EP1654340A1 - REDUCTION DES NOx DANS UNE OPERATION DE COMBUSTION PARTIELLE A FAIBLE QUANTITE DE CO A L'AIDE D'ADDITIFS POUR REGENERATEUR A COMBUSTION TOTALE - Google Patents

REDUCTION DES NOx DANS UNE OPERATION DE COMBUSTION PARTIELLE A FAIBLE QUANTITE DE CO A L'AIDE D'ADDITIFS POUR REGENERATEUR A COMBUSTION TOTALE

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Publication number
EP1654340A1
EP1654340A1 EP04754760A EP04754760A EP1654340A1 EP 1654340 A1 EP1654340 A1 EP 1654340A1 EP 04754760 A EP04754760 A EP 04754760A EP 04754760 A EP04754760 A EP 04754760A EP 1654340 A1 EP1654340 A1 EP 1654340A1
Authority
EP
European Patent Office
Prior art keywords
catalyst
groups
component
cracking
elements
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP04754760A
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German (de)
English (en)
Inventor
Duane R. Mcgregor
James O. Guerra
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ExxonMobil Technology and Engineering Co
Original Assignee
ExxonMobil Research and Engineering Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by ExxonMobil Research and Engineering Co filed Critical ExxonMobil Research and Engineering Co
Publication of EP1654340A1 publication Critical patent/EP1654340A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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

Definitions

  • the present invention relates to the reduction of the concentrations of nitrogen oxides (NO x ) from a fluid catalytic cracking (FCC) regenerator by operating the regenerator in partial CO burn mode with a NO x reducing catalyst system.
  • FCC fluid catalytic cracking
  • oxides of nitrogen are formed at high temperatures, such as the temperature at which catalyst utilized in a hydrocarbon cracking process is regenerated in the presence of carbon monoxide combustion promoters.
  • hydrocarbons such as petroleum feedstocks
  • coke is deposited on the catalyst particles.
  • the coke formation on the particles progressively decreases the activity of the catalyst particles.
  • This step which is normally referred to as regeneration, may be done on a batch or a continuous basis by contacting the catalyst particles with a hot regeneration gas, such as air. Coke is burned off, thus restoring catalyst activity and simultaneously heating the catalyst.
  • Flue gas formed by burning coke from the catalyst in the regenerator may be treated for removal of particulates and for conversion of CO to C0 2 , after which the flue gas is normally discharged into the atmosphere.
  • regenerators are designed for complete CO combustion, and usually produce a relatively coke-free regenerated catalyst, and flue gas with very little CO, and modest amounts of NO x .
  • the bubbling bed regenerator maintains the catalyst as a bubbling fluidized bed, to which spent catalyst is added and from which regenerated catalyst is removed.
  • These regenerators usually require more catalyst inventory than the high efficiency regenerator does, because gas/catalyst contacting is not as efficient in a bubbling fluidized bed as in a high efficiency regenerator.
  • Many bubbling bed regenerators operate in complete CO combustion mode, i.e., wherein the mole ratio of C0 2 /CO is at least 10. Refiners try to burn CO completely within the catalyst regenerator to conserve heat and to minimize air pollution.
  • An embodiment of the present invention provides a process for the catalytic cracking of a nitrogen-containing heavy hydrocarbonaceous feed to lighter products with reduced NO x emissions, which process comprises: a) cracking said feed by contacting said feed with a catalyst system in a fluidized catalytic cracking (FCC) reaction zone operating at catalytic cracking conditions to produce a mixture of cracked products and spent cracking catalyst having nitrogen compounds and coke deposited thereon, wherein said catalyst system comprises (i) at least one solid acid component, (ii) at least one metal- containing component comprised of one or more elements from Groups 1 and 3, and one or more elements from Groups 4-15 of the Periodic Table of the Elements; and at least one of oxygen and sulfur, wherein the elements from Groups 1 and 3, Groups 4 - 15 and the at least one of oxygen and sulfur are chemically bound both within and between the groups and (iii) at least one support, filler, or binder; b) separating said cracked products from said spent cracking catalyst to produce a cracked product
  • Another embodiment of the present invention provides a process for the catalytic cracking of a nitrogen-containing heavy hydrocarbonaceous feed to lighter products with reduced NO x emissions, which process comprises: a) cracking said feed by contacting said feed with a catalyst system in a fluidized catalytic cracking (FCC) reaction zone operating at catalytic cracking conditions to produce a mixture of cracked products and spent cracking catalyst having nitrogen compounds and coke deposited thereon, wherein said catalyst system comprises (i) at least one solid acid component, (ii) at least one metal- containing component comprised of one or more elements from Groups 1 and 3, and one or more elements from Groups 4-15 of the Periodic Table of the Elements; and at least one of oxygen and sulfur, wherein the elements from Groups 1 and 3, Groups 4 - 15 and the at least one of oxygen and sulfur are chemically bound both within and between the groups and (iii) at least one support, filler, or binder; b) separating said cracked products from said spent cracking catalyst to produce a cracked product
  • the reference to NO x refers to the various oxides of nitrogen that may be present in process streams such as, for example, the off-gas of the regenerator of a FCC unit.
  • the terms refer to all of the various oxides of nitrogen including nitric oxide (NO), nitrogen dioxide (N0 2 ), nitrous oxide (N 2 0), etc. and mixtures thereof.
  • NO nitric oxide
  • N0 2 nitrogen dioxide
  • N 2 0 nitrous oxide
  • the nitrogen oxides present in the regenerator off-gas NO typically makes up the majority of all NO x present. NO will usually represent 90% in the regenerator off-gas. Therefore, the presently claimed process is especially concerned with the reduction and control of NO.
  • the present invention provides a FCC process for cracking a nitrogen- containing heavy hydrocarbonaceous feed to lighter products with reduced NO x emissions.
  • the heavy hydrocarbonaceous feed passes to a FCC process unit which contains at least one reaction zone, a stripping zone, a catalyst regeneration zone, and a product fractionation zone.
  • the feed contacts a N0 X reducing catalyst system in a reaction zone at 425°C-600°C, preferably 460°C- 560°C.
  • the hydrocarbons crack, and deposit coke, sulfur, and nitrogen compounds on the catalyst.
  • the cracked products are separated from the coked or spent catalyst.
  • the coked catalyst is stripped of volatiles, usually with steam, in the stripping zone.
  • the stripping is preferably performed under low-severity conditions to minimize thermal cracking.
  • the stripped catalyst is then passed to the regeneration zone where it is regenerated by burning coke on the catalyst in the presence of an oxygen containing gas, preferably air or oxygen-enriched air.
  • This regeneration step restores catalyst activity and simultaneously heats the catalyst to a temperature from 1202°F (650°C) to 1382°F (750°C).
  • the environment in the regenerator reduces the amount of coke nitrogen that is converted to reduced nitrogen compounds, such as ammonia, and increases the amount of nitrogen oxides that are produced in the regeneration zone from coke nitrogen.
  • the total amount of oxygen in the regeneration zone is limited so that the regenerator is operated in partial combustion mode.
  • Any conventional FCC feed can be used in the present invention.
  • feeds typically include heavy hydrocarbonaceous feeds boiling in the range of 430°F to 1050°F (220°C-565°C), such as gas oils, heavy hydrocarbon oils comprising materials boiling above 1050°F (565°C); heavy and reduced petroleum crude oil; petroleum atmospheric distillation bottoms; petroleum vacuum distillation bottoms; pitch, asphalt, bitumen, other heavy hydrocarbon residues; tar sand oils; shale oil; liquid products derived from coal liquefaction processes; and mixtures thereof.
  • Such feeds typically contain an undesirable amount of nitrogen compounds that are converted to nitrogen oxides in the regenerator.
  • the FCC feed may also comprise recycled hydrocarbons, such as light or heavy cycle oils.
  • Preferred feeds in this process are vacuum gas oils boiling in the range above 650°F (343°C).
  • the N0 X reducing catalyst system utilized in the present invention comprises (i) at least one solid acid component, (ii) at least one metal-containing component comprised of one or more elements from Groups 1 and 3, and one or more elements from Groups 4-15 of the Periodic Table of the Elements; and at least one of oxygen and sulfur, wherein the elements from Groups 1 and 3, Groups 4 - 15 and at least one of oxygen and sulfur are chemically bound both within and between the groups and (iii) at least one support, filler or binder.
  • the solid acid component is preferably a conventional FCC catalyst including catalysts containing large-pore zeolites such as USY or REY. Additional zeolites, which can be employed in accordance with this invention include both natural and synthetic zeolites.
  • the large-pore zeolites include gmelinite, chabazite, dachiardite, clinoptilolite, faujasite, heulandite, analcite, levynite, erionite, sodalite, cancrinite, nepheline, lazurite, scolecite, natrolite, offretite, mesolite, mordenite, brewsterite, and ferrierite.
  • the more preferred large-pore zeolites are the faujasites, particularly zeolite Y, USY, and REY.
  • the catalysts useful in the present invention can also be a medium- pore zeolite or a large-pore and medium-pore zeolite mixture.
  • Medium-pore size zeolites that can be used in the practice of the present invention are described in " Atlas of Zeolite Structure Types", eds. W. H. Meier and D. H. Olson, Butterworth-Heineman, Third Edition, 1992, which is hereby incorporated by reference.
  • the medium-pore size zeolites generally have a an average pore diameter less than 0.7 nm, typically from 0.5 to 0.7 nm and includes for example, MFI, MFS, MEL, MTW, EUO, MTT, HEU, FER, and TON structure type zeolites (IUPAC Commission of Zeolite Nomenclature).
  • Non-limiting examples of such medium-pore size zeolites include ZSM-5, ZSM-12, ZSM-22, ZSM-23, ZSM-34, ZSM-35, ZSM-38, ZSM-48, ZSM-50, silicalite, and silicalite 2. The most preferred is ZSM-5, which is described in U.S. Pat. Nos. 3,702,886 and 3,770,614.
  • ZSM-11 is described in U.S. Pat. No. 3,709,979; ZSM-12 in U.S. Pat. No. 3,832,449; ZSM-21 and ZSM-38 in U.S. Pat. No. 3,948,758; ZSM-23 in U.S. Pat. No. 4,076,842; and ZSM-35 in U.S. Pat. No. 4,016,245. All of the above patents are incorporated herein by reference.
  • Other suitable medium-pore size zeolites include the silicoaluminophosphates (SAPO), such as SAPO-l 1, SAP0-34, SAPO-41, and SAP0-42, which are described in U.S. Pat. No.
  • SAPO silicoaluminophosphates
  • chromosilicates gallium silicates; iron silicates; aluminum phosphates (ALPO), such as ALPO-11 described in U.S. Pat. No. 4,310,440; titanium aluminosilicates (TASO), such as TAS0-45 described in EP-A No. 229,295; boron silicates, described in U.S. Pat. No. 4,254,297; titanium aluminophosphates (TAPO), such as TAPO-11 described in U.S. Pat. No. 4,500,651; and iron aluminosilicates.
  • the Si/Al ratio of said zeolites is greater than 40.
  • the medium-pore size zeolites can include "crystalline admixtures" which are thought to be the result of faults occurring within the crystal or crystalline area during the synthesis of the zeolites.
  • Examples of crystalline admixtures of ZSM-5 and ZSM-11 are disclosed in U.S. Pat. No. 4,229,424 which is incorporated herein by reference.
  • the crystalline admixtures are themselves medium-pore size zeolites and are not to be confused with physical admixtures of zeolites in which distinct crystals of crystallites of different zeolites are physically present in the same catalyst composite or hydrothermal reaction mixtures.
  • the large-pore and medium-pore catalysts of the present invention will be present in an inorganic oxide matrix component binder that binds the catalyst components together so that the catalyst product is hard enough to survive inter-particle and reactor wall collisions.
  • the inorganic oxide matrix can be made from an inorganic oxide sol or gel which is dried to "glue" the catalyst components together.
  • the inorganic oxide matrix is not catalytically active and will be comprised of oxides of silicon and aluminum. It is also preferred that separate alumina phases be incorporated into the inorganic oxide matrix.
  • Species of aluminum oxyhydroxides- ⁇ -alumina, boehmite, diaspore, and transitional aluminas such as ⁇ -alumina, ⁇ -alumina, ⁇ -alumina, ⁇ -alumina, s- alumina, ⁇ -alumina, and p-alumina can be employed.
  • the alumina species is an aluminum trihydroxide such as gibbsite, bayerite, nordstrandite, or doyelite.
  • the matrix material may also contain phosphorous or aluminum phosphate. It is within the scope of this invention that the large-pore catalysts and medium-pore catalysts be present in the same or different catalyst particles, in the aforesaid inorganic oxide matrix.
  • Supported acid materials are either crystalline or amorphous materials, which may or may not themselves be acidic, modified to increase the acid sites on the surface.
  • Non-limiting, illustrative examples are H 2 S0 4 , H 3 P0 4 , H 3 B0 3) CH 2 (C00H) 2 , mounted on silica, quartz, sand, alumina or diatomaceous earth., as well as heteropoly acids mounted on silica, quartz, sand, alumina or diatomaceous earth.
  • Non-limiting, illustrative examples of crystalline supported acid materials are acid-treated molecular sieves, sulfated zirconia, tungstated zirconia, phosphated zirconia and phosphated nobia.
  • the solid acid component is present with at least one metal-containing component comprised of one or more elements from Groups 1 and 3, and one or more elements from Groups 4-15 of the Periodic Table of the Elements.
  • the remaining component of the catalyst system in accordance with the invention can be at least one of sulfur and oxygen. Oxygen is preferred.
  • the elements) from Groups 1 and 3 can be any metal or combination of metals selected from lithium, sodium, potassium, rubidium, cesium, francium, scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium.
  • the elements from Groups 1 and 3 can be any metal or combination of metals selected from lanthanum and cerium.
  • the element(s) from Groups 4-15 can be any element or a mixture of elements from Groups 4- 15 of the Periodic Table of the Elements.
  • the elements) from Groups 4-15 is (are) at least one of titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, boron, aluminum, phosphorous, 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(s) from Groups 4-15 is (are) at least one of copper, palladium, and silver.
  • the catalyst system of the present invention can be prepared by physically mixing or chemically reacting with the metal-containing component and, optionally, combined with the binder to form catalyst particles or act as a filler to moderate the catalyst activity.
  • the weight ratio of solid acid component to the total weight of the metal-containing component can be from 1000:1 to 1 : 1000. Preferably, this ratio is 500: 1 to 1 :500. Most preferably, this ratio is 100:1 to 1:100.
  • the weight ratio of the metal-containing component to the matrix component can be 100:1 to 1:100.
  • the metal-containing or NO x reducing component of the catalyst system may be used as a separate additive particle or as an integral part of a FCC catalyst particle.
  • the NO x reducing component may contain minor amounts of other materials, which preferably do not adversely affect the NO x reducing function in a significant way. More preferably, however, the NO x reducing component consists essentially of items (ii)-(iii) mentioned above.
  • An effective amount is an amount, which is effective for reducing the NO x content in the regenerator flue gas below that which would be present in the absence of the additive.
  • the NO x reducing component may be combined with at least one support, filler, or binder to form particles suitable for use in a FCC process. If the particle NO x reduction component is an integral part of a FCC catalyst particle, it preferably contains from 0.001 to 10 percent by weight, and more preferably from 0.01 to 5 percent by weight, and most preferably from 0.05 to 1 percent by weight of the inventory of circulating particulate solids.
  • the NO x reducing catalyst system of the present invention is active for reducing the NO x content of FCC regenerator flue gas, it has a negligible effect on the hydrocarbon cracking reactions which occur during the FCC process.
  • the N0 X reducing catalyst system is compatible with CO oxidation promoters, which may be part of the inventory of circulating particulate solids.
  • the N0 X reducing catalyst system of the present invention may be used with additives that provide S0 X reduction. These S0 X additives may also provide NO x reduction.
  • the S0 X additives are preferred to be various forms of alumina, rare-earth oxides, alkaline earth oxides, and spinels.
  • the SO x additive is a magnesium-aluminum spinel.
  • SO x additives are available from several catalyst suppliers, such as Grace-Davison's DESOX or SUPERDESOX, or Intercafs SOXGETTER or Super-SOXGETTER.
  • CO concentrations are generally greater than 4.0 vol.% with very little NO being present, generally less than 50 ppm by volume NO.
  • the majority of nitrogen containing species exiting the regenerator at such high CO concentrations are in the form of HCN and NH 3 . This is not the optimum use for a NO x reducing catalyst system.
  • the CO concentration of the present invention is run in partial combustion mode with preferably 0.5 to 4.0 vol.% CO, more preferably from 0.75 to 3.0 vol.% CO, and most preferably from 1.00 to 2.0 vol.% CO.
  • NO concentration is preferably greater than 90 ppm by volume, more preferably greater than 150 ppm by volume, and most preferably greater than 200 ppm by volume.
  • CO concentration is reduced, more NO is produced, causing more NO reduction with CO, and thereby reducing NO x emissions.
  • the presence of a circulating NO x reducing catalyst system increases the rate of NO reduction by CO, thereby causing additional reduction in NO x emissions.
  • the hot regenerated catalyst is recycled to the FCC reaction zone where it contacts injected FCC feed.
  • the reactor operation will usually be conventional all riser cracking FCC, such as disclosed in U.S. Pat. No. 4,421,636 incorporated herein by reference.
  • Typical riser cracking reaction conditions include catalyst/oil ratios of 0.5:1 to 15:1, preferably 3:1 to 8:1, and a catalyst contact time of 0.1-50 seconds, preferably 0.5 to 10 seconds, most preferably 0.75 to 5 seconds, and riser top temperatures of 900°F to 1100°F, preferably 950°F to 1050°F.
  • a preferred hot stripper and catalyst cooler is shown in U.S. Pat. No. 4,820,404, Owen, incorporated herein by reference.
  • Conventional FCC steam stripping conditions can be used, with the spent catalyst having essentially the same temperature as the riser outlet, and with 0.5 to 5% stripping gas, preferably steam, added to strip spent catalyst.
  • the FCC reactor and stripper conditions, per se, can be conventional.
  • FCC regenerators Two types can be used in the process of the present invention, the high efficiency regenerator and the bubbling bed type.
  • bubbling bed regenerators much of the regeneration gas, usually air, passes through the bed in the form of bubbles. These pass through the bed, but contact it poorly. These units operate with large amounts of catalyst.
  • the bubbling bed regenerators are not very efficient at burning coke so a large catalyst inventory and long residence time in the regenerator are needed to produce clean burned catalyst.
  • the carbon levels on regenerated catalyst can be conventional, typically less than 0.3 wt % coke, preferably less than 0.15 wt % coke, and most preferably even less.
  • coke we mean not only carbon, but also minor amounts of hydrogen associated with the coke, and perhaps even very minor amounts of unshipped heavy hydrocarbons which remain on catalyst. Expressed as wt % carbon, the numbers are essentially the same, but 5 to 10% less.
  • the process or the present invention can also be used with high efficiency regenerators (HER), with a fast fluidized bed coke combustor, dilute phase transport riser, and second bed to collect regenerated catalyst. It will be necessary to operate these in partial CO bum mode to make CO specifications.
  • HER high efficiency regenerators
  • HERs inherently make excellent use of regeneration air. Most operate with 1 or 2 mole % 0 2 or more in the flue gas when in complete CO bum mode. When in partial CO bum mode most operate with little excess oxygen, usually in the ppm range, preferably less than 1/10th %. For HER's, significant reductions in the amount of air added may be necessary to produce a flue gas with the correct CO/0 2 ratio. Reducing or eliminating CO combustion promoter may be necessary to generate a flue gas with twice as much CO as oxygen.
  • regenerators are controlled primarily by adjusting the amount of regeneration air added, other equivalent control schemes are available which keep the air constant and change some other condition. Constant air rate, with changes in feed rate changing the coke yield, is an acceptable way to modify regenerator operation. Constant air, with variable feed preheat, or variable regenerator air preheat, are also acceptable. Finally, catalyst coolers can be used to remove heat from a unit. If a unit is not generating enough coke to stay in heat balance, torch oil, or some other fuel may be burned in the regenerator.
  • the present invention was tested and developed using a commercial FCC process unit.
  • CO concentration in the flue gas at the outlet of the FCC unit regenerator was varied from above approximately 0.5 vol.% to approximately 5.5 vol.%.
  • NO concentration varied from a maximum of 266 ppm by volume down to a minimum of approximately 31 ppm by volume (Table 1).
  • the accepted reaction mechanism for minimizing NO x emissions from the FCC unit regenerator requires operation in a regime where significant concentrations of both NO and CO exist.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)

Abstract

La présente invention permet de réduire les concentrations d'oxydes d'azote (NOx) émises par un régénérateur de craquage catalytique fluide (FCC) en faisant fonctionner le régénérateur en mode de combustion partielle de CO avec un système catalyseur réduisant les NOx.
EP04754760A 2003-06-24 2004-06-04 REDUCTION DES NOx DANS UNE OPERATION DE COMBUSTION PARTIELLE A FAIBLE QUANTITE DE CO A L'AIDE D'ADDITIFS POUR REGENERATEUR A COMBUSTION TOTALE Withdrawn EP1654340A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US48203703P 2003-06-24 2003-06-24
PCT/US2004/018242 WO2005005578A1 (fr) 2003-06-24 2004-06-04 Reduction des nox dans une operation de combustion partielle a faible quantite de co a l'aide d'additifs pour regenerateur a combustion totale

Publications (1)

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EP1654340A1 true EP1654340A1 (fr) 2006-05-10

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US (1) US20040262197A1 (fr)
EP (1) EP1654340A1 (fr)
JP (1) JP2007523217A (fr)
CN (1) CN100345941C (fr)
AU (1) AU2004256423A1 (fr)
CA (1) CA2527706A1 (fr)
TW (1) TW200502514A (fr)
WO (1) WO2005005578A1 (fr)

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CA2527706A1 (fr) 2005-01-20
JP2007523217A (ja) 2007-08-16
CN1813042A (zh) 2006-08-02
CN100345941C (zh) 2007-10-31
WO2005005578A1 (fr) 2005-01-20
AU2004256423A1 (en) 2005-01-20
TW200502514A (en) 2005-01-16
US20040262197A1 (en) 2004-12-30

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