CN101747933A - Modifying method for naphtha and light hydrocarbon aromatization - Google Patents
Modifying method for naphtha and light hydrocarbon aromatization Download PDFInfo
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- CN101747933A CN101747933A CN 200810227646 CN200810227646A CN101747933A CN 101747933 A CN101747933 A CN 101747933A CN 200810227646 CN200810227646 CN 200810227646 CN 200810227646 A CN200810227646 A CN 200810227646A CN 101747933 A CN101747933 A CN 101747933A
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Abstract
A modifying method for naphtha and light hydrocarbon aromatization comprises: contacting naphtha and C3-C5 light hydrocarbon with aromatization catalyst in the presence of hydrogen-containing gas to carry out aromatization modifying reaction, wherein the reaction temperature is 250-600 DEG C, and the volume ratio of hydrogen to naphtha is 20-400. The method can convert naphtha with low octane value and low-carbon hydrocarbon into gasoline component with high octane value and excellent liquefied gas, the final distilling point of liquid product and the carbon-accumulating speed of catalyst are obviously reduced, and the service life of catalyst is prolonged.
Description
Technical field
The present invention is a kind of light-hydrocarbon aromatized method for modifying, specifically, is a kind of with low octane rating petroleum naphtha and C
3～C
5The mixture of lighter hydrocarbons is a raw material, produces aromatic hydrocarbons or clean gasoline component, and the method for attached product high-quality liquefied gas.
Background technology
Along with the appearance of unleaded gasoline and new gasoline standard, part low octane value gasoline, light naphthars such as the tops of for example reforming, condensate oil, partial hydrogenation coker gasoline and straight-run spirit are badly in need of seeking suitable processing technology.Though this part petroleum naphtha is fit to do ethylene raw, because its vapour pressure is higher, transportation is difficulty relatively, if there is not ethylene unit near the enterprise, is difficult to ethylene raw.At present, oil refining enterprise is produced the main device or the catalytic reforming of aromatic hydrocarbons and high-octane rating clean gasoline blend component, but catalytic reforming is used the platiniferous noble metal catalyst, and raw material impurity is required harshness, invests huge.Late 1970s, because the discovery of ZSM-5 shape-selective molecular sieve, can be under the condition of not using noble metal catalyst, petroleum naphtha and carbon number is less, be mainly C
5The following hydrocarbon conversion is an aromatic hydrocarbons, while by-product hydrogen and high-quality liquefied gas, and its main products BTX aromatics is an important chemical material, also can mix with gasoline and convert, concoct, and improves gasoline octane rating.This technology is called aromatization technology.This has opened up an effective way for the utilization of refinery's low octane rating petroleum naphtha.
In addition, the carbon four component processing and utilization rates in China's refinery gas are very low, and except that being used on a small quantity produce gasoline alkylate and the MTBE, overall utilization is less than 20%, and all the other overwhelming majority are still as civil liquefied gas.In China, carbon four components are mainly from catalytic cracking unit, because its alkene, particularly based on the heavy carbon four component concentration height of butene-2, burning quality is poor, and directly acting as a fuel is very big waste.Simultaneously, market is growing to the demand of stop bracket gasoline blend component, therefore exploitation can be converted into the C 4 olefin in the mixed c 4 technology of stop bracket gasoline blend component or aromatic hydrocarbons, the clean gasoline component or the aromatic hydrocarbons of a part of high octane rating low olefin both can have been increased production, can also reduce simultaneously the olefin(e) centent in the civil liquefied gas, improve the liquefied gas quality, will have good economic and social benefit.
CN1032697C discloses a kind of catalytic modification of poor quality gasoline-aromatization method, this method contacts inferior patrol with catalyzer carries out the echelon reaction, be about to raw material and feed first fixed-bed reactor earlier, at 300～550 ℃, 0.05～1.2MPa, weight space velocity 0.2～1.0h
-1Conditions of non-hydrogen under react, resultant is through gas-liquid separation, C
5Above liquid obtains gasoline fraction by fractionation, in the reaction product less than C
4Gas send into second reactor through preheating, at 480～650 ℃, 0.05～1.5MPa, volume space velocity 20～2000h
-1Condition under carry out aromatization, the aromizing product obtains being rich in the gas and the aromatic hydrocarbons mixture of hydrogen after gas-liquid separation.Used aromatized catalyst is made up of the HZSM-5 molecular sieve and the binding agent of modification, described molecular sieve modified component is two or three in Zn, Al or the rare earth metal, and binding agent is selected from a kind of or aluminum oxide in aluminum oxide, silicon oxide or the clay and the mixture of silicon oxide.Described reactor be two in parallel can switch, the regenerated fixed bed, in about two weeks in catalyzer one way life-span, decaying catalyst is by feeding oxygen-containing gas, at 550～700 ℃ of coke burning regenerations in fixed bed.
CN1261535C discloses the method that a kind of straight-run spirit upgrading prepares gasoline with low olefine content, this method is mixed straight-run spirit with the C 4 olefin cut, under 0.2～0.6MPa, 300～500 ℃ condition, in fixed-bed reactor with contain the catalyzer contact reacts of HZSM-5, the dry gas in the separated product, liquefied gas and gasoline component then.Also can contain the modified component that is selected from antimony or mixed rare-earth oxide in the described catalyzer.
CN1212376C discloses a kind of lighter hydrocarbons non-hydrogen modifying catalyst and preparation method and application art.Described catalyzer is made up of the carrier of the mixed rare-earth oxide that contains 0.1～5.0 quality % or weisspiessglanz, 95.0～99.1 quality %, and wherein carrier is made up of the HZSM-5 zeolite of 50～80 quality % and the gama-alumina of 20～50 quality %.Described lighter hydrocarbons non-hydrogen upgrading carries out in fixed-bed reactor, and reaction product is separated liquid the stop bracket gasoline that obtains dry gas, high-quality liquefied gas and low olefin-content again through gas-liquid separation.Decaying catalyst is done resurgent gases with oxygen containing stack gas or nitrogen and is burnt carbon, and the resurgent gases oxygen level is 0.3～2.1%, and regeneration temperature is that 350～450 ℃, regeneration pressure are 0.1～0.3MPa.
CN1152121C discloses a kind of method for aromatizing light hydrocarbons, comprises refinery's low-pressure gas under the aromizing condition, with a kind of aromatized catalyst contact reacts, produces aromatic hydrocarbons and hydrogen.Consisting of of catalyst system therefor: Zn 0.8～3.5 heavy %, mixed rare earth oxide 0.2～1.5 heavy %, carrier 95.0～99.0 heavy %, wherein carrier is made up of the HZSM-5 zeolite of 50～80 heavy % and the gama-alumina of 20～50 heavy %, contains lanthanum trioxide 20～40 heavy %, cerium oxide 40～60 heavy %, Praseodymium trioxide 10～18 heavy %, Neodymium trioxide 2～10 heavy % in the mixed rare earth oxide.Aromatization switches in turn in the regenerated fixed-bed reactor at two and carries out, and the charcoal temperature of regenerated catalyst is 440～550 ℃, and resurgent gases is the nitrogen that contains oxygen 0.4～21 volume %.
CN1651141A discloses a kind of aromatized catalyst and preparation thereof and has used, and adopting Zn, phosphorus and rare-earth element modified HZSM-5 molecular sieve and REY molecular sieve is the catalyst activity component.With the lower inferior patrol of octane value is raw material, carries out the moving-bed aromatization under the non-hydrogen state, and temperature of reaction is 350～550 ℃, and pressure is 0.1～0.5MPa, and air speed is 0.5～5h
-1Catalyst regeneration temperature is 400～550 ℃, and the residence time in revivifier is 1～600 minute, adopts air regenesis.
CN1176187C discloses a kind of low-carbon hydrocarbon aromatization method, and catalyzer is a carrier with HZSM-5 zeolite and aluminum oxide, is active metal component with nickel and zinc.Low-carbon (LC) hydrocarbon raw material (mixed c 4 gas) enters in the fixed-bed reactor and contact with catalyzer and carry out aromatization after heating, and reaction product obtains BTX aromatics, hydrogen and high quality liquefied gas after cooling, separation.Reaction conditions is 500～600 ℃, 0.1～1.0MPa, and volume space velocity is 0.5～2h during liquid
-1
It is the technology of aromatization of low carbon hydrocarbon of raw material production aromatic hydrocarbons with carbon four hydrocarbon that CN1026316C discloses a kind of.With metal-modified ZSM-5 molecular sieves such as nickel, zinc or strontiums is catalyzer, makes carbon four hydrocarbon carry out aromatization in fixed-bed reactor, and reaction product obtains benzene mixed through refrigerated separation; After the reaction, flue gas is mixed with 1: 0.5～1.5 volume ratio with air, be heated to 300～650 ℃ and enter fixed bed, make the coke gasification on the catalyst surface, feed the unstripped gas activation that accounts for normal aromizing 1～10 weight % then.The regeneration of reaction and catalyzer hockets in the light-hydrocarbon aromatized process.
CN1485414A discloses the method for a kind of catalytically cracked gasoline non-hydrogen aromatization and desulfurization, this method is introduced the reactor that molecular sieve catalyst is housed with the full cut of catalytically cracked gasoline, carry out alkene aromizing and hydrodesulfurization reaction, again reacted product is carried out alkali-free sweetening, obtain gasoline products, its temperature of reaction is that 100～550 ℃, pressure are that 0.01～5.0MPa, air speed are 0.1～20h
-1The used aromatized catalyst active ingredient of this method is one or more in ZSM-5, ZSM-11, ZSM-12, ZSM-35, MCM-22, Y molecular sieve and the beta molecular sieve, and the modified component of molecular sieve is one or more of rare earth element, VIB, VIII family element, haloid element, Mg, Zn, P and Na.Aromatization can carry out in moving-bed, fluidized-bed or fixed bed, but does not provide concrete catalyst regeneration process.
USP4795845 discloses a kind of aliphatic hydrocarbon aromatization method that is the catalyst activity component with phosphorous and ZSM-5 molecular sieve gallium, and this method contacts the catalyzer of inactivation with oxygen containing resurgent gases, regenerate by burning.Regeneration can be carried out in fixed bed or moving-bed, and resurgent gases is capable of circulation.This patent points out that also the regeneration of decaying catalyst can be divided into for two steps, the first step uses the lower gas of oxygen level to burn, the burning process oxygen content gas is 1.0mol%, then oxygen content gas slowly is increased to 7.0mol% and burns again, basic identical until the out temperature of catalyst bed.
USP4724271 discloses a kind of continuous regeneration method of aromatized catalyst, and this method uses the ZSM-5 molecular sieve of Ga modification to be catalyzer.The scorch region of decaying catalyst by revivifier contained oxygen cycle gas with exsiccant contact, reclaim flue gas and air mixed from scorch region, the moisture of removing wherein through super-dry enters scorch region again, thereby forms the circulation of scorch region gas.Catalyzer after burning enters drying zone, utilizes dry air to carry out drying.Described scorch region is radially moving bed, and drying zone is an axial moving bed.
US6395664B1 discloses the continuous regeneration method of the ZSM-5 aromatized catalyst of a kind of Ga of comprising and P, catalyzer exposes inactivation in hydrogen to the open air under the high temperature more than 500 ℃, only burn and can not recover activity of such catalysts, the need use contains weakly acidic ammonium salt or aqueous acid is handled the catalyzer after burning.The regeneration of decaying catalyst divides four-stage: burn, cool off, handle and dry with ammonium salt-containing or faintly acid water vapor air-flow, wherein scorch region adopts resurgent gases round-robin mode to carry out moving-bed to burn for one section.
US4704494 disclose a kind of in fixed-bed reactor with lower carbon number hydrocarbons, be converted into the Catalyst And Method of aromatic hydrocarbons as propane.Temperature of reaction is 350～600 ℃, and catalyzer is the metal-modified zeolite of supporting Pt or Ga, and the Zeolite modifying metal is selected from Al, Ga, Ti, Zr, Ge, La, Mn, Cr, Sc, V, Fe, W, Mo or Ni, and aromatics yield can reach 20～30%.
USP4304657 discloses a kind of improved naphtha aromtization process, is catalyzer with the HZSM-5 of zinc modification, at 345～815 ℃, under the condition of 0.1～3.5MPa, with CO
2Or nitrogen dilutes petroleum naphtha and CO during dilution to petroleum naphtha
2Or the mol ratio of nitrogen is 1: 1～20.This method can improve the H in the naphtha aromtization gaseous product
2/ CH
4Mol ratio, and reduce C in the product liquid
10The content of above aromatic hydrocarbons.
US6245219B 1 discloses a kind of naphtha reforming method, the catalyzer that this method is used is carrier with mesopore acidic silicic acid salt, at least a oxide compound or the sulfide that is selected from Zn, Ga, In, Fe, Sn and B of load, and by carrying out modification with alkaline earth metal hydroxides or silicoorganic compound impregnated carrier, the preferred ZSM-5 of described silicate.Use the petroleum naphtha that contains 25% alkane and naphthenic hydrocarbon at least to be raw material, at 200～538 ℃, 70～2100KPa, weight space velocity 0.5～25h
-1, hydrogen/hydrocarbon mol ratio 0～10 is preferably under 4 the condition and carries out naphtha reforming, C in the products therefrom
1～C
4Gas yield significantly be reduced to below the 20 weight % and the C of product liquid
8Be rich in p-Xylol in the component.
" Liaoming Petrochemical Univ's journal " June in 2006, the 26th volume the 2nd phase 1-4 page or leaf reported that low-temperature mixed carbon four is at SO
4 2-/ TiO
2/ HZSM-5, tackiness agent are that the catalyzer of gama-alumina exists the aromatization that carries out down." oil and gas chemical industry " 1994 the 23rd volume the 1st phase 8-11 page or leaf has reported that butane or C 4 olefin content are 65% mixed c 4 is converted into aromatic hydrocarbons on the Ga/HZSM-5 catalyzer method.
Summary of the invention
The method that the purpose of this invention is to provide a kind of petroleum naphtha and light-hydrocarbon aromatized upgrading, this method can be produced stop bracket gasoline or aromatic hydrocarbons, produces the high-quality liquefied gas of low olefin-content simultaneously, reduces doing of catalyst carbon deposit speed and liquid product.
Light-hydrocarbon aromatized method for modifying provided by the invention comprises petroleum naphtha and C
3～C
5Lighter hydrocarbons in the presence of hydrogen-containing gas, contact and carry out the aromatization modification reaction with aromatized catalyst, described upgrading temperature of reaction is that 250～600 ℃, the volume ratio of hydrogen/petroleum naphtha are 20～400.
The inventive method makes low octane rating petroleum naphtha and lighter hydrocarbons carry out aromatization in the presence of hydrogen-containing gas, has significantly reduced the final boiling point of product and the coke deposit rate of catalyzer.When the inventive method is used for moving bed reaction-continuous regeneration set, revivifier is divided into buffer zone, scorch region, drying zone and cooling zone, the regenerative operation elasticity of catalyzer is increased, energy consumption reduces, favorable regeneration effect, work-ing life prolong.And under the situation of a plurality of reactors of polyphone, take to inject respectively the sectional feeding mode of lighter hydrocarbons to each reactor, can make temperature of reaction be convenient to control.In addition, scorch region is divided into two sections, can relaxes the operational condition of scorch region, the loss of burning specific surface area of catalyst in more abundant and the burning process is reduced.
Application the inventive method is carried out petroleum naphtha and is mixed the mixed c 4 aromatization modification, and yield of gasoline can reach 55～77 quality %, and liquefied gas yield reaches 20～44 quality %, low value byproduct-dry gas (C
1～C
2Hydrocarbon and small quantity of hydrogen) productive rate is 0.5～3.0 quality %.The oily research octane number (RON) RON that steams reaches 92, and olefin(e) centent is lower than 2.5 quality %, and benzene content is not more than 1.5 quality %, and the aromatic hydrocarbons total content is less than 40 quality %, and the gasoline final boiling point is about 210 ℃, the equal compliance with environmental protection requirements of every index.Institute's production fluid gasification is based on propane and butane, and olefin(e) centent is less than 5.0 quality %, and handling the back through desulfurization is the high-quality liquefied gas.
Description of drawings
Fig. 1 stacks polyphone up and down for the inventive method reaction zone adopts two reactors, and two sections scorch regions of revivifier adopt the process flow diagram of radial structure bed.
Fig. 2 stacks polyphone up and down for the inventive method reaction zone adopts two reactors, and two sections scorch regions of revivifier adopt the process flow diagram of footpath, axial arrangement bed.
Fig. 3 stacks polyphone in twos for the inventive method reaction zone adopts four reactors, and two sections scorch regions of revivifier adopt the process flow diagram of radial structure bed.
Fig. 4 stacks polyphone in twos for the inventive method reaction zone adopts four reactors, and two sections scorch regions of revivifier adopt the process flow diagram of footpath, axial arrangement bed.
Fig. 5 is the process flow diagram of reaction product fractionating system of the present invention.
Embodiment
The inventive method makes low octane value gasoline and lighter hydrocarbons carry out aromatization modification reaction in the presence of hydrogen, can reduce the coke deposit rate with catalyzer done of reformulated gasoline component.When in the device that uses moving-burden bed reactor and continuous catalyst regenerating, carrying out above-mentioned aromatization modification reaction, revivifier is divided into buffer zone, scorch region, drying zone and cooling zone from top to bottom successively, and pressure conversion and flow control district are arranged on the top of revivifier, make to burn under elevated pressures and carry out, cooperate the continuous flow of the buffer zone realization catalyzer of revivifier.In addition, but buffer zone preheating catalyst also reduces the operation energy consumption of revivifier.Carbon content with catalyzer in scorch region is reduced to below the 0.2 quality %, recovers activity of such catalysts.In drying zone, remove the moisture that catalyzer adsorbs in burning process.By the cooling zone catalyzer is cooled off, reduce the requirement of the follow-up pipeline of revivifier and equipment to material.The setting of buffer zone and cooling zone can suitably reduce plant energy consumption.In addition, two sections scorch regions that adopt in the inventive method, the temperature that can each scorch region of independent control and the oxygen level of inlet gas, make the revivifier turndown ratio big, burn more abundant, under the lower situation of scorch region inlet gas oxygen level, the local hot spots that the catalyzer burning process is produced reduces, burn more evenly, specific surface area of catalyst loss reduces, and prolong work-ing life.
Hydrogen-containing gas of the present invention can be the gas that contains hydrogen that any technology produces, and the content of hydrogen is 5～99.5 volume % in the hydrogen-containing gas, and all the other are not for influencing the gas of aromatization.Preferred hydrogen-containing gas is petroleum naphtha and C
3～C
5Lighter hydrocarbons carry out the dry gas that aromatization produces.Described dry gas is the noncondensable gas of hydrogen, methane, ethane and ethene, and wherein hydrogen content is generally 5～40 volume %.
Described petroleum naphtha is that initial boiling point is that 30～80 ℃, final boiling point are 130～200 ℃ hydrocarbon fraction, the naphtha fraction that preferred virgin naphtha, reformation tops, condensate oil or hydrogenation coking process produce.Olefin(e) centent is 15～98 quality % in the described lighter hydrocarbons, preferred 40～98 quality %, and all the other are C
3～C
5Alkane.Preferred lighter hydrocarbons are mixed c 4, and butene content is generally 40～95 quality % in the mixed c 4.
Used petroleum naphtha of the present invention and C
3～C
5The mass ratio of lighter hydrocarbons be 1～9: 9～1, preferred 3～7: 7～3.
Aromatization modification reaction of the present invention is preferably carried out in moving bed reaction-continuous regeneration set, and concrete operations are: with petroleum naphtha and C
3～C
5Lighter hydrocarbons enter the moving bed reaction district after mixing, contact with aromatized catalyst and to carry out aromatization, will be from the effusive reclaimable catalyst in bottom, moving bed reaction district, through the reclaimable catalyst lifter, the spent riser line, reclaimable catalyst separates hopper and pressure conversion and flow control district and enters catalyst regenerator from the top, pass through the buffer zone in the catalyst regenerator from top to bottom successively, scorch region, drying zone and cooling zone, in scorch region, feed the coke burning regeneration that oxygen containing resurgent gases is carried out reclaimable catalyst, again regenerated catalyst is promoted, enter moving-burden bed reactor from the top.
Described scorch region comprises at least two sections scorch regions of arranged vertical from top to bottom, comes one section preferred radial bed of scorch region on top, and two sections scorch regions that come the bottom can be radial bed or axial bed.The flue gas of two sections scorch region generations can be discharged from the bottom or the top of one section scorch region.
After the flue gas process desulfurization and drying that above-mentioned catalyst regenerator scorch region is discharged, become resurgent gases with air mixed and return scorch region.Preferable methods be will discharge from scorch region flue gas through desulfurization and drying after, be mixed into resurgent gases with the gas mixture of air or air and nitrogen, resurgent gases is divided into two strands, after heating, enter two sections scorch regions respectively.
The mode that two bursts of resurgent gaseses enter scorch region can have multiple, can enter the reclaimable catalyst bed of one section scorch region and two sections scorch regions respectively from the middle part as two bursts of resurgent gaseses, it is radial bed that this mode is suitable for one section scorch region of two sections scorch regions, and two sections scorch regions are the situation of axial bed.In addition, in two bursts of resurgent gaseses one can be from the middle part of superposed one section scorch region enters the reclaimable catalyst bed of one section scorch region in mode entad, another strand enters the reclaimable catalyst bed of two sections scorch regions in the centrifugal mode from the bottom of two sections scorch regions, this mode is suitable for the situation that two sections scorch regions are radial bed.
The temperature in that aforesaid method enters the resurgent gases of one section scorch region is 350～600 ℃, preferred 400～500 ℃, and the oxygen content in the resurgent gases is 0.1～3.0 volume %, preferred 0.3～2.0 volume %; Enter preferred 400～600 ℃, more preferably 440～550 ℃ of the temperature ins of the resurgent gases of two sections scorch regions, the oxygen content in the resurgent gases is 0.2～5.0 volume %, preferred 0.3～3.0 volume %.
The pressure of catalyst regenerator of the present invention is 0.1～2.0MPa, preferred 0.3～1.0MPa, and reclaimable catalyst is 10～600 minutes, preferred 60～480 minutes in the residence time of scorch region.
The bottom of the described catalyst regenerator of the inventive method is the cooling zone, and top, cooling zone is drying zone.During operation, earlier cold gas is fed the cooling zone of catalyst regenerator, the gas that is come out by the cooling zone mixes with dry gas again, enters drying zone after heating.Described cold gas and dry gas are selected from the miscellany of nitrogen, air or nitrogen and air, and the oxygen content in cold gas and the dry gas is not more than 21 volume %.
The temperature of described drying zone inlet gas is 200～600 ℃, preferred 250～500 ℃.The temperature of cooling zone exit gas is not more than 200 ℃.
The drying zone expellant gas can be discharged system or be introduced the scorch region recycle, and the flue gas that is about to after drying zone expellant gas and the desulfurization is mixed, and the moisture that the drying device removes wherein enters scorch region with the mixed formation of air resurgent gases again.
Can there be a plurality of reactors of polyphone each other in moving bed reaction of the present invention district, preferably includes two to four placed in-line moving bed radial reactors.The arrangement mode of described a plurality of reactors can be and stacks up and down or place side by side, and when adopting four reactors, two reactors can be stacked up and down becomes one group, two bank of reactor is placed side by side again, and catalyst devator is set between every group.
Because light olefin is main superimposed, cracking and the aromatization of taking place in aromatization, be stronger thermopositive reaction, and the naphtha aromtization reaction is thermo-negative reaction.During actually operating, do suitable adjustment according to olefin(e) centent in the ratio of petroleum naphtha blending lighter hydrocarbons and the lighter hydrocarbons to reaction process, the temperature rise of control reaction.Preferable methods is only before first reactor process furnace to be set, and no longer establishes process furnace before the follow-up reactor.Petroleum naphtha and C
3～C
5Lighter hydrocarbons mix after process furnace enters first reactor in moving bed reaction district, enter each follow-up reactor more successively, preferably with C
3～C
5Lighter hydrocarbons be divided into multiply, wherein one mixes through process furnace with petroleum naphtha and enters first reactor, all the other each strand lighter hydrocarbons are introduced respectively in each reactor of first reactor downstream polyphone.
The catalytic temperature of petroleum naphtha of the present invention and light hydrocarbon mixture and catalyzer is 250～600 ℃, preferred 280～560 ℃, pressure is 0.1～2.0MPa, preferred 0.3～1.0MPa, more preferably 0.3～0.8MPa, and suitable naphtha feed mass space velocity is 0.1～5.0h
-1, preferred 0.2～1.0h
-1Reaction raw materials need not to give refining, directly uses to get final product.Described being reflected under the condition that hydrogen-containing gas exists carried out, and the volume ratio of hydrogen and petroleum naphtha is 20～400, preferred 50～200.
The aromatized catalyst active ingredient that the inventive method is used is for high silicon pentasil zeolites or contain zinc or the high silicon pentasil zeolites of gallium, rare earth element and VA family element.
The preferred catalyzer of the inventive method comprises complex carrier and is that content that benchmark calculates is the rare earth oxide of ZnO, 0.1～3.0 quality % of 0.5～3.0 quality % and the VA family element of 1.0～5.0 quality % with the complex carrier that described complex carrier comprises the high silicon five-element circular type zeolite of 30～50 quality % and the binding agent of 50～70 quality %.
The preferred ZSM-5 of described high silicon pentasil zeolites, ZSM-11 or ZSM-12 zeolite, the mol ratio of its silica is preferred 10～200, and more preferably 20～100, described zeolite is h-type zeolite.The preferred mishmetal of described rare earth element wherein contains lanthanum trioxide 20～40 quality %, cerium oxide 40～60 quality %, Praseodymium trioxide 10～18 quality %, Neodymium trioxide 2～10 quality %.The preferred phosphorus of described VA family's element, antimony or bismuth.
Binding agent in the catalyzer is selected from silicon-dioxide or aluminum oxide, preferred aluminum oxide.
Describe preferred implementation of the present invention in detail below in conjunction with accompanying drawing, but the present invention is not limited to this.
The flow process of reaction raw materials is among Fig. 1: from the petroleum naphtha of pipeline 101, the part lighter hydrocarbons of pipeline 102 mix with the hydrogen-containing gas from pipeline 322, after pipeline 103 enters interchanger 104 and reaction product heat exchange, after pipeline 105 enters process furnace 106 heating, enter first reactor 108 through pipeline 107, with wherein catalyzer radially contact the back take place that aromizing sends out should, reacting rear material is through pipeline 109, with enter second reactor 111 after lighter hydrocarbons from pipeline 110 mix, with wherein catalyzer radially contact the back continue to take place aromizing send out should, reacted material enters interchanger 104 and raw material heat exchange after pipeline 301 goes fractionating system through pipeline 112.
The flow process of catalyzer is: from the effusive reclaimable catalyst in reactor 111 bottoms, enter reclaimable catalyst lifter 114 through pipeline 113, be promoted to reclaimable catalyst with circulating nitrogen gas by lift line 115 and separate hopper 201.Reclaimable catalyst and lifting stream of nitrogen gas are separately in separating hopper 201, the stream of nitrogen gas of carrying the part dust enters dust collecting system through pipeline 200, with dust and nitrogen separation wherein, separated nitrogen is re-used as catalyzer and promotes gas recycle (not marking among the figure), reclaimable catalyst enters pressure conversion and flow hopper 203 by catalyzer tremie pipe 202, enters catalyst regenerator 205 through pipeline 204 and regenerates.In catalyst regenerator 205, one section scorch region 208 (radial bed) that reclaimable catalyst passes through buffer zone 206 (axially bed), catalyzer tremie pipe 207 from top to bottom successively, surrounded by screen cloth, catalyzer tremie pipe 209, the two sections scorch regions 210 (radial bed), catalyzer tremie pipe 211, drying zone 212 (axially bed), catalyzer tremie pipe 213, cooling zone 214 (the axially bed) that surround by screen cloth.The regenerated catalyst that comes out from revivifier 205, enter regenerated catalyst lifter 218 through pipeline 215, bottom hopper 216, pipeline 217 successively, regenerated catalyst is separated hopper 220 by the regenerated catalyst that pipeline 219 is promoted to reactor 108 tops with circulating nitrogen gas.In separating hopper 220, regenerated catalyst separates with stream of nitrogen gas, and the stream of nitrogen gas of carrying the part dust enters dust collecting system through pipeline 221, and regenerated catalyst enters reactor 108 by catalyzer tremie pipe 116.In reactor 108, catalyzer relies on self gravitation to enter second reactor 111, relies on self gravitation to enter reclaimable catalyst lifter 114 again, carries out the circulation of a new round again.
In above-mentioned catalyst reaction-reprocessing cycle, promoting the used nitrogen of catalyzer can be replenished by reclaimable catalyst lifter 114, regenerated catalyst lifter 218 and bottom hopper 216 places.
Gas circulation in the catalyst regenerator is: the flue gas that comes out from one section scorch region 208 bottom enters the high-temperature flue gas digester 224 that fume desulfurizing agent is housed through pipeline 223.Fume desulfurizing agent can adopt the known technology of calcium-based desulfurizing agent or other high-temperature flue gas desulfurization.Remove SO through digester 224
2After flue gas come out from pipeline 225, a part directly gives off system by pipeline 226, most of process pipeline 225 enters interchanger 227, after resurgent gases heat exchange after the cooled dehydrated, enter moisture eliminator 231 through pipeline 228, air cooler 229, pipeline 230 successively, with water-content wherein reduce to 2000ppm, preferred 1000ppm, more preferably below the 200ppm after, through the freezing air of pipeline 232 and pipeline 233 or air with become resurgent gases after the mixed gas of nitrogen mixes.Resurgent gases behind pipeline 234, regeneration blower fan 235, enters the hot flue gas heat exchange of interchanger 227 and scorch region generation successively through pipeline 236.A part of then resurgent gases enters electric heater 238 through pipeline 237 and is heated to 350～600 ℃, preferred 400～500 ℃, enter the top of one section scorch region 208 through pipeline 239 from annular space 255, the oxygen content in the control resurgent gases is 0.1～3.0 volume %, preferred 0.3～2.0 volume %; Resurgent gases is the bed by reclaimable catalyst radially with radial inflow, contacts with spent agent and burns, and burns the flue gas that the back produces and enters space 253, discharges revivifiers through pipeline 223 then and carries out recycle.Another part resurgent gases is through pipeline 240, with from the air of pipeline 256 or nitrogen with after AIR MIXTURES is mixed, enter electric heater 242 through pipeline 241 and be heated to 400～600 ℃, preferred 440～550 ℃, oxygen content in the control resurgent gases is 0.2～5.0 volume %, preferred 0.3～3.0 volume %.Resurgent gases enters space 254 through pipeline 243, and with the reclaimable catalyst bed 210 of centrifugal radial by second section scorch region, after catalyzer contacted, the gas of generation carried out recycle through pipeline 223.
From the nitrogen of pipeline 244 and after the air mixed of pipeline 245, enter catalyzer cooling zone 214 through pipeline 246, the gas that comes out from cooling zone 214 through pipeline 248 and part from the nitrogen of pipeline 247 or nitrogen with after Air mixing gas mixes, enter electric heater 250 through pipeline 249 and be heated to 120～600 ℃, preferred 250～500 ℃, enter catalyzer drying zone 212 through pipeline 251 then.From drying zone 212 expellant gas by pipeline 252 discharge systems, or after pipeline 257 enters interchanger 227 heat exchange, the 231 dry back recycles of drying device.
The flow process of Fig. 2 and Fig. 1 is basic identical, and different is that one section scorch region of catalyst regenerator 208 is radial bed, and two sections scorch regions 211 are axial bed.Connect by catalyzer tremie pipe 209 between two sections scorch regions.Enter beds from the resurgent gases of pipeline 239 from the middle part of one section scorch region, contact with reclaimable catalyst.Another burst resurgent gases enters two sections scorch regions 211 through pipeline 243 from the middle part, the gas that produces is through grid distributor 254 ' the enter space 253 that one section scorch region surrounds, after the flue gas of one section scorch region generation mixes, discharge from the top of one section scorch region, circulate through pipeline 223.The excess air of drying zone is directly discharged through pipeline 252.
The difference of Fig. 3 and Fig. 1 flow process is reactive moieties.With after hydrogen-containing gas from pipeline 322 mixes, enter interchanger 104 and reaction product heat exchange from the part lighter hydrocarbons of the petroleum naphtha of pipeline 101, pipeline 102, enter process furnace 106 heating through pipeline 105 through pipeline 103.Mixing raw material after the heating enters first reactor 108 through pipeline 107 and radially contacts the generation aromatization with catalyzer.Reacting rear material is mixed into second reactor 111 through pipeline 109 and lighter hydrocarbons from pipeline 110, radially contacts with catalyzer and proceeds aromatization.Reacting rear material is mixed into the 3rd reactor 114 through pipeline 112 and lighter hydrocarbons from pipeline 113, radially contacts with catalyzer and proceeds aromatization.Reacting rear material is mixed into the 4th reactor 117 through pipeline 115 and lighter hydrocarbons from pipeline 116, radially contacts with catalyzer and proceeds aromatization.Reacted product goes interchanger 104 and reaction raw materials heat exchange through pipeline 118, goes the product fractionating system through pipeline 301 again.
Enter lifter 120 from the effusive catalyzer in second reactor, 111 bottoms through catalyzer tremie pipe 119, utilize circulating nitrogen gas catalyzer to be promoted to the catalyst separating hopper 122 at the 3rd reactor 114 tops through lift line 121, catalyzer and lifting stream of nitrogen gas are separated, carry the stream of nitrogen gas of dust and remove dust collecting system through pipeline 123, the nitrogen circulation of removing behind the dust is used.The catalyzer of separating relies on self gravitation through the 3rd reactor 114 and the 4th reactor 117 through catalyzer tremie pipe 124, enter reclaimable catalyst lifter 126 through catalyzer tremie pipe 125, utilize circulating nitrogen gas the reclaimable catalyst that reclaimable catalyst is promoted to the catalyst regenerator top to be separated hopper 201 through pipeline 127, will catalyzer with promote nitrogen separation after enter pressure conversion and flow control hopper 203, and then the buffer zone that enters the catalyst regenerator top carries out the regeneration of decaying catalyst.
The reactive moieties of flow process shown in Figure 4 is identical with Fig. 3, and regeneration section is identical with Fig. 2.
Fig. 5 is the fractionation schematic flow sheet of the inventive method aromatization reaction products.Through pipeline 301, enter 302 coolings of product water cooler from the material of reactive system, enter primary separator 304, in primary separator 304, be separated into gas-liquid two-phase through pipeline 303.After the pipeline 305 of the gas that is rich in lighter hydrocarbons by primary separator 304 tops enters compressor 306 superchargings, enter second-stage separator 308 through pipeline 307.Carry out gas-liquid separation once more in second-stage separator 308 after, dry gas is discharged through pipeline 317 from second-stage separator 308 cats head, and as hydrogen-containing gas, another part dry gas is through pipeline 318 discharge systems through pipeline 322 Returning reacting systems for wherein a part of dry gas.The liquid of separating from the primary separator of pipeline 309 and through the second-stage separator 308 isolated liquid of pipeline 310 after mixing by pipeline 311, enters stabilizer tower 314 through pump 312 and pipeline 313.Liquefied gas by stabilizer tower 314 top through pipeline 316 discharge systems, stable gasoline at the bottom of the tower through pipeline 315 discharge systems.
Further specify the present invention below by example, but the present invention is not limited to this.
Example 1
(1) preparation complex carrier
Get 67.6 kilograms of pseudo-boehmite powder (Sasol company produces,
Alumina content 74 quality %), under the agitation condition, joining 300 kilograms of concentration is in the aqueous nitric acid of 1.1 quality %, stir 2 hours peptizations after, add 55.0 kilograms of silica and be 60 HZSM-5 zeolite powder (zeolite content 91%), high-speed stirring 3 hours.The slurries of making are splashed in the oil ammonia column that 8 quality % ammoniacal liquor are housed, the wet bulb that forms in the oil ammonia column is taken out, 60 ℃ of dryings 10 hours, 550 ℃ of roastings 3 hours obtain complex carrier, for containing the alumina globule of HZSM-5 zeolite 50 quality %.
(2) preparation catalyzer
Get 50 kilograms of complex carriers, with 50 kilograms contain zinc nitrate 4.7 quality %, (wherein lanthanum trioxide accounts for 31% to chlorination mishmetal 3.0 quality %, cerium oxide 51%, Praseodymium trioxide 14%, Neodymium trioxide 4%), the mixing solutions of phosphoric acid 6.6 quality % dipping is 30 minutes, 110 ℃ of dryings 24 hours, 550 ℃ of roastings 5 hours are handled in 550 ℃ with water vapor then and were obtained catalyst A in 4 hours.
Catalyst A contains zinc oxide 2.0 quality %, phosphorus 2.0 quality %, mixed rare-earth oxide 1.0 quality %, and all the other are complex carrier.The specific surface area of catalyst A is 303m
2/ g.
Example 2
By technical process shown in Figure 1, use catalyst A, with the lighter hydrocarbons shown in virgin naphtha shown in the 60 quality % tables 1 and the 40 quality % tables 2 is that raw material carries out the aromatization test, be reflected under the hydrogen-containing gas round-robin condition and carry out, the content of hydrogen is 21.4 volume % in the hydrogen-containing gas, and the volume ratio of hydrogen and petroleum naphtha is 150.Controlling each reactor feedstocks temperature in is 400 ℃, and reaction pressure is 0.5MPa, and raw material charging mass space velocity is 0.5h
-1Lighter hydrocarbons are divided into two strands, and one mixes with virgin naphtha after process furnace 106 enters first reactor 108, and another strand lighter hydrocarbons directly enter second reactor 111 with the form of cold burden.Revivifier pressure 0.7MPa, one section scorch region resurgent gases temperature in is 470 ℃, oxygen content is 0.5 volume %; Two sections scorch region resurgent gases temperature ins are 480 ℃, and oxygen content is 0.6 volume %, and resurgent gases and reclaimable catalyst volume ratio are 3000: 1, and reclaimable catalyst is 120 minutes in the residence time of revivifier scorch region.The temperature of drying zone inlet gas is 490 ℃, and the temperature of cooling zone exit gas is 165 ℃.Test-results sees Table 3, and the yield of gasoline of relative virgin naphtha is meant C in the table 3
5 +The ratio of gasoline output and the inlet amount of virgin naphtha.
Example 3
By technical process shown in Figure 2, use catalyst A, with the lighter hydrocarbons shown in virgin naphtha shown in the 60 quality % tables 1 and the 40 quality % tables 2 is that raw material carries out the aromatization test, be reflected under the hydrogen-containing gas round-robin condition and carry out, the content of hydrogen is 22.0 volume % in the hydrogen-containing gas, and the volume ratio of hydrogen and petroleum naphtha is 150.All with example 2, different is that resurgent gases enters two sections scorch regions respectively from the middle part in the temperature of the residence time, drying zone and the cooling zone of scorch region for the operational condition of reactive moieties and revivifier and reclaimable catalyst, and test-results sees Table 3.
Comparative Examples 1
Using catalyst A, is that raw material carries out the aromatization test with the lighter hydrocarbons shown in virgin naphtha shown in the 60 quality % tables 1 and the 40 quality % tables 2, and the mode of connection of reactive moieties reactor is reflected under the conditions of non-hydrogen and carries out with example 2.Regeneration section adopts prior art, i.e. pressure conversion and flow control district are positioned at the revivifier bottom; Revivifier is made up of scorch region and drying zone two portions, and wherein scorch region is one section radial bed, burns the flue gas drying of generation, and with additional air mixed after return the revivifier scorch region.The temperature in of each reactor feedstocks of reaction zone is 400 ℃, and reaction pressure 0.5MPa, charging mass space velocity are 0.5h
-1, lighter hydrocarbons are divided into two strands, and one mixes with virgin naphtha after process furnace enters reaction zone from first reactor, and another strand directly enters second reactor with the form of cold burden.Revivifier pressure 0.35MPa, scorch region resurgent gases temperature in is 480 ℃, and oxygen content is 0.75 volume %, and resurgent gases and reclaimable catalyst volume ratio are 3000: 1, and the residence time of reclaimable catalyst in the revivifier scorch region is 120 minutes.Test-results sees Table 3.
Comparative Examples 2
By technical process shown in Figure 1, test conditions and method are with example 2, and different is to be reflected under the conditions of non-hydrogen to carry out, and test-results sees Table 3.
Comparative Examples 3
By technical process shown in Figure 2, test conditions and method are with example 3, and different is to be reflected under the conditions of non-hydrogen to carry out, and test-results sees Table 3.
Example 4
By technical process shown in Figure 3, use catalyst A, with the lighter hydrocarbons shown in virgin naphtha shown in the 60 quality % tables 1 and the 40 quality % tables 2 is that raw material carries out the aromatization test, be reflected under the hydrogen-containing gas round-robin condition and carry out, hydrogen content is 21.3 volume % in the hydrogen-containing gas, and the volume ratio of hydrogen and petroleum naphtha is 100.Controlling each reactor feedstocks temperature in and be 400 ℃, reaction pressure 0.5MPa, charging mass space velocity is 0.5h
-1, lighter hydrocarbons are divided into two strands, and one mixes with virgin naphtha after process furnace enters first reactor 108, and remaining three strands of lighter hydrocarbons directly enters second reactor 111, the 3rd reactor 114, the 4th reactor 117 respectively with the form of cold burden.Control revivifier pressure is 0.7MPa, and one section scorch region resurgent gases temperature in is 470 ℃, and the oxygen content in the resurgent gases is 0.5 volume %; Two sections scorch region resurgent gases temperature ins are 480 ℃, and oxygen content is 0.6 volume % in the resurgent gases, and resurgent gases and reclaimable catalyst volume ratio are 3000: 1, and reclaimable catalyst is 120 minutes in the residence time of revivifier scorch region.The temperature of drying zone inlet gas is 490 ℃, and the temperature of cooling zone exit gas is 165 ℃.Test-results sees Table 4.
Example 5
By technical process shown in Figure 4, use catalyst A, with the lighter hydrocarbons shown in virgin naphtha shown in the 60 quality % tables 1 and the 40 quality % tables 2 is that raw material carries out the aromatization test, be reflected under the hydrogen-containing gas round-robin condition and carry out, hydrogen content is 20.9 volume % in the hydrogen-containing gas, and the volume ratio of hydrogen and petroleum naphtha is 100.All with example 4, different is that resurgent gases enters two sections scorch regions respectively from the middle part in the temperature of the residence time, drying zone and the cooling zone of scorch region for the operational condition of reactive moieties and revivifier and reclaimable catalyst, and test-results sees Table 4.
Comparative Examples 4
Using catalyst A, is that raw material carries out the aromatization test with the lighter hydrocarbons shown in virgin naphtha shown in the 60 quality % tables 1 and the 40 quality % tables 2, and the mode of connection of reactive moieties reactor is reflected under the conditions of non-hydrogen and carries out with example 4.Regeneration section adopts prior art, i.e. pressure conversion and flow control district are positioned at the revivifier bottom; Revivifier is made up of scorch region and drying zone two portions, and wherein scorch region is one section radial bed, burns the flue gas drying of generation, and with additional air mixed after return the revivifier scorch region.The temperature in of each reactor feedstocks of reaction zone is 400 ℃, and reaction pressure 0.5MPa, charging mass space velocity are 0.5h
-1, lighter hydrocarbons are divided into four strands, and one mixes with virgin naphtha after process furnace enters first reactor, and its excess-three thigh lighter hydrocarbons directly enter second reactor, the 3rd reactor, the 4th reactor respectively with the form of cold burden.Control revivifier pressure 0.35MPa, scorch region resurgent gases temperature in is 480 ℃, and wherein oxygen content is 0.75 volume %, and resurgent gases and reclaimable catalyst volume ratio are 3000: 1, and the residence time of reclaimable catalyst in the revivifier scorch region is 120 minutes.Test-results sees Table 4.
Comparative Examples 5
By technical process shown in Figure 3, test conditions and method are with example 4, and different is to be reflected under the non-hydrogen atmosphere to carry out, and test-results sees Table 4.
Comparative Examples 6
By technical process shown in Figure 4, test conditions and method are with example 5, and different is to be reflected under the non-hydrogen atmosphere to carry out, and test-results sees Table 4.
Table 1
| Boiling range, ℃ | ??36～158 |
| Alkane, quality % | ??58.6 |
| Naphthenic hydrocarbon, quality % | ??36.5 |
| Aromatic hydrocarbons, quality % | ??4.9 |
| Basic nitrogen, μ g/g | ??1.4 |
| S content, μ g/g | ??157 |
Table 2
| Component | Content, quality % |
| Propylene | ??0.11 |
| Propane | ??1.33 |
| Trimethylmethane | ??35.49 |
| Iso-butylene | ??0.30 |
| N-butene-1 | ??30.82 |
| Normal butane | ??7.93 |
| Anti-butene-2 | ??10.26 |
| Maleic-2 | ??12.55 |
| Pentane | ??1.21 |
| The butylene total content, quality % | ??53.9 |
Table 3
Table 4
Claims (19)
1. a petroleum naphtha and light-hydrocarbon aromatized method for modifying comprise petroleum naphtha and C
3～C
5Lighter hydrocarbons in the presence of hydrogen-containing gas, contact and carry out the aromatization modification reaction with aromatized catalyst, described upgrading temperature of reaction is that 250～600 ℃, the volume ratio of hydrogen/petroleum naphtha are 20～400.
2. in accordance with the method for claim 1, it is characterized in that containing in the described hydrogen-containing gas hydrogen of 5～99.5 volume %.
3. in accordance with the method for claim 1, it is characterized in that described hydrogen-containing gas is petroleum naphtha and C
3～C
5Lighter hydrocarbons carry out the dry gas that aromatization produces.
4. in accordance with the method for claim 1, it is characterized in that described petroleum naphtha and C
3～C
5The mass ratio of lighter hydrocarbons be 1～9: 9～1.
5. in accordance with the method for claim 1, it is characterized in that described petroleum naphtha is that initial boiling point is that 30～80 ℃, final boiling point are 130～200 ℃ hydrocarbon fraction, described lighter hydrocarbons are mixed c 4.
6. in accordance with the method for claim 1, it is characterized in that described aromatization modification is reflected in moving bed reaction-regenerating unit carries out.
7. according to claim 1 or 6 described methods, it is characterized in that petroleum naphtha, C
3～C
5Lighter hydrocarbons with send into the moving bed reaction district after hydrogen-containing gas mixes, contact with aromatized catalyst and to carry out aromatization, enter the catalyst regenerator top from the effusive reclaimable catalyst in bottom, moving bed reaction district, pass through buffer zone, scorch region, drying zone and cooling zone in the catalyst regenerator from top to bottom successively, the catalyzer after the regeneration reenters moving-burden bed reactor.
8. in accordance with the method for claim 7, it is characterized in that flue gas that the catalyst regenerator scorch region discharges is through desulfurization and drying after, become resurgent gases with air mixed and return scorch region.
9. in accordance with the method for claim 7, it is characterized in that described scorch region comprises at least two sections scorch regions of arranged vertical from top to bottom.
10. in accordance with the method for claim 9, the temperature in that it is characterized in that entering the resurgent gases of one section scorch region is 350～600 ℃, and the oxygen content in the resurgent gases is 0.1～3.0 volume %; The temperature in that enters the resurgent gases of two sections scorch regions is 400～600 ℃, and the oxygen content in the resurgent gases is 0.2～5.0 volume %.
11. in accordance with the method for claim 7, the pressure that it is characterized in that catalyst regenerator is 0.1～2.0MPa, and reclaimable catalyst is 10～600 minutes in the residence time of scorch region.
12. in accordance with the method for claim 7, it is characterized in that earlier cold gas being fed the cooling zone of catalyst regenerator, the gas that is come out by the cooling zone mixes with dry gas again, enter drying zone after heating, described cold gas and dry gas are selected from the miscellany of nitrogen, air or nitrogen and air.
13. in accordance with the method for claim 7, the temperature that it is characterized in that the drying zone inlet gas is 200～600 ℃, and the cooling zone Outlet Gas Temperature is not more than 200 ℃.
14. in accordance with the method for claim 7, it is characterized in that the drying zone expellant gas is discharged system or introduced the scorch region recycle.
15. in accordance with the method for claim 7, it is characterized in that described moving bed reaction district comprises two to four placed in-line moving bed radial reactors.
16. it is characterized in that in accordance with the method for claim 15, with C
3～C
5Lighter hydrocarbons be divided into multiply, wherein one mixes through process furnace with petroleum naphtha and enters first reactor, all the other each strand lighter hydrocarbons are introduced respectively in each reactor of first reactor downstream polyphone.
17. in accordance with the method for claim 1, it is characterized in that described aromatized catalyst active ingredient is high silicon pentasil zeolites or contains zinc or the high silicon pentasil zeolites of gallium, rare earth element and VA family element.
18. in accordance with the method for claim 1, it is characterized in that described aromatized catalyst comprises complex carrier and be that content that benchmark calculates is the rare earth oxide of ZnO, 0.1～3.0 quality % of 0.5～3.0 quality % and the VA family element of 1.0～5.0 quality % with the complex carrier that described complex carrier comprises the high silicon five-element circular type zeolite of 30～50 quality % and the binding agent of 50～70 quality %.
19. according to claim 17 or 18 described methods, it is characterized in that described high silicon pentasil zeolites is selected from ZSM-5, ZSM-11 or ZSM-12 zeolite, described rare earth is a mishmetal, VA family element is phosphorus, antimony or bismuth.
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