CN1813042A - Reduction of nox in low co partial-burn operation using full burn regenerator additives - Google Patents
Reduction of nox in low co partial-burn operation using full burn regenerator additives Download PDFInfo
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- CN1813042A CN1813042A CNA2004800178704A CN200480017870A CN1813042A CN 1813042 A CN1813042 A CN 1813042A CN A2004800178704 A CNA2004800178704 A CN A2004800178704A CN 200480017870 A CN200480017870 A CN 200480017870A CN 1813042 A CN1813042 A CN 1813042A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
- C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
- C10G11/182—Regeneration
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Abstract
The present invention relates to the reduction of the concentrations of nitrogen oxides (NOx) from a fluid catalytic cracking (FCC) regenerator by operating the regenerator in partial CO bum mode with a NOx reducing catalyst system.
Description
Technical field
The present invention relates to reduce NO by using
xCatalyst system reduce the nitrogen oxide (NO that comes from fluid catalystic cracking (FCC) revivifier with incomplete CO combustion mode operation revivifier
x) concentration.
Background technology
Have been found that oxynitride (mainly is NO and NO
2) form down at high temperature (for example catalyzer that uses in hydrocarbon cracking process regenerated temperature in the presence of the CO burning promotor).When hydrocarbon (for example petroleum) cracking, sedimentation of coke is on granules of catalyst.Be formed at coke on the particle and reduce the activity of this granules of catalyst gradually.The coke that last activity of such catalysts drops to wherein must be from the stage of burn off on the particle.This step is commonly called regeneration, can be by described granules of catalyst being contacted with the regeneration gas (as air) of heat and carrying out in batches or continuously.Coke is burnt, thereby has recovered activity of such catalysts, and has heated catalyzer simultaneously.Can be to handling, to remove degranulation and CO is converted into CO by the stack gas that the burn off coke forms from the catalyzer in revivifier
2, stack gas generally is discharged into atmosphere then.
Present most of FCC equipment uses has high reactivity and zeolite containing catalyst optionally.These catalyzer are considered to performance the best use of when the amount of coke on the catalyzer is low after regeneration.Usually use two types FCC revivifier, i.e. highly efficient regeneration device and ebullated bed revivifier.The highly efficient regeneration device mixes the regenerated catalyst of recirculation with spent catalyst, in fast fluidized bed coke burner from the spent catalyst the most of coke of burn off, then catalyzer and stack gas are upwards entered dilute phase transmission riser tube, in this riser tube, carry out the burning of extra coke, and be CO most of CO afterfires
2These revivifiers are designed for complete CO burning, and generation does not relatively have the regenerated catalyst of coke and has stack gas and the minor N O of CO very on a small quantity usually
xThe ebullated bed revivifier keeps catalyzer with fluidizing fluid-bed form, and spent catalyst adds wherein, and therefrom removes regenerated catalyst.These revivifiers usually need be than the more catalyst inventory of highly efficient regeneration device, because the contact of gas/catalyzer does not have in the highly efficient regeneration device abundant in the boiling fluidized bed.Many ebullated bed revivifiers move with complete CO combustion mode, i.e. CO wherein
2/ CO mol ratio is at least 10.Refinery attempts in catalyst regenerator CO perfect combustion saving heat, and atmospheric pollution is dropped to minimum level.Difficulty be all coke of perfect combustion and do not having NO in catalyst regenerator
xFollow under the condition of revivifier flue gas emissions and transform CO.The emission standard of the government specifications regulation of increasingly stringent has limited and can be present in the NO that is discharged in the atmospheric flue gas stream
xAmount.For to environment protection, seeking reduction NO
xMany effort have been paid on the discharge method.
Multiple reduction NO has been proposed
xThe method of quantity discharged, comprising using catalyzer or the additive compatible with the FCC reactor, these catalyzer or additive have suppressed NO
xFormation, or its reduction of catalysis in the revivifier under being in complete CO combustion mode.But the inventor is surprised to find that utilization with the revivifier of incomplete combustion mode operation, is usually used in the minimizing NO of complete CO burning revivifier under low CO concentration
xCatalyst system the minimizing NO of improvement can be provided
xEffect.
Brief summary of the invention
Embodiment of the present invention provide a kind of and have reduced NO
xUnder the situation of discharging be the method for product gently with nitrogenous heavy hydrocarbon kind of raw materials catalytic cracking, this method comprises:
A) in the fluid catalystic cracking under running on catalytic cracking condition (FCC) reaction zone described raw material is contacted with catalyst system and with this raw material cracking, to produce crackate and to deposit the mixture of the inefficacy cracking catalyst of nitrogen compound and coke on it, wherein said catalyst system comprises (i) at least a solid acid component, (ii) at least a one or more elements that come from the periodic table of elements the 1st family and the 3rd family and one or more of comprising come from least a in the metallic component of element of periodic table of elements 4-15 family and oxygen and the sulphur, wherein said the 1st family and the 3rd family of coming from, in the element of 4-15 family and oxygen and the sulphur at least a within each family or between Chemical bond and (iii) at least a carrier, filler or binding agent;
B) described crackate is separated with described inefficacy cracking catalyst,, described vapor phase flow is added fractionation zone, described spent catalyst is added stripping zone to produce the crackate vapor phase flow and to deposit the spent catalyst of nitrogen compound and coke on it;
C) at the volatile compound of described stripping zone stripping spent catalyst, to produce the spent catalyst that deposits coke and nitrogen compound on it through steam stripped;
D) make in the breeding blanket that runs on incomplete CO combustion conditions with oxygen-containing gas described through catalyst regeneration steam stripped, that lost efficacy, described breeding blanket can effectively produce regenerated catalyst and comprise 0.5-4 volume %CO and greater than the flue gas stream of 90 volume ppm NO, wherein NO in described flue gas stream
xContent has reduced; With
E) described regenerated catalyst is introduced reaction zone from the breeding blanket.
Another embodiment of the present invention provides a kind of and has reduced NO
xUnder the situation of discharging be the method for product gently with nitrogenous heavy hydrocarbon kind of raw materials catalytic cracking, this method comprises:
A) in the fluid catalystic cracking under running on catalytic cracking condition (FCC) reaction zone described raw material is contacted with catalyst system and with this raw material cracking, to produce crackate and to deposit the mixture of the inefficacy cracking catalyst of nitrogen compound and coke on it, wherein said catalyst system comprises (i) at least a solid acid component, (ii) at least a one or more elements that come from the periodic table of elements the 1st family and the 3rd family and one or more of comprising come from least a in the metallic component of element of periodic table of elements 4-15 family and oxygen and the sulphur, wherein said the 1st family and the 3rd family of coming from, in the element of 4-15 family and oxygen and the sulphur at least a within each family or between Chemical bond and (iii) at least a carrier, filler or binding agent;
B) described crackate is separated with described inefficacy cracking catalyst,, described vapor phase flow is added fractionation zone, described spent catalyst is added stripping zone to produce the crackate vapor phase flow and to deposit the spent catalyst of nitrogen compound and coke on it;
C) at the volatile compound of described stripping zone stripping spent catalyst, to produce the spent catalyst that deposits coke and nitrogen compound on it through steam stripped;
D) make in the breeding blanket that runs on incomplete CO combustion conditions with oxygen-containing gas described through catalyst regeneration steam stripped, that lost efficacy, described breeding blanket can effectively produce regenerated catalyst and comprise 0.5-1 volume %CO and greater than the flue gas stream of 263 volume ppm NO, wherein NO in described flue gas stream
xContent has reduced; With
E) described regenerated catalyst is introduced reaction zone from the breeding blanket.
Detailed Description Of The Invention
When being used for herein, code name NO
xOr nitrogen oxide refers to be present in the various nitrogen oxides in the process flow (for example waste gas of FCC equipment revivifier).Therefore, these terms refer to all various nitrogen oxides, comprise nitrogen protoxide (NO), nitrogen peroxide (NO
2), nitrous oxide (N
2And their mixture O) etc.In the nitrogen oxide in being present in regenerator off-gas, NO generally constitutes existing all NO
xMajor part.NO generally accounts for 90% of regenerator off-gas.Therefore, the inventive method is particularly related to minimizing and the control of NO.
The invention provides a kind of NO with reduction
xDischarging, be used for the FCC method of nitrogenous heavy hydrocarbon raw material cracking for light product.In the FCC processing unit of described heavy hydrocarbon raw material feeding comprising at least one reaction zone, stripping zone, catalyst regeneration zones and product fractionation zone.This raw material under 425 ℃-600 ℃, preferred 460 ℃-560 ℃ in reaction zone with reduce NO
xCatalyst system contact.Hydrocarbon cracking, and coke, sulphur and nitrogen compound be deposited on the catalyzer.Crackate is separated with coke or spent catalyst.The catalyzer of coking is gone out volatile matter (using steam stripped usually) at stripping zone by stripping.Stripping preferably carries out under the low severity condition, so that thermo-cracking is dropped to minimum degree.Then stripped catalyzer is sent into the breeding blanket, therein by in the presence of oxygen-containing gas (preferred air or rich oxygen containing air), the burning of the coke on the catalyzer being regenerated.This regeneration step has been recovered activity of such catalysts and simultaneously catalyzer has been heated to 1202 °F (650 ℃)-1382 °F (750 ℃).Environment in the described revivifier has reduced the amount (it is converted into the reductive nitrogen compound, as ammonia) of coking nitrogen, and has increased the amount of the oxynitride that is produced by coking nitrogen in this breeding blanket.The total amount of oxygen in the restriction breeding blanket is so that this revivifier is with the incomplete combustion mode operation.
Any traditional FCC raw material all can be used for the present invention.Such raw material generally comprises ebullient heavy hydrocarbon raw material, for example gasoline in 430-1050 (220 ℃-565 ℃) scopes; Be included in the heavy-hydrocarbon oil that is higher than 1050 (565 ℃) ebullient materials; Heavy and reductive petroleum crude oil; Oil air distillation substrate; Oil vacuum distilling substrate; Tar-bitumen, pitch, pitch earth, other heavy hydrocarbon residue; Tar sand; Shale oil; Handle the deutero-liquid product by gelatin liquefaction; With their mixture.These raw materials generally comprise the not nitrogen compound that is converted into oxynitride in revivifier of desired amount.The FCC raw material also may comprise recycle hydrocarbons, for example lightweight or heavy recycle stock.Preferred raw material is to be higher than the scope ebullient vacuum gas oil of 650 (343 ℃) in this method.
The minimizing NO of Shi Yonging in the methods of the invention
xCatalyst system comprise (i) at least a solid acid component, (ii) at least a one or more elements that come from the periodic table of elements the 1st family and the 3rd family and one or more of comprising come from least a in the metallic component of element of periodic table of elements 4-15 family and oxygen and the sulphur, in the wherein said element that comes from the 1st family and the 3rd family, 4-15 family and oxygen and the sulphur at least a within each family or between Chemical bond and (iii) at least a carrier, filler or binding agent.
Described solid acid component is traditional F CC catalyzer preferably, and it comprises the catalyzer that wherein comprises large pore zeolite (as USY or REY).Can comprise natural and synthetic zeolite according to other zeolites that the present invention uses.Described large pore zeolite comprises sarcolite, chabazite, dachiardite, clinoptilolite, faujusite, heulandite, euthalite, levyne, erionite, sodalite, cancrinite, nepheline, lazurite, scolecite, natrolite, offretite, mesolite, mordenite, brusterite and ferrierite.Comprise X zeolite, Y, A, L.ZK-4, ZK-5, B, E, F, H, J, M, Q, T, W, Z in the synthetic zeolite, α, β, ω and USY zeolite.Preferred large pore zeolite is a faujusite, particularly Y, USY and REY zeolite.
Can be used for the mixture that catalyzer of the present invention can also be mesopore zeolite or macropore and mesopore zeolite.Can be used for " Atlas of Zeolite StructureTypes " that the mesopore zeolite of the present invention practice is described in, W.H.Meier and D.H.Olson compile, Butterworth-Heineman, and the third edition, in 1992, the document is by with reference to incorporating this paper into.Mesopore zeolite has the average pore diameter less than 0.7nm usually, is generally 0.5-0.7nm, and comprises, for example MFI, MFS, MEL, MTW, EUO, MTT, HEU, FER and TON structure type zeolite (IUPAC zeolite NK).The non-limiting example of these mesopore zeolites comprises ZSM-5, ZSM-12, ZSM-22, ZSM-23, ZSM-34, ZSM-35, ZSM-38, ZSM-48, ZSM-50, silicalite and silicalite 2.ZSM-5 most preferably, it is described in United States Patent (USP) 3,702, and No. 886 and 3,770, No. 614.ZSM-11 is described in United States Patent (USP) 3,709, No. 979; ZSM-12 is described in United States Patent (USP) 3,832, No. 449; ZSM-21 and ZSM-38 are described in United States Patent (USP) 3,948, No. 758; ZSM-23 is described in United States Patent (USP) 4,076, No. 842; ZSM-35 is described in United States Patent (USP) 4,016, No. 245.Above-mentioned all patents are incorporated this paper into by reference.Other suitable mesopore zeolite comprises silicon aluminium phosphate (SAPO), for example SAPO-11, SAPO-34, SAPO-41 and SAPO-42, and they are at United States Patent (USP) 4,440, describe in No. 871; Silicic acid chromium; The silicic acid gallium; Ferric metasilicate; Aluminum phosphate (ALPO), for example at United States Patent (USP) 4,310, the ALPO-11 that describes in 440; Manosil AS titanium (TASO), for example TASO-45 that in European patent EP-A 229,295, describes; Borosilicate is described in United States Patent (USP) 4,254,297; Aluminium titanium phosphate (TAPO) for example is described in United States Patent (USP) 4,500,651 TAPO-11; With manosil AS iron.In one embodiment of the invention, the Si/Al of described zeolite ratio is greater than 40.
Mesopore zeolite can comprise " crystalline mixture " (" crystalline admixtures "), and it is considered in the zeolite synthesis process result of the mistake that occurs at crystal or crystal region.The example of the crystalline mixture of ZSM-5 and ZSM-1 is disclosed in United States Patent (USP) 4,229, and No. 424, it incorporates this paper into by reference.Described crystalline mixture itself is a mesopore zeolite, and can not obscure mutually with zeolite physical mixture or hydro-thermal reaction mixture that the different crystal physics of the crystallite of different zeolites wherein is present in identical crystalline complex.
Macropore of the present invention and medium-pore catalyst are present in the inorganic oxide matrix component binding agent, and this binding agent bonds together catalyst component, so that this catalyst product is enough firm, can bear the collision between particle and the reactor wall.Described inorganic oxide matrix can be by inorganic oxide sol or preparing gel, and they are dried with catalyst component " gummed " together.Preferably, described inorganic oxide matrix is not a catalytic activity, and will be made up of the oxide compound of silicon and aluminium.Further preferably independent aluminum oxide is sneaked in the inorganic oxide matrix.Operable kind is aluminum oxyhydroxide-gama-alumina, boehmite, diaspore and transitional alumina, as Alpha-alumina, beta-alumina, gama-alumina, δ-aluminum oxide, ε-aluminum oxide, κ-aluminum oxide and ρ-aluminum oxide.Preferably, aluminum oxide thing class is three aluminium hydroxides, as gibbsite, bayerite, nordstrandite or doyelite.Described substrate material can also comprise phosphorus or aluminum phosphate.Macroporous catalyst and medium-pore catalyst are present in the above-mentioned inorganic oxide matrix with identical or different granules of catalyst, and this is also in protection domain of the present invention.
The sour material of load can be crystallization or amorphous material, they itself may be or may not be tart, go up acid sites through modification to increase the surface.Nonrestrictive example is fixed on silicon-dioxide, quartz, sand, aluminum oxide or diatomaceous H
2SO
4, H
3PO
4, H
3BO
3, CH
2(COOH)
2, and be fixed on silicon-dioxide, quartz, sand, aluminum oxide or diatomaceous heteropolyacid.The non-limiting example of the sour material of crystallization load has through acid-treated molecular sieve, Sulfated zirconium white, tungsten acidifying zirconium white, the zirconium white of phosphorylation and the nobia of phosphorylation.
Described solid acid component exists with the metallic components of the element of at least a element that comprises one or more periodic table of elements the 1st families and the 3rd family and one or more periodic table of elements 4-15 family.All the other components of catalyst system of the present invention can be at least a in sulphur and the oxygen.Preferred oxygen.The element that comes from the 1st family and the 3rd family can be any metal or the metallic combination that is selected from lithium, sodium, potassium, rubidium, caesium, francium, scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium.Preferably, the element that comes from the 1st family and the 3rd family can be any metal or the metallic combination that is selected from lanthanum and cerium.The element that comes from 4-15 family can be any element or the element mixture that comes from periodic table of elements 4-15 family.Preferably, the element that comes from 4-15 family is at least a in the following element: titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, boron, aluminium, phosphorus, gallium, germanium, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, silver, indium, tin, antimony, hafnium, tungsten, rhenium, iridium, platinum, gold, lead and bismuth.More preferably, the element that comes from 4-15 family is at least a in copper, palladium and the silver.
Catalyst system of the present invention can be by preparing with metallic component physical mixed or chemical reaction, and randomly combine with binding agent to form granules of catalyst or to relax catalyst activity as filler.The weight ratio of solid acid component and metallic components gross weight can be 1000: 1-1: 1000.This ratio is preferably 500: 1-1: 500.This ratio most preferably is 100: 1-1: 100.The weight ratio of described metallic components and matrix components can be 100: 1-1: 100.
The metallic components of described catalyst system or minimizing NO
xComponent can be used as the independent interpolation particle of FCC granules of catalyst or whole part is used.Reduce NO
xComponent can comprise a spot of other materials, it does not preferably influence unfriendly in significant mode and reduces NO
xFunction.But more preferably reduce NO
xComponent mainly by (ii) above-mentioned-(iii) form.When reducing NO
xComponent when using with independent interpolation particle, it is with effective minimizing NO
xAmount add in the total amount of circulation FCC granules of catalyst.Described significant quantity is following amount: it is effectively with the NO in the revivifier stack gas
xContent when content is reduced to and is lower than described additive and does not exist.Reduce NO
xComponent can combine the particle that is suitable for the FCC method with formation with at least a carrier, filler or binding agent.If described minimizing NO
xComponent particles be the part of FCC granules of catalyst integral body, it is preferably the 0.001-10 weight % of circulation granular solids total amount, more preferably 0.01-5 weight %, 0.05-1 weight % most preferably.
Though the present invention reduces NO
xCatalyst system to reducing the NO of FCC revivifier stack gas
xContent has a positive effect, but it has negative impact to the hydrocarbon cracking reaction of carrying out in the FCC process.In addition, described minimizing NO
xCatalyst system with can be that the CO oxidation promoters of a circulation granular solids total amount part is compatible.In addition, the present invention reduces NO
xCatalyst system can with reduce SO
xAdditive use together.These SO
xAdditive also can reduce NO
xDescribed SO
xThe preferably various forms of aluminum oxide of additive, rare earth oxide, alkaline-earth oxide and spinel.Described SO
xAdditive is more preferably magnesium-aluminate.SO
xAdditive can obtain from a plurality of catalyzer supply merchants, for example Grace-Davison ' s DESOX or SUPERDESOX, perhaps Intercat ' s SOXGETTER or Super-SOXGETTER.
In the revivifier under running on typical incomplete combustion mode condition, CO concentration is generally greater than 4.0 volume %, and exists very small amount of NO, NO generally to be lower than 50 volume ppm.Under this high CO concentration, the major part of leaving the nitrogenous substances of revivifier is HCN and NH
3Form.For reducing NO
xCatalyst system, this is not a best applications.And CO concentration of the present invention run on preferred 0.5-4.0 volume %CO, more preferably 0.75-3.0 volume %CO, most preferably under the incomplete combustion pattern of 1.00-2.0 volume %CO.In addition, NO concentration is preferably greater than 90 volume ppm, more preferably greater than 150 volume ppm, and most preferably greater than 200 volume ppm.Along with CO concentration reduces, produced more NO, cause more NO to be reduced, and therefore reduced NO by CO
xDischarging.Round-robin reduces NO
xThe existence of catalyst system improved the speed of utilizing the CO reductive NO, thereby additionally reduced NO
xDischarging.
Hot regenerated catalyst recycle contacts with the FCC raw material that injects therein to the FCC reaction zone.
The reactor operation generally is traditional full riser cracking FCC, and as United States Patent (USP) 4,421, No. 636 disclosed, and it incorporates this paper into by reference.Typical riser cracking reaction conditions comprises that the catalyst/oil ratio is 0.5: 1-15: 1, preferred 3: 1-8: 1, and catalyzer duration of contact is 0.1-50 second, preferred 0.5-10 second, be 900 °F-1100 °F most preferably 0.75-5 second, and riser tube top temperature, preferred 950 °F-1050 °F.
Preferably utilize conventional art to make raw material and catalyzer, for example add a large amount of atomizing steams, use multi-nozzle, use atomizing nozzle and similar techniques in riser reactor bottom well blend.The Atomax nozzle that can obtain from M.W.Kellogg CO is preferred.The details of the nozzle that is suitable for are disclosed in United States Patent (USP) 5,289, and in 976 and 5,306,418, it is by with reference to incorporating this paper into.Preferred but non-essential be to have riser tube catalyzer acceleration zone in the bottom of riser tube.Same preferred but non-essential be that riser tube feeds the cyclone separation system of sealing rapidly crackate is separated with spent catalyst.Authorize in people's such as Haddad the United States Patent (USP) 4,502,947 and disclose the sealing cyclone system, it is by with reference to incorporating this paper into.Same preferred but non-essentially be this catalyzer of rapid stripping when catalyzer leaves the riser tube that is positioned at the catalyst stripping equipment upstream.Can use the stripper cyclonic separator in the United States Patent (USP) 4,173,527 that is disclosed in Schatz and Heffley, it incorporates this paper into by reference.Preferred but the non-essential thermocatalyst stripper that is to use.Hot stripper is by heating spent catalyst in the catalyzer of the regenerated adding spent catalyst with heat.Hot stripper is disclosed in people's such as Owen the United States Patent (USP) 3,821,103, and it is by with reference to incorporating this paper into.Behind hot stripping, catalyst cooler can be with its cooling before the catalyzer that heats be admitted to revivifier.Preferred hot stripper and catalyst cooler are disclosed in the United States Patent (USP) 4,820,404 of Owen, and it incorporates this paper into by reference.Can adopt traditional FCC steam stripped condition, wherein spent catalyst has with riser tube and exports essentially identical temperature, and adds 0.5-5% stripping gas (preferred steam) with the stripping spent catalyst.The condition itself of described FCC reactor and stripper can be conventional.
Two types FCC revivifier can be used in the inventive method, i.e. highly efficient regeneration device and ebullated bed type revivifier.In the ebullated bed revivifier, most of regeneration gas (being generally air) passes through bed with bubble form.They pass through from bed, but relatively poor with contacting of bed.These equipment use a large amount of catalyzer to operate.The ebullated bed revivifier is not very effective aspect combustion of coke, so needs a large amount of catalyst inventory and the long residence time in the revivifier, to produce the catalyzer of the burning of cleaning.Carbon amount on the regenerated catalyst can be conventional, generally is lower than 0.3 weight % coke, preferably is lower than 0.15 weight % coke, most preferably even lower.Coke not only refers to carbon, but also comprises a spot of hydrogen that links to each other with coke, in addition may be very small amount of remain on the catalyzer not by steam stripped heavy hydrocarbon.Represent that with weight % carbon this is identical for base, but be 5 to being lower than 10%.
Should there be competent CO in the stack gas, so that can utilize the control techniques relevant to control the FCC revivifier reliably with incomplete CO burning.
The inventive method can also be with second highly efficient regeneration device (HER) use that has fast fluidized bed coke burner, dilute phase transport riser tube and collect regenerated catalyst.Must operate these equipment with incomplete CO combustion mode, so that CO conforms to the standard.
Highly efficient regeneration device itself can utilize regeneration air admirably.When being in complete CO combustion mode, they are most with 1 or 2 mole of % or higher O in the described stack gas
2Operate.When being in incomplete CO combustion mode, its majority is with excessive hardly oxygen operation, and oxygen preferably is lower than 1/10th hundredths (1/10th%) generally in the ppm scope.For the highly efficient regeneration device, may must significantly reduce the air capacity that adds and have correct CO/O with generation
2The stack gas of ratio.Reduce or eliminate the CO combustion cocatalyst and may be and produce CO to double the stack gas of oxygen necessary.
Although mainly by regulating the amount control of the regeneration air that adds, other keep the equivalent control scheme of air constant and some other condition of change also can use to most revivifiers.Air speed is constant, and the feed rate that change can change coking yield is a kind of mode of the change revivifier operation that can accept.Air constant, raw material preheating change or revivifier preheating of air variation also is an acceptable.At last, catalyst cooler can be used in the slave unit except that reducing phlegm and internal heat.Be not enough to keep thermally equilibrated coke if equipment produces, combustion oil or other fuel can be in the revivifier internal combustion.
Embodiment 1:
Utilize commercial FCC processing unit test and improve the present invention.In this experiment, the concentration of CO in the stack gas of FCC equipment revivifier exit changes to about 5.5 volume % from being higher than about 0.5 volume %.In above-mentioned CO concentration range, NO concentration is dropped to the minimum value (table 1) of about 31 volume ppm by the maximum value of 266 volume ppm.That generally acknowledges is used to make FCC equipment revivifier NO
xDischarging drops to the reaction mechanism of minimum level and need operate under the situation of NO that has very big concentration and CO.
In partial-burn operation, under very high CO concentration, exist seldom can be used for that (nitrogen thing class mainly is NH with CO reductive NO
3And HCN).And, find higher NO
xDischarging.When CO concentration reduces, produced more NO, cause more NO to be reduced, and therefore reduced NO by CO
xDischarging.Be lower than 1%CO, NO concentration is near constant maximum value, and NO
xDischarging is in Schwellenwert.Referring to table 1 and Fig. 1.
Low-down CO concentration range is similar to can be at low excessive O
2CO and the NO concentration found in the following full CO burn operation.For this full combustion equipment, reduce NO
xCatalyst system confirmed it is effective.In incomplete combustion equipment, CO concentration generally is higher than 4 volume %, and these reduce NO
xCatalyst system relative nullity.The present invention recognizes in very low CO operation, reduces NO
xCatalyst system more effective than general partial-burn operation because key substance (NO and CO) all exists with big concentration.
Table 1
| NO concentration is in maximum value under low CO concentration | |
| CO (volume %) | NO(vppm) |
| 0.50 | 266 |
| 0.75 | 266 |
| 1.00 | 263 |
| 1.25 | 257 |
| 1.50 | 248 |
| 1.75 | 237 |
| 2.00 | 223 |
| 2.25 | 209 |
| 2.50 | 193 |
| 2.75 | 176 |
| 3.00 | 158 |
| 3.25 | 141 |
| 3.50 | 123 |
| 3.75 | 106 |
| 4.00 | 90 |
| 4.25 | 75 |
| 4.50 | 62 |
| 4.75 | 50 |
| 5.00 | 41 |
| 5.25 | 35 |
| 5.50 | 32 |
| 5.75 | 31 |
Claims (13)
1. one kind is being reduced NO
xUnder the situation of discharging be the method for product gently with nitrogenous heavy hydrocarbon kind of raw materials catalytic cracking, this method comprises:
A) make described raw material in the fluid catalystic cracking under running on catalytic cracking condition (FCC) reaction zone and reduce NO
xCatalyst system contact and with this raw material cracking, to produce crackate and to deposit the mixture of the inefficacy cracking catalyst of nitrogen compound and coke on it, wherein said catalyst system comprises (i) at least a solid acid component, (ii) at least a one or more elements that come from the periodic table of elements the 1st family and the 3rd family and one or more of comprising come from least a in the metallic component of element of periodic table of elements 4-15 family and oxygen and the sulphur, wherein said the 1st family and the 3rd family of coming from, in the element of 4-15 family and oxygen and the sulphur at least a within each family or between Chemical bond and (iii) at least a carrier, filler or binding agent;
B) described crackate is separated with described inefficacy cracking catalyst,, described vapor phase flow is added fractionation zone, described spent catalyst is added stripping zone to produce the crackate vapor phase flow and to deposit the spent catalyst of nitrogen compound and coke on it;
C) at the volatile compound of described stripping zone stripping spent catalyst, to produce the spent catalyst that deposits coke and nitrogen compound on it through steam stripped;
D) make in the breeding blanket that runs on incomplete CO combustion conditions with oxygen-containing gas described through catalyst regeneration steam stripped, that lost efficacy, described breeding blanket can effectively produce regenerated catalyst and comprise 0.5-4 volume %CO and greater than the flue gas stream of 90 volume ppm NO, wherein NO in described flue gas stream
xContent has reduced; With
E) described regenerated catalyst is introduced reaction zone from the breeding blanket.
2. the method as claimed in any one of the preceding claims, wherein described solid acid component and described metallic components physical mixed.
3. the method as claimed in any one of the preceding claims, wherein described solid acid component and described metallic components Chemical bond.
4. the method as claimed in any one of the preceding claims, wherein described solid acid component is at least a in one or more crystalline solid acid, one or more load acid and composition thereof.
5. the method as claimed in any one of the preceding claims, wherein oxygen is isolating with described metallic components.
6. one or more elements that the method as claimed in any one of the preceding claims, wherein come from the 1st family and the 3rd family are following at least a in the column element: lithium, sodium, potassium, rubidium, caesium, francium, scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium.
7. one or more elements that the method as claimed in any one of the preceding claims, wherein come from 4-15 family are titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, boron, aluminium, phosphorus, gallium, germanium, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, silver, indium, tin, antimony, hafnium, tungsten, rhenium, iridium, platinum, gold, lead and bismuth.
8. the method as claimed in any one of the preceding claims, wherein the weight ratio of solid acid component and metallic components gross weight is 1000: 1-1: 1000.
9. the method as claimed in any one of the preceding claims, wherein described minimizing NO
xCatalyst system comprise the cracking component that wherein contains at least a following material: have 8 yuan or surpass 8 yuan oxygen ring in the aluminate or phosphate of the aluminosilicate of the silicate of crystalline silicate, crystalline substituted, crystalline aluminosilicate, crystalline substituted, crystalline aluminium phosphoric acid salt, crystalline substituted, zeolite-combination-zeolite, the structure.
10. the method as claimed in any one of the preceding claims, wherein described minimizing NO
xThe cracking component of catalyst system be selected from the group of forming by large pore zeolite, mesopore zeolite and composition thereof.
11. the method as claimed in any one of the preceding claims, wherein described large pore zeolite is a faujusite.
12. the method as claimed in any one of the preceding claims, wherein described mesopore zeolite is selected from ZSM series.
13. the method as claimed in any one of the preceding claims, wherein described solid acid component and metallic components also comprise at least a carrier, filler or binding agent.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US48203703P | 2003-06-24 | 2003-06-24 | |
| US60/482,037 | 2003-06-24 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1813042A true CN1813042A (en) | 2006-08-02 |
| CN100345941C CN100345941C (en) | 2007-10-31 |
Family
ID=34061936
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004800178704A Expired - Fee Related CN100345941C (en) | 2003-06-24 | 2004-06-03 | Reduction of nox in low co partial-burn operation using full burn regenerator additives |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US20040262197A1 (en) |
| EP (1) | EP1654340A1 (en) |
| JP (1) | JP2007523217A (en) |
| CN (1) | CN100345941C (en) |
| AU (1) | AU2004256423A1 (en) |
| CA (1) | CA2527706A1 (en) |
| TW (1) | TW200502514A (en) |
| WO (1) | WO2005005578A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104099129A (en) * | 2013-04-08 | 2014-10-15 | 中石化洛阳工程有限公司 | Short-reaction-time catalytic cracking method |
| CN106170659A (en) * | 2014-01-17 | 2016-11-30 | 三菱日立动力系统美洲股份有限公司 | Operate under the conditions of low-load gas turbine generating set |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050100494A1 (en) | 2003-11-06 | 2005-05-12 | George Yaluris | Ferrierite compositions for reducing NOx emissions during fluid catalytic cracking |
| JP5383184B2 (en) * | 2005-04-27 | 2014-01-08 | ダブリュー・アール・グレイス・アンド・カンパニー−コネチカット | Compositions and methods for reducing NOx emissions during fluid catalytic cracking |
| RU2007144186A (en) * | 2005-04-29 | 2009-06-10 | В.Р.Грейс Энд Ко.-Конн. (Us) | COMPOSITIONS FOR REDUCING THE NUMBER OF NOx INTENDED FOR USE IN FCC PARTIAL COMBUSTION METHODS |
| US7678735B2 (en) * | 2005-11-28 | 2010-03-16 | Engelhard Corporation | FCC additive for partial and full burn NOx control |
| US20100290963A1 (en) * | 2007-04-26 | 2010-11-18 | Johnson Matthey Public Limited Company | Transition metal / zeolite scr catalysts |
| DE102009055942C5 (en) * | 2009-11-26 | 2015-12-17 | Chemisch-Thermische Prozesstechnik Gmbh | Process and apparatus for purifying exhaust gases |
| EP2377613B1 (en) * | 2009-12-18 | 2014-10-15 | JGC Catalysts and Chemicals Ltd. | Metal-supported crystalline silica aluminophosphate catalyst and process for producing the same |
| US20120014866A1 (en) * | 2010-07-15 | 2012-01-19 | Ivor Bull | Copper Containing ZSM-34, OFF And/Or ERI Zeolitic Material For Selective Reduction Of NOx |
| US9221015B2 (en) * | 2010-07-15 | 2015-12-29 | Basf Se | Copper containing ZSM-34, OFF and/or ERI zeolitic material for selective reduction of NOx |
| US10703986B1 (en) * | 2019-01-30 | 2020-07-07 | Exxonmobil Research And Engineering Company | Selective oxidation using encapsulated catalytic metal |
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| US4235704A (en) * | 1979-08-20 | 1980-11-25 | Exxon Research & Engineering Co. | Method of reducing oxides of nitrogen concentration in regeneration zone flue gas |
| US4350615A (en) * | 1979-10-12 | 1982-09-21 | Standard Oil Company (Indiana) | Catalytic cracking with reduced emission of noxious gas |
| US4309309A (en) * | 1980-06-27 | 1982-01-05 | Chevron Research Company | Adding fuel in catalyst regeneration |
| US4440725A (en) * | 1980-10-03 | 1984-04-03 | Phillips Petroleum Company | Regenerator temperature control |
| US4354957A (en) * | 1980-10-03 | 1982-10-19 | Phillips Petroleum Company | Regenerator temperature control |
| US4790982A (en) * | 1986-04-07 | 1988-12-13 | Katalistiks International, Inc. | Metal-containing spinel composition and process of using same |
| US4744962A (en) * | 1987-07-22 | 1988-05-17 | Shell Oil Company | Process for the reduction of ammonia in regeneration zone off gas by select addition of NOx to the regeneration zone or to the regeneration zone off gas |
| US4988432A (en) * | 1989-12-28 | 1991-01-29 | Mobil Oil Corporation | Reducing NOx emissions with antimony additive |
| US5002654A (en) * | 1989-12-28 | 1991-03-26 | Mobil Oil Corporation | Reducing NOx emissions with zinc catalyst |
| US5077252A (en) * | 1990-07-17 | 1991-12-31 | Mobil Oil Corporation | Process for control of multistage catalyst regeneration with partial co combustion |
| US5268089A (en) * | 1992-06-24 | 1993-12-07 | Mobil Oil Corporation | FCC of nitrogen containing hydrocarbons and catalyst regeneration |
| US5382352A (en) * | 1992-10-20 | 1995-01-17 | Mobil Oil Corporation | Conversion of NOx in FCC bubbling bed regenerator |
| US5364517A (en) * | 1993-02-19 | 1994-11-15 | Chevron Research And Technology Company | Perovskite-spinel FCC NOx reduction additive |
| US5372706A (en) * | 1993-03-01 | 1994-12-13 | Mobil Oil Corporation | FCC regeneration process with low NOx CO boiler |
| US6355094B1 (en) * | 1994-01-06 | 2002-03-12 | Akzo Nobel N.V. | Material for the removal of gaseous impurities from a gas mixture |
| CA2156464C (en) * | 1994-09-30 | 1999-07-20 | Raghu K. Menon | Reduction of emissions from fcc regenerators |
| AU718321B2 (en) * | 1995-05-05 | 2000-04-13 | W.R. Grace & Co.-Conn. | Compositions for reduced NOx and combustion promotion in FCC processes |
| US6129834A (en) * | 1995-05-05 | 2000-10-10 | W. R. Grace & Co. -Conn. | NOx reduction compositions for use in FCC processes |
| US5830346A (en) * | 1995-08-30 | 1998-11-03 | Mobil Oil Corporation | FCC regenerator in partial CO burn with downstream air addition |
| US5705053A (en) * | 1995-08-30 | 1998-01-06 | Mobil Oil Corporation | FCC regenerator NOx reduction by homogeneous and catalytic conversion |
| EP1013743B1 (en) * | 1998-12-21 | 2005-02-02 | INDIAN OIL CORPORATION Ltd. | A fluid catalytic cracking (FCC) process |
| US6800586B2 (en) * | 2001-11-23 | 2004-10-05 | Engelhard Corporation | NOx reduction composition for use in FCC processes |
| US6660683B1 (en) * | 2002-10-21 | 2003-12-09 | W.R. Grace & Co.-Conn. | NOx reduction compositions for use in FCC processes |
-
2004
- 2004-04-21 US US10/828,974 patent/US20040262197A1/en not_active Abandoned
- 2004-05-26 TW TW093114992A patent/TW200502514A/en unknown
- 2004-06-03 JP JP2006517206A patent/JP2007523217A/en active Pending
- 2004-06-03 CN CNB2004800178704A patent/CN100345941C/en not_active Expired - Fee Related
- 2004-06-04 CA CA002527706A patent/CA2527706A1/en not_active Abandoned
- 2004-06-04 WO PCT/US2004/018242 patent/WO2005005578A1/en active Application Filing
- 2004-06-04 EP EP04754760A patent/EP1654340A1/en not_active Withdrawn
- 2004-06-04 AU AU2004256423A patent/AU2004256423A1/en not_active Abandoned
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104099129A (en) * | 2013-04-08 | 2014-10-15 | 中石化洛阳工程有限公司 | Short-reaction-time catalytic cracking method |
| CN106170659A (en) * | 2014-01-17 | 2016-11-30 | 三菱日立动力系统美洲股份有限公司 | Operate under the conditions of low-load gas turbine generating set |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100345941C (en) | 2007-10-31 |
| AU2004256423A1 (en) | 2005-01-20 |
| US20040262197A1 (en) | 2004-12-30 |
| WO2005005578A1 (en) | 2005-01-20 |
| JP2007523217A (en) | 2007-08-16 |
| TW200502514A (en) | 2005-01-16 |
| EP1654340A1 (en) | 2006-05-10 |
| CA2527706A1 (en) | 2005-01-20 |
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