flue gas and incomplete regen-eration catalyst enter the dense-phase bed 4 of regenerator 6 through dilute phase pipe 3, purity oxygen also enters the bottom of dense-phase bed 4 through pipeline 21, thus makes the catalyst of incomplete regen-eration burn further, regenerate.For controlling the temperature of dense-phase bed, be provided with external warmer 22.The flue gas of dense-phase bed leaves regenerator through regenerator dilute-phase zone 5, cyclone separation system 7.Directly enter smoke energy recovering system 8 from a regenerator flue gas part out to recover energy, another part returns to the bottom of dense-phase bed 4 through pipeline 10 circulation, can realize the lifting of the carbon dioxide in flue gas concentration entering carbon dioxide separating system 9.Enter carbon dioxide separating system 9 from energy-recuperation system 8 flue gas out, realize the trapping of carbon dioxide.Regenerated catalyst after regeneration enters catalyst cooler 30 through regenerator sloped tube 11, activator 31 is entered by inclined tube 27 after catalyst cooling, overheated steam also enters activator 31 through pipeline 29, regenerated catalyst after activation enters bottom riser reactor 14 through inclined tube 28, pre-lift medium enters through pipeline 12 that to promote regenerated catalyst bottom riser reactor up, feedstock oil enters riser reactor through pipeline 13 and to contact with regenerated catalyst and to carry out catalytic cracking reaction, reaction oil gas is successively through settler 16, cyclone separation system 17 and oil-gas pipeline 18 enter oil and gas separating system 19 and obtain various product.Reclaimable catalyst enters inclined tube 1 to be generated and turns back to burning tank 2 and regenerate after stripping section 15 stripping, thus realizes recycling.
The following examples will be further described the present invention, but not thereby limiting the invention.The feedstock oil used in embodiment and comparative example is decompression residuum, and its character lists 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 lists in table 2.
Embodiment
Embodiment is carried out on catalytic cracking demonstration plant, as shown in drawings.Demonstration plant does not have smoke energy recovering system and carbon dioxide separating system.The wherein internal diameter 20 centimetres of burning tank, the internal diameter of dense-phase bed is 50 centimetres.According to renovation process proposed by the invention, catalyst is regenerated, pass into pure oxygen gas respectively at burning tank and dense-phase bed, return bottom dense-phase bed from regenerator cyclone separation system flue gas partial out simultaneously.The temperature of burning tank is 650 DEG C, and regenerator dense-phase bed temperature is 640 DEG C.Catalyst is 60 seconds in the time of staying of burning tank, is 2 minutes at the mean residence time of dense-phase bed.In burning tank, gas superficial linear velocity is 1.4m/s, and in dense-phase bed, gas superficial linear velocity is 0.6m/s.The density of catalyst of the catalyst cooler in activation system is 550Kg/m3, and catalyst temperature after cooling is 620 DEG C.Hot water steaming device pressure 3.4MPa is pressed through, temperature 425 DEG C, density of catalyst 350kg/m in activator in activation system
3, the time of staying of catalyst in activator is 3 minutes.From activation system out after catalyst enter reactor, contact with the feedstock oil listed by table 1, carry out catalytic cracking reaction, regeneration condition, reaction condition, regenerated catalyst carbon content and flue gas composition, product distribution all list in table 3.
Comparative example
Comparative example is also carried out on mutually isostructural catalytic cracking demonstration plant, does not have smoke energy recovering system and carbon dioxide separating system and catalyst activation system.Burning tank is different with embodiment with the internal diameter of dense bed, the internal diameter of burning tank 40 centimetres, and the internal diameter of dense-phase bed is 200 centimetres, and other physical dimension is identical with embodiment.The renovation process pair reclaimable catalyst identical with embodiment routinely regenerates, and burning tank and dense-phase bed pass into air respectively, and the middle portion temperature of burning tank is 685 DEG C, and regenerator dense-phase bed temperature is 690 DEG C.Catalyst is 3 minutes in the time of staying of burning tank, is 8 minutes at the mean residence time of dense-phase bed.In burning tank, gas superficial linear velocity is 1.5m/s, and in dense-phase bed, gas superficial linear velocity is 0.5m/s.Catalyst after regeneration enters reactor, contacts with the feedstock oil listed by table 1, carries out catalytic cracking reaction, and regeneration condition, reaction condition, regenerated catalyst carbon content and flue gas composition, product distribution all list in table 3.
As can be seen from the Comparative result of operating condition and table 3, compared with comparative example, the present invention is in burning tank size and regeneration dense bed size significantly reduces, device general reserve significantly reduces, consume prerequisite that wind index obviously reduces under, adopt renovation process proposed by the invention, on regenerated catalyst, carbon content reduces more, in addition, CO and N is not contained in the flue gas that this catalyst recovery process produces
2, gas concentration lwevel, up to 57%, is conducive to separation and the trapping of carbon dioxide.In addition, embodiment is owing to adopting catalyst activation system, and the ratio dry gas yied of comparing reduces by 0.6 percentage point, and coke yield reduces by 0.7 percentage point, gasoline and diesel yield increase, and total liquid yield (liquefied gas, gasoline, diesel yield sum) increases by 1.1 percentage points.
Table 1
| Feedstock oil title | Decompression residuum |
| Density (20 DEG C), kg/m 3 | 920.9 |
| Kinematic viscosity, millimeter 2/ second | |
| 100℃ | 114.4 |
| Carbon residue, heavy % | 8.2 |
| Condensation point, DEG C | 25 |
| 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 |
| Boiling range, DEG C | |
| HK (initial boiling point) | 415 |
| 10％ | 545 |
| 30％ | / |
| 50％ | / |
| 70％ | / |
| KK (end point of distillation) | / |
Table 2
| Catalyst commercial product is numbered | MLC-500 |
| Chemical composition, heavy % | |
| Aluminium oxide | 50.2 |
| Sodium oxide molybdena | 0.321 |
| Apparent density, kg/m 3 | 700 |
| Pore volume, mL/g | 0.38 |
| Specific area, m 2/g | 229 |
| Abrasion index, during heavy % -1 | 1.9 |
| Size consist, heavy % | |
| 0 ~ 40 micron | 17.3 |
| 40 ~ 80 microns | 49.3 |
| > 80 microns | 33.4 |
Table 3
| Embodiment | Comparative example | |
| Device catalyst general reserve, ton | 1 | 5 |
| Cracking hydrocarbon reaction member | ||
| Outlet temperature of riser, DEG C | 500 | 500 |
| Catalyst/feed weight ratio | 6 | 6 |
| Reaction time, second | 3 | 3 |
| Water vapour/raw material weight ratio | 0.05 | 0.05 |
| Product distributes, heavy % | ||
| Dry gas | 3.0 | 3.6 |
| Liquefied gas | 14.0 | 14.8 |
| Gasoline | 39.2 | 38.4 |
| Diesel oil | 28.3 | 27.2 |
| Heavy oil | 6.8 | 6.6 |
| Coke | 8.7 | 9.4 |
| Regeneration unit | ||
| Burning tank internal diameter, cm | 20 | 40 |
| Dense bed internal diameter, cm | 50 | 200 |
| Consumption wind index, Nm 3/kg | 3 | 14 |
| Carbon content on regenerated catalyst, heavy % | 0.02 | 0.08 |
| Regenerated flue gas forms, % | ||
| N 2 | 0 | 79.4 |
| CO 2 | 57.28 | 15.44 |
| CO | 0 | 1.09 |
| O 2 | 42.72 | 4.07 |
Claims (12)
1. one kind is reduced CO2 emission and improves optionally catalyst recovery process, it is characterized in that the method adopts the regenerating unit pattern of burning tank, dilute phase pipe series connection dense bed, burning tank is fast bed operation, and dense bed is bubbling bed operation, and the method comprises:
(1) the band Pd/carbon catalyst from catalytic cracking unit stripping section first adopts pure oxygen gas to regenerate in burning tank, and coke combustion reaction occurs, and the ratio of burning in burning tank is 40-50%;
(2) from burning tank, catalyst out and flue gas enter dense-phase bed through dilute phase pipe, pure oxygen gas is supplemented further bottom dense-phase bed, make that the catalyst of incomplete regen-eration burns further in dense-phase bed, holomorphosis, the ratio of burning of dense-phase bed is 50-60%;
(3) dense-phase bed arranges heat collector and carries out heat-obtaining to catalyst, is no more than 750 DEG C with the temperature controlling dense-phase bed;
(4) from replenishment cycles flue gas bottom burning tank, keep being not less than 30% from the oxygen concentration regenerator cyclone separation system flue gas out;
(5) flue gas enters smoke energy recovering system after cyclone separator is separated, and enters carbon dioxide separating system subsequently, traps after separating carbon dioxide;
(6) regenerator sloped tube arranges catalyst activation system, and this system comprises catalyst cooler and activator, enters reactor cycles again use from regenerator regenerated catalyst out after catalyst activation system.
2., according to the method for claim 1, it is characterized in that the operating condition of described burning tank is: temperature 550-720 DEG C, catalyst mean residence time is 20.0-90.0 second, and gas superficial linear velocity is 1.0-3.0m/s.
3., according to the method for claim 2, it is characterized in that the operating condition of described burning tank is: catalyst mean residence time is 30.0-80.0 second, and gas superficial linear velocity is 1.2-2.0m/s.
4., according to the method for claim 1, it is characterized in that the operating condition of described dense-phase bed is: temperature 600 ~ 750 DEG C, catalyst mean residence time is 1.0-4.0 minute, and gas superficial linear velocity is 0.4-0.8m/s.
5., according to the method for claim 4, it is characterized in that the operating condition of described dense-phase bed is: catalyst mean residence time is 1.0-3.0 minute, and gas superficial linear velocity is 0.4-0.6m/s.
6. according to the method for claim 1, it is characterized in that step (3) described heat collector be interior heat collector or/and external warmer, heat collector is one or more.
7., according to the method for claim 1, it is characterized in that the temperature of step (3) control dense-phase bed is no more than 720 DEG C.
8., according to the method for claim 1, it is characterized in that the oxygen concentration in step (4) described flue gas is not less than 40%.
9., according to the method for claim 1, it is characterized in that catalyst is close in described catalyst cooler and operate mutually, density is 300-700kg/m
3.
10., according to the method for claim 1, it is characterized in that catalyst is close in described activator and operate mutually, density is 300-500kg/m
3, the catalyst time of staying is wherein 2-8 minute; Fluidizing agent presses through hot water and steam in being, its pressure is 3.0-3.5MPa, and temperature is 400-450 DEG C.
11., according to the method for claim 10, is characterized in that the time of staying of catalyst in described activator is 3-6 minute.
12. 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 and is: the heavy % of the heavy %-70 of the heavy % of the heavy %-50 of zeolite 1, the heavy % of the heavy %-99 of inorganic oxide 5, clay 0.
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| CN105521834B (en) * | 2014-09-30 | 2018-03-20 | 中国石油化工股份有限公司 | A kind of catalytic cracking catalyst renovation process and equipment |
| CN107262162B (en) * | 2016-04-06 | 2020-12-04 | 中国石油化工股份有限公司 | Regeneration method of coking catalyst |
| CN106890681A (en) * | 2017-04-20 | 2017-06-27 | 上海蓝科石化环保科技股份有限公司 | A kind of catalytic cracked regenerated system and method |
| CN113663741B (en) * | 2021-08-13 | 2023-10-27 | 中国石油化工股份有限公司 | Regeneration method of coking catalyst |
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| US4542114A (en) * | 1982-08-03 | 1985-09-17 | Air Products And Chemicals, Inc. | Process for the recovery and recycle of effluent gas from the regeneration of particulate matter with oxygen and carbon dioxide |
| CN1131584A (en) * | 1994-09-30 | 1996-09-25 | 波克股份有限公司 | Process for decoking catalysts |
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