CN103055961A - Catalyst regeneration method with characteristic of emission reduction - Google Patents
Catalyst regeneration method with characteristic of emission reduction Download PDFInfo
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- CN103055961A CN103055961A CN2011103179236A CN201110317923A CN103055961A CN 103055961 A CN103055961 A CN 103055961A CN 2011103179236 A CN2011103179236 A CN 2011103179236A CN 201110317923 A CN201110317923 A CN 201110317923A CN 103055961 A CN103055961 A CN 103055961A
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Abstract
The invention relates to a catalyst regeneration method with characteristic of emission reduction, which is characterized in that a catalyst to be generated is contacted with oxygen-rich gas and carbon dioxide gas in a dense-phase fluidized bed reactivator, a coke combustion reaction is generated under the condition that the temperature is 550-750 DEG C and the average stay time of the catalyst is 0.5-10.0 minutes, the regenerated catalyst is introduced in a reactor, the flue gas is divided into two parts through a cyclone separator, one part is circulated to an air inlet system of the reactivator and is mixed with oxygen-rich gas, and the other part is introduced in a flue gas energy recovery system for recovering carbon dioxide without discharge. The method can reach zero discharge of carbon, oxygen with 40% volume fraction can fully combust the coke to totally generate CO2, N2 is not contained in flue gas, CO2 is recovered for convenient recycle, and the catalyst regeneration method has good economic benefit and social benefit.
Description
Technical field
The present invention relates to contain in the catalytic cracking process renovation process that Pd/carbon catalyst burns.
Background technology
In October, 2009, country has announced the action target of control greenhouse gas emission: namely arrive the year two thousand twenty nationwide units GDP CO
2Discharging descended 40% to 45% than 2005, and clearly proposed per GDP carbon dioxide emission reduction 17% during " 12 ", and country might impose " carbon tax " in good time during " 12 " simultaneously.Therefore in petroleum refining and the chemical process effectively the minimizing carbon emission seem and be even more important, capture, seal up for safekeeping and manage CO
2To become refinery's vital task in future.Carbon emission in the processing of heavy oil process mainly is the carbon emission of catalytic cracking burning, hydrogen production process and the energy consumption of technical process.Catalytic cracking unit is the core process units of refinery, becomes CO owing to catalyst burns
2One of main source of discharging.
It is seasonable that mink cell focus carries out Catalytic Cracking Unit of Measure, except generating light Fuel, also generates considerable coke, is deposited on its activity and selectivity is reduced.Catalyst regeneration is divided into holomorphosis and incomplete regen-eration, and holomorphosis is under the condition of oxygen surplus, and the coke on the catalyst all fully burns and generates CO
2Incomplete regen-eration refers to that the coke on the catalyst is imperfect combustion, contains a certain amount of CO in the flue gas after the burning.
CN1600431A discloses a kind of incomplete regen-eration smoke combustion technology, employing replenishes the way of air in the incomplete regen-eration flue gas between catalyst regenerator and flue gas turbine inlet, CO in the incomplete regen-eration flue gas is burnt away, thereby make flue-gas temperature be increased to 660～760 ℃, it is final so that the flue gas turbine inlet temperature reaches 640～700 ℃, improve cigarette machine organic efficiency, thereby reduce plant energy consumption with recovered flue gas pressure energy to greatest extent.Adopt the present invention, replenish air capacity 20～300Nm according to the concentration of unit scale and CO and/or entraining hydrocarbon
3/ min, 20～80 ℃ of energy Effective Raise flue-gas temperatures improve the cigarette engine efficiency.For the single hop incomplete regen-eration, in flue, replenish air and also can make flue gas carry hydro carbons secretly fully to burn, eliminate it to the impact of cigarette machine, have simple in structure, control flexibly, the advantage of stable operation.
CN1052688A discloses a kind of two-stage oxidizing regenerative method of fluid catalyst, reclaimable catalyst at first contacts with oxygen-containing gas in the first fluidized bed and burns reaction, wherein the gas superficial linear speed is 0.8～2.5m/s, the catalyst time of staying is 0.6～1.0 minute, and regeneration temperature is 650～750 ℃; The catalyst of partial regeneration and oxygen gas also flow to together and pass distributor in the first fluidized bed, enter the second fluid bed, contact with oxygen-containing gas again and continue to burn reaction, the gas superficial linear velocity of the second fluid bed is 1.2～3.0m/s, the catalyst mean residence time is 1.0～2.2 minutes, regeneration temperature is 700～800 ℃, obtains regenerated catalyst and flue gas; Regenerated catalyst is with after flue gas separates, and a part of regenerated catalyst enters reactor, and another part turns back to the first fluidized bed to improve bed temperature.The method adopts high gas line speed operation, and reproduction speed is fast, has simplified simultaneously regenerative system structure and flow process.
Conventional catalyst coke burning regeneration method is to pass into air or oxygen-containing gas is regenerated in fluid bed.Air is mainly by O
2And N
2Form, so contain a large amount of N in the regeneration gas that produces behind the catalyst coke burning regeneration
2, CO
2With a small amount of O
2And CO.Because the flue gas separating difficulty is large, cost is high, therefore under normal condition, flue gas directly discharges after entering energy-recuperation system, thereby causes greenhouse effects.
The average coke productive rate of China's catalytic cracking unit output is greater than the required coke yield of device autothermal equilibrium, therefore improve the efficient of catalytic cracking front end, middle-end and terminal each process, adopt combined technique for processing heavy oil to adjust C, the H distribution in product, to reduce coke yield, be significant.But so far, accomplish in the catalytic cracking process that decrease even zero carbon emission are still the problem of needing solution badly.
Summary of the invention
The objective of the invention is to provide on the basis of existing technology a kind of catalyst recovery process of reduction of discharging, to accomplish effectively to reduce carbon emission even zero carbon emission from the source.
The catalyst recovery process of reduction of discharging provided by the invention comprises: reclaimable catalyst is in the dense-phase fluidized bed regenerator, contact with carbon dioxide with oxygen rich gas, be that 0.5～10.0 minute condition issues the combustion reaction of green coke charcoal at 550～750 ℃ of temperature, catalyst mean residence time, catalyst after the regeneration enters reactor, flue gas is divided into two parts behind cyclone separator, wherein a part is circulated to the regenerator gas handling system and mixes with oxygen rich gas, and another part enters smoke energy recovering system and reclaims carbon dioxide and do not discharge.
Described oxygen rich gas is selected from pure oxygen (obtaining from the sky approach that grades), nonnitrogenous gas; Described carbon dioxide is the flue gas recirculation thing, controls simultaneously in the regenerator air inlet oxygen total volume fraction and is not more than 40% and preferably is not more than 30%; Described flue gas is the carbon dioxide that coke fully burns and produces.
Described temperature is preferably 650～700 ℃; Described catalyst mean residence time is preferably 0.5～10.0 minute, more preferably 1.0～6.0 minutes; The gas superficial linear velocity of dense-phase fluidized bed regenerator is 0.2～2.0m/s, is preferably 0.5～1.0m/s.
When heat in the regenerator was superfluous, or/and the interior heat collector heat-obtaining namely can be delivered to external warmer 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 respectively total catalyst weight and is: 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 active component, be selected from mesopore zeolite and/or optional large pore zeolite, mesopore zeolite accounts for the heavy % in 10 heavy % of zeolite gross weight～100, the heavy % in preferred 20 heavy %～80, large pore zeolite accounts for the heavy % in 0 heavy % of zeolite gross weight～90, the heavy % in preferred 20 heavy %～80.Mesopore zeolite is selected from one or more mixtures and/or the ZRP zeolite in the ZSM series zeolite, also can carry out modification with transition metals such as the nonmetalloids such as phosphorus and/or iron, cobalt, nickel to above-mentioned mesopore zeolite.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 consist of.
Inorganic oxide is selected from silica and/or alundum (Al2O3) or both mixtures as catalyst carrier.
Clay is selected from one or more in kaolin, imvite, diatomite, saponite, rectorite, sepiolite, hydrotalcite and the bentonite as bonding agent.
Compare with existing renovation process, major advantage of the present invention is following two aspects:
1, not only activity and selectivity is higher for regenerated catalyst, most critical be that the method can reach zero carbon emission all generate CO because the oxygen of 40% volume fraction can make coke fully burn
2, and do not contain N in the flue gas
2, reclaim CO
2Recycling is convenient, and good economic benefit and social benefit are arranged.
2, this new catalyst regeneration technology, not only plant modification and the investment seldom, and the device operating flexibility also more flexible.
Description of drawings
Accompanying drawing is the basic procedure schematic diagram with the catalyst recovery process of reduction of discharging provided by the invention.
The specific embodiment
Further specify 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 be reduction of discharging provided by the invention catalyst recovery process the basic procedure schematic diagram.
As shown in drawings, reclaimable catalyst enters dense-phase fluidized bed regenerator 2 through inclined tube 1 to be generated, oxygen rich gas and carbon dioxide mixture are entered the bottom of dense-phase fluidized bed regenerator 2 by distribution grid 4 through pipeline 3, contact the combustion reaction of concurrent green coke charcoal with reclaimable catalyst, flue gas is through regenerator dilute phase section 5, cyclone separator 6 and flue gas pipeline 7, a part enters smoke energy recovering system 8, then enter carbon dioxide recovery system, in accordance 9 recyclings, a part is circulated to the regenerator gas handling system and pipeline 3 converges through pipeline 10, wherein control the carbon dioxide internal circulating load by valve until stable, oxygen purity is 30% in the air inlet of control regenerator; Regenerated catalyst after the regeneration enters riser reactor 14 bottoms through regenerator sloped tube 11, it is up that the pre-lift medium enters riser reactor bottom lifting regenerated catalyst through pipeline 12, feedstock oil enters riser reactor through pipeline 13 and contacts with regenerated catalyst and carry out catalytic cracking reaction, and reaction oil gas enters piece-rate system 19 through settler 16, cyclone separator 17 and oil-gas pipeline 18 successively and obtains the purpose product.Reclaimable catalyst enters inclined tube 1 to be generated and turns back to dense-phase fluidized bed regenerator 2 and carry out next round regeneration behind settler 16 and stripping section 15 strippings.
The following examples will be further described 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 at kitty cracker, as shown in drawings.According to renovation process proposed by the invention catalyst is regenerated, catalyst property is listed in table 2, pass into oxygen rich gas and carbon dioxide, the oxygen total volume fraction is 25% in the regenerator air inlet, regeneration temperature is 650 ℃, the catalyst mean residence time is 2 minutes, the gas superficial linear velocity is 1.0m/s, catalyst after the regeneration enters reactor, the feedstock oil listed with table 1 contacts, carry out catalytic cracking reaction, regeneration condition, reaction condition, regenerated catalyst carbon content and flue gas composition are all listed in table 3.
Comparative Examples
Comparative Examples also is to carry out at identical kitty cracker, pair reclaimable catalyst identical with embodiment of renovation process routinely regenerated, the regenerator air inlet only is air, the gas superficial linear velocity is 0.6m/s, and the catalyst mean residence time is 3 minutes, and regeneration temperature is 700 ℃, catalyst after the regeneration enters reactor, the feedstock oil listed with table 1 contacts, and carries out catalytic cracking reaction, and regeneration condition, reaction condition, regenerated catalyst carbon content and flue gas composition are all listed in table 3.
As can be seen from Table 3, compare with Comparative Examples, adopt renovation process proposed by the invention, carbon content reduces morely on the regenerative agent, the most important thing is in the flue gas that this catalyst recovery process produces without CO and N
2, do not efflux carbon dioxide.
Table 1
| The feedstock oil title | Decompression residuum |
| Density (20 ℃), kg/m 3 | 920.9 |
| Kinematic viscosity (100 ℃), millimeter 2/ second | 114.4 |
| Carbon residue, heavy % | 8.2 |
| Condensation point, ℃ | 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, ℃ | |
| HK (initial boiling point) | 415 |
| 10％ | 545 |
| 30％ | / |
| 50％ | / |
| 70％ | / |
| KK (end point of distillation) | / |
Table 2
| The catalyst goods number | 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 is 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 Examples | |
| Regeneration unit | ||
| The gas superficial linear velocity, m/s | 1.0 | 0.6 |
| The catalyst mean residence time, minute | 2.0 | 3.0 |
| Regeneration temperature, ℃ | 650 | 700 |
| Carbon content on the regenerated catalyst, heavy % | 0.04 | 0.08 |
| The cracking hydrocarbon reaction member | ||
| Outlet temperature of riser, ℃ | 500 | 500 |
| The catalyst/ |
6 | 6 |
| Reaction time, second | 3 | 3 |
| Steam/raw material weight ratio | 0.05 | 0.05 |
| Regenerated flue gas forms, % | ||
| N 2 | 0 | 79.5 |
| CO 2 | 99.08 | 15.37 |
| CO | 0 | 4.36 |
| O 2 | 0.92 | 0.77 |
Claims (7)
1. the catalyst recovery process of a reduction of discharging, it is characterized in that reclaimable catalyst is in the dense-phase fluidized bed regenerator, contact with carbon dioxide with oxygen rich gas, be that 0.5～10.0 minute condition issues the combustion reaction of green coke charcoal at 550～750 ℃ of temperature, catalyst mean residence time, catalyst after the regeneration enters reactor, flue gas is divided into two parts behind cyclone separator, wherein a part is circulated to the regenerator gas handling system and mixes with oxygen rich gas, and another part enters smoke energy recovering system and reclaims carbon dioxide and do not discharge.
2. according to the method for claim 1, it is characterized in that described oxygen rich gas is selected from pure oxygen, described carbon dioxide is the flue gas recirculation thing, controls simultaneously that the oxygen total volume fraction is not more than 40% in the regenerator air inlet; Described flue gas is the carbon dioxide that coke fully burns and produces.
3. according to the method for claim 2, it is characterized in that controlling that the oxygen total volume fraction is not more than 30% in the regenerator air inlet.
4. according to the method for claim 1, it is characterized in that described temperature is 600～700 ℃, described catalyst mean residence time is 1.0～6.0 minutes, and the gas superficial linear velocity of dense-phase fluidized bed regenerator is 0.2～2.0m/s.
5. according to the method for claim 4, it is characterized in that described catalyst mean residence time is 1.2～5.0 minutes, the gas superficial linear velocity of dense-phase fluidized bed regenerator is 0.5～1.0m/s.
6. according to the method for claim 1, it is characterized in that when heat in the regenerator is superfluous, or/and the interior heat collector heat-obtaining namely can be delivered to external warmer with the internal regenerator divided catalyst and cool off, cooled catalyst turns back to regenerator to described internal regenerator divided catalyst again through external warmer.
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 respectively total catalyst weight and is: the heavy % in zeolite 1 heavy %～50, the heavy % in the heavy % in inorganic oxide 5 heavy %～99, clay 0 heavy %～70.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104549565A (en) * | 2013-10-17 | 2015-04-29 | 中国石油化工股份有限公司 | Regenerator for catalytic conversion and regeneration method |
| CN104549567B (en) * | 2013-10-17 | 2017-07-25 | 中国石油化工股份有限公司 | Reduce the catalyst recovery process of nitride in flue gas |
| CN110876958A (en) * | 2018-09-06 | 2020-03-13 | 中国科学院大连化学物理研究所 | Method for regenerating carbon deposition catalyst and co-producing carbon monoxide |
| CN115055212A (en) * | 2022-06-10 | 2022-09-16 | 中国石油大学(北京) | Regeneration method for preparing olefin from methanol with zero emission of carbon dioxide |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104549565A (en) * | 2013-10-17 | 2015-04-29 | 中国石油化工股份有限公司 | Regenerator for catalytic conversion and regeneration method |
| CN104549567B (en) * | 2013-10-17 | 2017-07-25 | 中国石油化工股份有限公司 | Reduce the catalyst recovery process of nitride in flue gas |
| CN104549565B (en) * | 2013-10-17 | 2017-09-29 | 中国石油化工股份有限公司 | A kind of regenerator and renovation process for catalyzed conversion |
| CN110876958A (en) * | 2018-09-06 | 2020-03-13 | 中国科学院大连化学物理研究所 | Method for regenerating carbon deposition catalyst and co-producing carbon monoxide |
| CN115055212A (en) * | 2022-06-10 | 2022-09-16 | 中国石油大学(北京) | Regeneration method for preparing olefin from methanol with zero emission of carbon dioxide |
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