CN101747933B - Modifying method for naphtha and light hydrocarbon aromatization - Google Patents
Modifying method for naphtha and light hydrocarbon aromatization Download PDFInfo
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- CN101747933B CN101747933B CN 200810227646 CN200810227646A CN101747933B CN 101747933 B CN101747933 B CN 101747933B CN 200810227646 CN200810227646 CN 200810227646 CN 200810227646 A CN200810227646 A CN 200810227646A CN 101747933 B CN101747933 B CN 101747933B
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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 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, the part low octane value gasoline, light naphthars such as reforming topped oil, condensate oil, partial hydrogenation coker gasoline and straight-run spirit is badly in need of finding suitable processing technology.Although this part petroleum naphtha is applicable to doing ethylene raw, because its vapour pressure is higher, transport more difficultly, if there is no ethylene unit near enterprise, be difficult to ethylene raw.At present, oil refining enterprise is produced main device or the catalytic reforming of aromatic hydrocarbons and clean gasoline with high octane blend component, but catalytic reforming is used the noble metal catalyst of platiniferous, and raw material impurity is required to harshness, invests huge.Late 1970s, due to 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 aromatic hydrocarbons, while by-product hydrogen and high-quality liquefied gas, and its main products BTX aromatics is important industrial chemicals, also can convert, concoct with gasoline is mixed, improves gasoline octane rating.This technology is called aromatization technology.This has opened up an effective way to 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 on a small quantity, for the production of gasoline alkylate and 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, due to its alkene, particularly take butene-2 as main heavy carbon four component concentrations high, burning quality is poor, directly acting as a fuel is very large 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 mixed c 4 the technology of stop bracket gasoline blend component or aromatic hydrocarbons, 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 the olefin(e) centent in civil liquefied gas simultaneously, improve the liquefied gas quality, will there is good economic and social benefit.
CN1032697C discloses a kind of catalytic modification of poor quality gasoline-aromatization method, this method contacts inferior patrol and carries out the echelon reaction with catalyzer, be about to raw material and first pass into first fixed-bed reactor, at 300～550 ℃, 0.05～1.2MPa, weight space velocity 0.2～1.0h
-1conditions of non-hydrogen under reacted, resultant is through gas-liquid separation, C
5above liquid obtains gasoline fraction by fractionation, is less than C in reaction product
4gas send into the second reactor through preheating, at 480～650 ℃, 0.05～1.5MPa, volume space velocity 20～2000h
-1condition under carry out aromatization, the aromizing product, after gas-liquid separation, obtains being rich in gas and the aromatic hydrocarbons mixture of hydrogen.Aromatized catalyst used is comprised of HZSM-5 molecular sieve and the binding agent of modification, described molecular sieve modified component is two or three in Zn, Al or rare earth metal, and binding agent is selected from a kind of or aluminum oxide in aluminum oxide, silicon oxide or clay and the mixture of silicon oxide.Described reactor is two fixed beds that can switch, regenerate in parallel, catalyzer single pass life approximately two weeks, and decaying catalyst by passing into oxygen-containing gas, at 550～700 ℃ of coke burning regenerations in fixed bed.
CN1261535C discloses a kind of method that Gasoline 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, the condition of 300～500 ℃, in fixed-bed reactor with containing the catalyzer contact reacts of HZSM-5, the then dry gas in separated product, liquefied gas and gasoline component.Also can contain the modified component that is selected from antimony or mixed rare-earth oxide in described catalyzer.
CN1212376C discloses a kind of lighter hydrocarbons non-hydrogen modifying catalyst and preparation method and application art.Described catalyzer is comprised of the carrier containing the mixed rare-earth oxide of 0.1～5.0 quality % or weisspiessglanz, 95.0～99.1 quality %, and wherein carrier is comprised 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 through gas-liquid separation, then liquid is separated to the stop bracket gasoline that obtains dry gas, high-quality liquefied gas and low olefin-content.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.The heavy % in consisting of of used catalyst: Zn0.8～3.5, the heavy % of mixed rare earth oxide 0.2～1.5, the heavy % of carrier 95.0～99.0, wherein carrier is comprised of the HZSM-5 zeolite of 50～80 heavy % and the gama-alumina of 20～50 heavy %, in mixed rare earth oxide, containing the heavy % of lanthanum trioxide 20～40, the heavy % of cerium oxide 40～60, the heavy % of Praseodymium trioxide 10～18, Neodymium trioxide 2～10, weighs %.Aromatization carries out in two fixed-bed reactor that switching is regenerated in turn, and the charcoal temperature of regenerated catalyst is 440～550 ℃, and resurgent gases is the nitrogen containing oxygen 0.4～21 volume %.
CN1651141A discloses a kind of aromatized catalyst and preparation and application thereof, and adopting Zn, phosphorus and rare-earth element modified HZSM-5 molecular sieve and REY molecular sieve is the catalyst activity component.The inferior patrol that the octane value of take is lower 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
-1.Catalyst 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 it is carrier that catalyzer be take HZSM-5 zeolite and aluminum oxide, take nickel and zinc as active metal component.Low-carbon (LC) hydrocarbon raw material (mixed c 4 gas), after heating, enters in fixed-bed reactor and contact with catalyzer and carry out aromatization, 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 during liquid, volume space velocity is 0.5～2h
-1.
CN1026316C discloses a kind of technology of aromatization of low carbon hydrocarbon that carbon four hydrocarbon are raw material production aromatic hydrocarbons of take.The metal-modified ZSM-5 molecular sieves such as nickel, zinc or strontium of take are catalyzer, in fixed-bed reactor, make carbon four hydrocarbon carry out aromatization, and reaction product obtains benzene mixed through refrigerated separation; After reaction, flue gas is mixed with the volume ratio of 1:0.5～1.5 with air, be heated to 300～650 ℃ and enter fixed bed, make the coke gasification on catalyst surface, then pass into the unstripped gas activation that accounts for normal aromizing 1～10 % by weight.In light-hydrocarbon aromatized process, the regeneration of reaction and catalyzer hockets.
CN1485414A discloses a kind of method of catalytically cracked gasoline non-hydrogen aromatization and desulfurization, this method is introduced distillate the reactor that molecular sieve catalyst is housed, carry out alkene aromizing and hydrodesulfurization reaction, again reacted product is carried out to 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
-1.This method aromatized catalyst active ingredient used is one or more in ZSM-5, ZSM-11, ZSM-12, ZSM-35, MCM-22, Y molecular sieve and 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 phosphorous and that ZSM-5 molecular sieve gallium is the catalyst activity component of take, and this method contacts the catalyzer of inactivation with oxygen containing resurgent gases, by burning, regenerated.Regeneration can be carried out in fixed bed or moving-bed, and resurgent gases is capable of circulation.This patent also points out that the regeneration of decaying catalyst can be divided into two steps, the first step is used the lower gas of oxygen level to be burnt, the burning process oxygen content gas is 1.0mol%, then oxygen content gas slowly is increased to 7.0mol% and is burnt again, until the out temperature of catalyst bed is basic identical.
USP4724271 discloses a kind of continuous regeneration method of aromatized catalyst, and it is catalyzer that this method is used the ZSM-5 molecular sieve of Ga modification.By decaying catalyst, by the scorch region of revivifier and dry contacting containing oxygen cycle gas, from scorch region recovered flue gas and air mixed, 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 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 the activity that can not recover catalyzer, the need use contains weakly acidic ammonium salt or aqueous acid is processed the catalyzer after burning.The regeneration of decaying catalyst divides four-stage: burn, cooling, with the water vapor air-flow of ammonium salt-containing or weak acid, process and dry, wherein scorch region adopts the mode of resurgent gases circulation to carry out one section of moving-bed to burn.
US4704494 disclose a kind of in fixed-bed reactor by lower carbon number hydrocarbons, as the transformation of propane Catalyst And Method that is aromatic hydrocarbons.Temperature of reaction is 350～600 ℃, the metal-modified zeolite that catalyzer is 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, and the HZSM-5 of zinc modification of take is catalyzer, at 345～815 ℃, under the condition of 0.1～3.5MPa, with CO
2or nitrogen diluted petroleum naphtha, petroleum naphtha and CO during dilution
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 product liquid
10the content of above aromatic hydrocarbons.
US6245219B1 discloses a kind of naphtha reforming method, it is carrier that the catalyzer that this method is used be take mesopore acidic silicic acid salt, at least one is selected from oxide compound or the sulfide of Zn, Ga, In, Fe, Sn and B load, and by with alkaline earth metal hydroxides or silicoorganic compound impregnated carrier, carrying out modification, the preferred ZSM-5 of described silicate.Using the petroleum naphtha that at least contains 25% alkane and naphthenic hydrocarbon is raw material, at 200～538 ℃, and 70～2100KPa, weight space velocity 0.5～25h
-1, hydrogen/hydrocarbon mol ratio 0～10, be preferably under 4 condition and carry out naphtha reforming, C in products therefrom
1～C
4gas yield significantly be reduced to below 20 % by weight, and the C of product liquid
8be rich in p-Xylol in component.
" Liaoming Petrochemical Univ's journal " June the 26th in 2006, volume the 2nd phase 1-4 page reported that low-temperature mixed carbon four is at SO
4 2-/ TiO
2/ HZSM-5, the aromatization that the catalyzer that tackiness agent is gama-alumina carries out under existing." oil and gas chemical industry " the 23rd volume the 1st phase 8-11 page in 1994 has reported that the mixed c 4 that butane or C 4 olefin content are 65% is converted into the method for aromatic hydrocarbons on the Ga/HZSM-5 catalyzer.
Summary of the invention
A kind of method that the purpose of this invention is to provide 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, comprise petroleum naphtha and C
3～C
5lighter hydrocarbons contact with aromatized catalyst and carry out the aromatization modification reaction under the existence of hydrogen-containing gas, 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 under hydrogen-containing gas exists, and has significantly reduced the final boiling point of product and the coke deposit rate of catalyzer.During for moving bed reaction-continuous regeneration set, revivifier is divided into to buffer zone, scorch region, drying zone and cooling zone when the inventive method, the regenerative operation elasticity of catalyzer is increased, Energy Intensity Reduction, favorable regeneration effect, work-ing life extend.And, in the situation that a plurality of reactors of series winding take to inject respectively to each reactor the sectional feeding mode of lighter hydrocarbons, can make temperature of reaction be convenient to control.In addition, scorch region is divided into to two sections, can relaxes the operational condition of scorch region, the loss that makes to burn specific surface area of catalyst in more abundant and burning process reduces.
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 a small amount 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 approximately 210 ℃, and indices all meets environmental requirement.The liquefied gas that produces be take propane and butane as main, and olefin(e) centent is less than 5.0 quality %, after desulfurization is processed, is the high-quality liquefied gas.
The accompanying drawing explanation
Fig. 1 is that the inventive method reaction zone adopts two reactors to stack up and down series winding, and two sections scorch regions of revivifier adopt the process flow diagram of radial structure bed.
Fig. 2 is that the inventive method reaction zone adopts two reactors to stack up and down series winding, and two sections scorch regions of revivifier adopt the process flow diagram of footpath, axial arrangement bed.
Fig. 3 is that the inventive method reaction zone adopts four reactors to stack in twos series winding, and two sections scorch regions of revivifier adopt the process flow diagram of radial structure bed.
Fig. 4 is that the inventive method reaction zone adopts four reactors to stack in twos series winding, and two sections scorch regions of revivifier adopt the process flow diagram of footpath, axial arrangement bed.
The process flow diagram that Fig. 5 is reaction product fractionating system of the present invention.
Embodiment
The inventive method makes low octane value gasoline and lighter hydrocarbons carry out aromatization modification to react under hydrogen exists, and can reduce the coke deposit rate with catalyzer of doing of reformulated gasoline component.While carrying out above-mentioned aromatization modification reaction in the device that uses moving-burden bed reactor and continuous catalyst regenerating, revivifier is divided into to buffer zone, scorch region, drying zone and cooling zone from top to bottom successively, and pressure conversion and flow control district are arranged on to the top of revivifier, make to burn under elevated pressures and carry out, the buffer zone of cooperation revivifier is realized the continuous flow of catalyzer.In addition, but buffer zone preheating catalyst also reduces the operation energy consumption of revivifier.In scorch region, the carbon content of catalyzer is reduced to below 0.2 quality %, recovers the activity of catalyzer.The moisture that Removal of catalyst adsorbs in burning process in drying zone.By cooling zone, that catalyzer is cooling, reduce the requirement to material to the follow-up pipeline of revivifier and equipment.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, can control separately the temperature of each scorch region and the oxygen level of inlet gas, make the revivifier turndown ratio large, burn more abundant, in the situation that scorch region inlet gas oxygen level is lower, can make the local hot spots that the catalyzer burning process produces reduce, burn more evenly, specific surface area of catalyst loss reduces, and extend work-ing life.
Hydrogen-containing gas of the present invention can be the gas that contains hydrogen that any technique produces, and in hydrogen-containing gas, the content of hydrogen is 5～99.5 volume %, and all the other are not for affecting the gas of aromatization.Preferred hydrogen-containing gas is petroleum naphtha and C
3～C
5the lighter hydrocarbons dry gas that carries out the aromatization generation.The noncondensable gas that described dry gas is hydrogen, methane, ethane and ethene, wherein hydrogen content is generally 5～40 volume %.
Described petroleum naphtha is that initial boiling point is the hydrocarbon fraction that 30～80 ℃, final boiling point are 130～200 ℃, the naphtha fraction that preferably virgin naphtha, reforming topped oil, condensate oil or hydrogenation coking process produce.In described lighter hydrocarbons, olefin(e) centent is 15～98 quality %, preferred 40～98 quality %, and all the other are C
3～C
5alkane.Preferred lighter hydrocarbons are mixed c 4, and in mixed c 4, butene content is generally 40～95 quality %.
The present invention's petroleum naphtha used 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: by petroleum naphtha and C
3～C
5lighter hydrocarbons enter the moving bed reaction district after mixing, contact with aromatized catalyst and carry out aromatization, the reclaimable catalyst that will flow out from bottom, moving bed reaction district, through the reclaimable catalyst lifter, the spent riser line, reclaimable catalyst separates hopper and the pressure conversion enters catalyst regenerator with the flow control district from top, pass through successively from top to bottom the buffer zone in catalyst regenerator, scorch region, drying zone and cooling zone, pass into the coke burning regeneration that oxygen containing resurgent gases is carried out reclaimable catalyst in scorch region, again regenerated catalyst is promoted, enter moving-burden bed reactor from top.
Described scorch region comprises at least two sections scorch regions arranged vertically from top to bottom, comes one section preferred radial bed of scorch region on top, and two sections scorch regions that come bottom can be radial bed or axial bed.The flue gas of two sections scorch region generations can be discharged from bottom or the top of one section scorch region.
The flue gas that above-mentioned catalyst regenerator scorch region is discharged, after desulfurization and drying, becomes resurgent gases with air mixed and returns to scorch region.Preferred method be the flue gas of will discharge from scorch region after desulfurization and drying, be mixed into resurgent gases with the gas mixture of air or air and nitrogen, resurgent gases is divided into to two strands, enter respectively two sections scorch regions after heating.
The mode that two bursts of resurgent gaseses enter scorch region can have multiple, as two bursts of resurgent gaseses can enter respectively the reclaimable catalyst bed of one section scorch region and two sections scorch regions from middle part, it is radial bed that this mode is suitable for one section scorch region of two sections scorch regions, two sections situations that scorch region is axial bed.In addition, one in two bursts of resurgent gaseses can enter the reclaimable catalyst bed of one section scorch region from the middle part of superposed one section scorch region in centripetal mode, another strand enters the reclaimable catalyst bed of two sections scorch regions from the bottom of two sections scorch regions in centrifugal mode, 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 ℃, preferably 400～500 ℃, and the oxygen content in resurgent gases is 0.1～3.0 volume %, preferably 0.3～2.0 volume %; Enter preferably 400～600 ℃, more preferably 440～550 ℃ of the temperature ins of the resurgent gases of two sections scorch regions, the oxygen content in 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, preferably 60～480 minutes in the residence time of scorch region.
The bottom of the described catalyst regenerator of the inventive method is cooling zone, and top, cooling zone is drying zone.During operation, ，You cooling zone, the cooling zone gas out that first cold gas is passed into to catalyst regenerator mixes with dry gas again, after heating, enters drying zone.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 dry gas is not more than 21 volume %.
The temperature of described drying zone inlet gas is 200～600 ℃, preferably 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 be about to from drying zone expellant gas and desulfurization is mixed, and the moisture that the drying device removes wherein enters scorch region with the mixed resurgent gases that forms of air again.
Can there be a plurality of reactors of series winding each other in moving bed reaction of the present invention district, preferably includes the moving bed radial reactor of two to four series connection.The arrangement mode of described a plurality of reactors can be and stacks up and down or place side by side, while adopting four reactors, two reactors can be stacked up and down and becomes one group, then two group reaction devices are placed side by side, and catalyst devator is set between every group.
Due to light olefin main superimposed, cracking and aromatization of occurring in aromatization, be stronger thermopositive reaction, and the naphtha aromtization reaction is thermo-negative reaction.During actually operating, do suitable adjustment to reaction process according to olefin(e) centent in the ratio of petroleum naphtha blending lighter hydrocarbons and lighter hydrocarbons, control the temperature rise of reaction.Preferred method is only before first reactor, process furnace to be set, and no longer establishes process furnace before follow-up reactor.Petroleum naphtha and C
3～C
5lighter hydrocarbons mix and to enter first reactor in moving bed reaction district by process furnace, then enter successively each follow-up reactor, preferably by C
3～C
5lighter hydrocarbons be divided into multiply, wherein one mixes through process furnace and enters first reactor with petroleum naphtha, all the other each strand of lighter hydrocarbons are introduced respectively in each reactor of first reactor downstream series winding.
The catalytic temperature of petroleum naphtha of the present invention and light hydrocarbon mixture and catalyzer is 250～600 ℃, preferably 280～560 ℃, pressure is 0.1～2.0MPa, preferably 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
-1.Reaction raw materials is refining without giving, and directly uses and gets final product.Under the condition that described reaction exists at hydrogen-containing gas, carry out, the volume ratio of hydrogen and petroleum naphtha is 20～400, preferably 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 take the rare earth oxide of ZnO, 0.1～3.0 quality % that content that complex carrier is benchmark is 0.5～3.0 quality % and the VA family element of 1.0～5.0 quality %, and 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/alumina preferably 10～200, more preferably 20～100, described zeolite is h-type zeolite.The preferred mishmetal of described rare earth element, wherein containing 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 catalyzer is selected from silicon-dioxide or aluminum oxide, preferential oxidation aluminium.
Describe the preferred embodiment of the present invention in detail below in conjunction with accompanying drawing, but the present invention is not limited to this.
In Fig. 1, the flow process of reaction raw materials is: 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 the first reactor 108 through pipeline 107, radially contacting with catalyzer wherein that rear generation aromizing sends out should, reacting rear material is through pipeline 109, with enter the second reactor 111 after lighter hydrocarbons from pipeline 110 mix, radially contacting with catalyzer wherein that rear continuation generation aromizing sends out should, reacted material enters interchanger 104 through pipeline 112 and goes fractionating system with the raw material heat exchange by pipeline 301.
The flow process of catalyzer is: the reclaimable catalyst flowed out from reactor 111 bottoms, enter reclaimable catalyst lifter 114 through pipeline 113, and be promoted to reclaimable catalyst with circulating nitrogen gas by lift line 115 and separate hopper 201.In separating hopper 201, reclaimable catalyst and lifting stream of nitrogen gas are separately, the stream of nitrogen gas of carrying the part dust enters dust collecting system through pipeline 200, by dust and nitrogen separation wherein, isolated nitrogen is re-used as catalyzer and promotes gas recycle (not marking in figure), reclaimable catalyst enters pressure conversion and flow hopper 203 by catalyzer tremie pipe 202, enters catalyst regenerator 205 through pipeline 204 and is regenerated.In catalyst regenerator 205, reclaimable catalyst passes through buffer zone 206 (axially bed), catalyzer tremie pipe 207, the one section scorch region 208 (radial bed) surrounded by screen cloth, catalyzer tremie pipe 209, the two sections scorch regions 210 (radial bed) that surrounded by screen cloth, catalyzer tremie pipe 211, drying zone 212 (axially bed), catalyzer tremie pipe 213, cooling zone 214 (axially bed) from top to bottom successively.The regenerated catalyst out from revivifier 205, enter regenerated catalyst lifter 218 through pipeline 215, bottom hopper 216, pipeline 217 successively, the regenerated catalyst that regenerated catalyst is promoted to reactor 108 tops by pipeline 219 with circulating nitrogen gas separates hopper 220.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 the second reactor 111, then relies on self gravitation to enter reclaimable catalyst lifter 114, re-starts the circulation of a new round.
In above-mentioned catalyst reaction-reprocessing cycle, promoting catalyzer nitrogen used can be supplemented by reclaimable catalyst lifter 114, regenerated catalyst lifter 218 and bottom hopper 216 places.
Gas circulation in catalyst regenerator is: from one section scorch region 208 bottoms flue gas out, enter 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 from pipeline 225 out, a part directly gives off system by pipeline 226, most of process pipeline 225 enters interchanger 227, after resurgent gases heat exchange after cooled dehydrated, enter moisture eliminator 231 through pipeline 228, air cooler 229, pipeline 230 successively, by water-content wherein be down to 2000ppm, preferably 1000ppm, more preferably below 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 after pipeline 234, regeneration blower fan 235, enters the hot flue gas heat exchange of interchanger 227 and scorch region generation successively through pipeline 236.Then a part of resurgent gases enters electric heater 238 through pipeline 237 and is heated to 350～600 ℃, preferably 400～500 ℃, enter the top of one section scorch region 208 from annular space 255 through pipeline 239, the oxygen content of controlling in resurgent gases is 0.1～3.0 volume %, preferably 0.3～2.0 volume %; Resurgent gases, contacts and burns with spent agent radially by the bed of reclaimable catalyst with radial inflow, and the flue gas that burns rear generation enters space 253, then through pipeline 223, discharges revivifier and carries out recycle.Another part resurgent gases is through pipeline 240, with air from pipeline 256 or nitrogen with after the mixture of air mixes, enter electric heater 242 through pipeline 241 and be heated to 400～600 ℃, preferably 440～550 ℃, the oxygen content of controlling in resurgent gases is 0.2～5.0 volume %, preferably 0.3～3.0 volume %.Resurgent gases enters space 254 through pipeline 243, and with centrifugal radial, by the reclaimable catalyst bed 210 of second segment scorch region, after catalyzer contacts, the gas of generation carries 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, from cooling zone 214 gas out through pipeline 248 and part from the nitrogen of pipeline 247 or nitrogen with after the mixed gas of air mixes, enter electric heater 250 through pipeline 249 and be heated to 120～600 ℃, preferably 250～500 ℃, then through pipeline 251, enter catalyzer drying zone 212.From drying zone 212 expellant gas by pipeline 252 discharge systems, or after pipeline 257 enters interchanger 227 heat exchange, recycles after drying device 231 is dry.
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.Between two sections scorch regions, by catalyzer tremie pipe 209, connect.Resurgent gases from pipeline 239 enters beds from the middle part of one section scorch region, with reclaimable catalyst, contacts.Another burst of resurgent gases enters two sections scorch regions 211 from middle part through pipeline 243, the gas produced enters through grid distributor 254 ＇ the space 253 that one section scorch region surrounds, after the flue gas produced with one section scorch region mixes, from the top of one section scorch region, discharge, circulated 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, through pipeline 103, enter interchanger 104 and reaction product heat exchange from the part lighter hydrocarbons of the petroleum naphtha of pipeline 101, pipeline 102, through pipeline 105, enter process furnace 106 heating.Mixing raw material after heating enters the first reactor 108 through pipeline 107 and radially contacts the generation aromatization with catalyzer.Reacting rear material is mixed into the second reactor 111 through pipeline 109 and the lighter hydrocarbons from pipeline 110, with catalyzer, radially contacts and proceeds aromatization.Reacting rear material is mixed into the 3rd reactor 114 through pipeline 112 and the lighter hydrocarbons from pipeline 113, with catalyzer, radially contacts and proceeds aromatization.Reacting rear material is mixed into the 4th reactor 117 through pipeline 115 and the lighter hydrocarbons from pipeline 116, with catalyzer, radially contacts and proceeds aromatization.Reacted product goes interchanger 104 and reaction raw materials heat exchange through pipeline 118, then goes the product fractionating system through pipeline 301.
The catalyzer flowed out from the second reactor 111 bottoms enters lifter 120 through catalyzer tremie pipe 119, utilize circulating nitrogen gas through lift line 121, catalyzer to be promoted to the catalyst separating hopper 122 at the 3rd reactor 114 tops, 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 after 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, the reclaimable catalyst that utilizes circulating nitrogen gas, through pipeline 127, reclaimable catalyst is promoted to the catalyst regenerator top separates hopper 201, 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 Fig. 4 is identical with Fig. 3, and regeneration section is identical with Fig. 2.
The fractionation process schematic diagram that Fig. 5 is the inventive method aromatization reaction products.Through pipeline 301, enter product water cooler 302 cooling from the material of reactive system, through pipeline 303, enter primary separator 304, in primary separator 304, be separated into gas-liquid two-phase.After the pipeline 305 of the gas that is rich in lighter hydrocarbons by primary separator 304 tops enters compressor 306 superchargings, through pipeline 307, enter second-stage separator 308.Again carry out gas-liquid separation in second-stage separator 308 after, dry gas is discharged through pipeline 317 from second-stage separator 308 tower tops, and wherein as hydrogen-containing gas, another part dry gas is through pipeline 318 discharge systems through pipeline 322 Returning reacting systems for a part of dry gas.The liquid of separating from the primary separator of pipeline 309 and through the isolated liquid of second-stage separator 308 of pipeline 310, after mixing by pipeline 311, enter stabilizer tower 314 through pump 312 and pipeline 313.Liquefied gas by stabilizer tower 314 top through pipeline 316 discharge systems, stable gasoline from the bottom of tower through pipeline 315 discharge systems.
Further illustrate the present invention below by example, but the present invention is not limited to this.
Example 1
(1) prepare complex carrier
(Sasol company produces, PURAL to get 67.6 kilograms of pseudo-boehmite powder
sB, alumina content 74 quality %), under agitation condition, join in the aqueous nitric acid that 300 kilograms of concentration are 1.1 quality %, after stirring 2 hours peptizations, add the HZSM-5 zeolite powder that 55.0 kilograms of silica/alumina molar ratio are 60 (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 oil ammonia column is taken out, 60 ℃ of dryings 10 hours, 550 ℃ of roastings 3 hours, obtain complex carrier, is the alumina globule containing HZSM-5 zeolite 50 quality %.
(2) Kaolinite Preparation of Catalyst
Get 50 kilograms of complex carriers, with 50 kilograms containing 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, then process and within 4 hours, obtain catalyst A in 550 ℃ with water vapor.
Catalyst A is containing 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
Press the technical process shown in Fig. 1, use catalyst A, the lighter hydrocarbons shown in the virgin naphtha shown in 60 quality % tables 1 and 40 quality % tables 2 of take carry out the aromatization test as raw material, reaction is carried out under the condition of hydrogen-containing gas circulation, in hydrogen-containing gas, the content of hydrogen is 21.4 volume %, 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
-1.Lighter hydrocarbons are divided into two strands, and one mixes with virgin naphtha by process furnace 106 and enters the first reactor 108, and another strand of lighter hydrocarbons directly enter the 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 is in Table 3, and in table 3, the yield of gasoline of relative virgin naphtha refers to C
5 +the ratio of gasoline output and the inlet amount of virgin naphtha.
Example 3
Press the technical process shown in Fig. 2, use catalyst A, the lighter hydrocarbons shown in the virgin naphtha shown in 60 quality % tables 1 and 40 quality % tables 2 of take carry out the aromatization test as raw material, reaction is carried out under the condition of hydrogen-containing gas circulation, in hydrogen-containing gas, the content of hydrogen is 22.0 volume %, and the volume ratio of hydrogen and petroleum naphtha is 150.The operational condition of reactive moieties and revivifier and reclaimable catalyst are in the temperature of the residence time, drying zone and the cooling zone of scorch region all with example 2, and different is that resurgent gases enters respectively two sections scorch regions from middle part, and test-results is in Table 3.
Comparative Examples 1
Use catalyst A, the lighter hydrocarbons shown in the virgin naphtha shown in 60 quality % tables 1 and 40 quality % tables 2 of take carry out the aromatization test as raw material, and the mode of connection of reactive moieties reactor is with example 2, and reaction is carried out under conditions of non-hydrogen.Regeneration section adopts prior art, i.e. pressure conversion is positioned at the revivifier bottom with the flow control district; Revivifier is comprised 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 supplementary air mixed after return to the revivifier scorch region.The temperature in of each reactor feedstocks of reaction zone is 400 ℃, reaction pressure 0.5MPa, and the charging mass space velocity is 0.5h
-1, lighter hydrocarbons are divided into two strands, and one mixes by process furnace and enters reaction zone from the first reactor with virgin naphtha, and another burst of direct form with cold burden enters the second reactor.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 is in Table 3.
Comparative Examples 2
Press the technical process shown in Fig. 1, test conditions and method are with example 2, and different is that reaction is carried out under conditions of non-hydrogen, and test-results is in Table 3.
Comparative Examples 3
Press the technical process shown in Fig. 2, test conditions and method are with example 3, and different is that reaction is carried out under conditions of non-hydrogen, and test-results is in Table 3.
Example 4
Press the technical process shown in Fig. 3, use catalyst A, the lighter hydrocarbons shown in the virgin naphtha shown in 60 quality % tables 1 and 40 quality % tables 2 of take carry out the aromatization test as raw material, reaction is carried out under the condition of hydrogen-containing gas circulation, in hydrogen-containing gas, hydrogen content is 21.3 volume %, 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 by process furnace and enters the first reactor 108, and remaining three strands of lighter hydrocarbons directly enters respectively the second reactor 111, the 3rd reactor 114, the 4th reactor 117 with the form of cold burden.Controlling revivifier pressure is 0.7MPa, and one section scorch region resurgent gases temperature in is 470 ℃, and the oxygen content in resurgent gases is 0.5 volume %; Two sections scorch region resurgent gases temperature ins are 480 ℃, and in resurgent gases, 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 is in Table 4.
Example 5
Press the technical process shown in Fig. 4, use catalyst A, the lighter hydrocarbons shown in the virgin naphtha shown in 60 quality % tables 1 and 40 quality % tables 2 of take carry out the aromatization test as raw material, reaction is carried out under the condition of hydrogen-containing gas circulation, in hydrogen-containing gas, hydrogen content is 20.9 volume %, and the volume ratio of hydrogen and petroleum naphtha is 100.The operational condition of reactive moieties and revivifier and reclaimable catalyst are in the temperature of the residence time, drying zone and the cooling zone of scorch region all with example 4, and different is that resurgent gases enters respectively two sections scorch regions from middle part, and test-results is in Table 4.
Comparative Examples 4
Use catalyst A, the lighter hydrocarbons shown in the virgin naphtha shown in 60 quality % tables 1 and 40 quality % tables 2 of take carry out the aromatization test as raw material, and the mode of connection of reactive moieties reactor is with example 4, and reaction is carried out under conditions of non-hydrogen.Regeneration section adopts prior art, i.e. pressure conversion is positioned at the revivifier bottom with the flow control district; Revivifier is comprised 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 supplementary air mixed after return to the revivifier scorch region.The temperature in of each reactor feedstocks of reaction zone is 400 ℃, reaction pressure 0.5MPa, and the charging mass space velocity is 0.5h
-1, lighter hydrocarbons are divided into four strands, and one mixes by process furnace and enters the first reactor with virgin naphtha, and its excess-three thigh lighter hydrocarbons directly enter respectively the second reactor, the 3rd reactor, the 4th reactor 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 is in Table 4.
Comparative Examples 5
Press the technical process shown in Fig. 3, test conditions and method are with example 4, and different is that reaction is carried out under non-hydrogen atmosphere, and test-results is in Table 4.
Comparative Examples 6
Press the technical process shown in Fig. 4, test conditions and method are with example 5, and different is that reaction is carried out under non-hydrogen atmosphere, and test-results is in 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 contact with aromatized catalyst and carry out the aromatization modification reaction under the existence of hydrogen-containing gas, described upgrading temperature of reaction is that 250～600 ℃, the volume ratio of hydrogen/petroleum naphtha are 20～400, described petroleum naphtha is that initial boiling point is the hydrocarbon fraction that 30～80 ℃, final boiling point are 130～200 ℃, is selected from the naphtha fraction that virgin naphtha, reforming topped oil, condensate oil or hydrogenation coking process produce.
2. in accordance with the method for claim 1, it is characterized in that the hydrogen that contains 5～99.5 volume % in described hydrogen-containing gas.
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
5the lighter hydrocarbons dry gas that carries out the aromatization generation.
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 lighter hydrocarbons are mixed c 4.
6. in accordance with the method for claim 1, it is characterized in that the reaction of described aromatization modification carries out in moving bed reaction-regenerating unit.
7. according to the described method of claim 1 or 6, 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 carry out aromatization, the reclaimable catalyst flowed out from bottom, moving bed reaction district enters the catalyst regenerator top, pass through successively from top to bottom buffer zone, scorch region, drying zone and cooling zone in catalyst regenerator, the catalyzer after regeneration reenters moving-burden bed reactor.
8. in accordance with the method for claim 7, it is characterized in that the flue gas of catalyst regenerator scorch region discharge, after desulfurization and drying, becomes resurgent gases with air mixed and returns to 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 arranged vertically 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 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 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 first cold gas being passed into the cooling zone of catalyst regenerator, by cooling zone, gas out 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 to 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 the moving bed radial reactor of two to four series connection.
16. in accordance with the method for claim 15, it is characterized in that the lighter hydrocarbons of C3～C5 are divided into to multiply, wherein one mixes through process furnace and enters first reactor with petroleum naphtha, and all the other each strand of lighter hydrocarbons are introduced respectively in each reactor of first reactor downstream series winding.
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 take the rare earth oxide of ZnO, 0.1～3.0 quality % that content that complex carrier is benchmark is 0.5～3.0 quality % and the VA family element of 1.0～5.0 quality %, 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 the described method of claim 17 or 18, 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 mishmetal, VA family element is phosphorus, antimony or bismuth.
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| CN109401785B (en) * | 2017-08-16 | 2021-09-07 | 中国石油化工股份有限公司 | Naphtha modification method |
| CN109401781B (en) * | 2017-08-16 | 2021-09-07 | 中国石油化工股份有限公司 | Naphtha and light hydrocarbon modification method |
| CN109569714B (en) * | 2017-09-28 | 2021-11-16 | 中国石油化工股份有限公司 | Fischer-Tropsch synthesis naphtha conversion catalyst and preparation method thereof |
| CN107941047A (en) * | 2017-11-21 | 2018-04-20 | 宁波东鼎石化装备有限公司 | A kind of heat exchanger, the four Hydrogenation iso-butane device and method of mixing carbon using the heat exchanger |
| CN111073693B (en) * | 2018-10-19 | 2022-01-04 | 中国石油化工股份有限公司 | Naphtha modification method |
| CN111073694B (en) * | 2018-10-19 | 2022-01-04 | 中国石油化工股份有限公司 | Naphtha and light hydrocarbon modification method |
| CN109280561B (en) * | 2018-11-29 | 2020-11-27 | 北京惠尔三吉绿色化学科技有限公司 | Method for preparing propylene and coproducing aromatic hydrocarbon through naphtha or light hydrocarbon low-temperature catalytic reaction |
| CN112920837A (en) * | 2021-02-03 | 2021-06-08 | 崔秋生 | Naphtha and pre-ether C4 mixed aromatization device and use method thereof |
| CN112920838A (en) * | 2021-02-03 | 2021-06-08 | 崔秋生 | Naphtha and methanol mixed aromatization device and use method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1724166A (en) * | 2005-07-19 | 2006-01-25 | 白跃华 | Tech. for regenerating reforming catalyst back charring and its regenerator |
| CN101020844A (en) * | 2006-02-15 | 2007-08-22 | 中国科学院大连化学物理研究所 | Catalyst for reducing olefin content in mixed material of liquified gas and gasoline |
-
2008
- 2008-11-28 CN CN 200810227646 patent/CN101747933B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1724166A (en) * | 2005-07-19 | 2006-01-25 | 白跃华 | Tech. for regenerating reforming catalyst back charring and its regenerator |
| CN101020844A (en) * | 2006-02-15 | 2007-08-22 | 中国科学院大连化学物理研究所 | Catalyst for reducing olefin content in mixed material of liquified gas and gasoline |
Non-Patent Citations (1)
| Title |
|---|
| 叶娜.纳米ZSM-5沸石上C_4液化气低温芳构化反应研究.《大连理工大学硕士学位论文》.2006,正文37-38页. * |
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