CN1216315A - Continuous catalytic reforming combined with zeolitic reforming for increased BTX yield - Google Patents
Continuous catalytic reforming combined with zeolitic reforming for increased BTX yield Download PDFInfo
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- CN1216315A CN1216315A CN 97114124 CN97114124A CN1216315A CN 1216315 A CN1216315 A CN 1216315A CN 97114124 CN97114124 CN 97114124 CN 97114124 A CN97114124 A CN 97114124A CN 1216315 A CN1216315 A CN 1216315A
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Abstract
A naphtha feedstock is catalytically reformed in a combination sequence comprising a continuous-reforming zone, consisting essentially of a moving-bed catalytic reforming zone with continuous regeneration of catalyst particles, followed by a zeolitic-reforming zone containing a catalyst comprising a platinum-group metal and a nonacidic zeolite operating on the effluent from the combination reforming zone. The unique process combination permits higher severity, higher BTX aromatics yields and/or increased throughput in the continuous-reforming zone, thus showing surprising benefits over prior-art processes, and is particularly useful in upgrading existing moving-bed reforming facilities with continuous catalyst regeneration.
Description
The present invention relates to a kind of improving one's methods of being used for that hydrocarbon transforms, is the improving one's methods of catalytic reforming that is used for gasoline boiling range cut hydrocarbon specifically.
In recent years, occurred using moving-bed of catalyst to reform and be the method for avoiding its inactivation to carry out the continuous catalytic reforming of cyclic regeneration moving-bed of catalyst, this method is occupied an leading position in novel reformer unit is operated.The world today, almost each the refining of petroleum factory of aromatic hydrocarbons intermediate that is used for oil-chemical industry or the detonans of engine is had a gasoline component of high damping for production has all adopted gasoline boiling range cut hydrocarbon feed has been carried out catalytic reforming.For the requirement of aromatic hydrocarbons supply greater than the aromatic hydrocarbons raw materials for production.Yet because environmental limit and need improve gasolines to the raising of the requirement of high performance internal combustion engine, this requirement also requires to improve with gasoline octane rating and comes the damping action of metric gasoline component to detonans.Therefore, the catalytic reforming unit in certain refinery usually must improve its processing power to satisfy the needs that these increase aromatic hydrocarbons and improve the octane value of gasoline.The grade that people wish to be applied to continuous catalytic reforming technology improves process and can effectively utilize existing reformation and catalysis-reclaim equiment.
Generally speaking, catalytic reforming is applied in the raw material of rich paraffinic hydrocarbons and naphthenic hydrocarbon and by various reactions and carries out catalytic reforming: described reaction is that naphthenic hydrocarbon is dehydrogenated to aromatic hydrocarbons, paraffin dehydrogenation is cyclized into light hydrocarbon, paraffinic hydrocarbons and naphthenic hydrocarbon be isomerizated into light hydrocarbon, the dealkylation of alkylaromatic hydrocarbon becomes light hydrocarbon, the hydrocracking of paraffinic hydrocarbons becomes light hydrocarbon, and generates sedimentation of coke on catalyzer.The diversion that the needs of increase aromatic hydrocarbons and boosting of octane rating make people is to paraffinic hydrocarbons-dehydrocyclization, and this effect is than other aromatization, and is not too favourable from traditional reformation thermodynamics and kinetics aspect.When suppressing the coke generation to greatest extent, produce tangible leverage to improving desirable product yield through catalytic reforming by the hydrocracking reaction that promotes dehydrocyclization reaction and inhibition and its competition is next.Continuous catalytic reforming can be used for dehydrocyclization effectively with the high activated catalyst that produces by the cyclic regeneration catalyzer, with lower pressure operation.
The catalytic validity of reformation that contains the dehydrocyclization that is used for paraffinic hydrocarbons of nonacid L-zeolite and platinum metals is known by people in the art, discloses to use these reforming catalysts to produce aromatic hydrocarbons from paraffinic hydrocarbons raffinate and naphthenic hydrocarbon.Yet this dehydrocyclization technology its process of industrialization in nervous and lasting evolution is very slow.The invention provides a kind of new method, use the L-zeolite technology to replenish.
US-A-4,645,586 point out to make the reforming catalyst of the bifunctional of containing metal oxide carrier and VIII family metal to contact with raw material, then make raw material and contain large aperture zeolite, the zeolitic reforming catalyst contact of preferred L zeolite, by using first kind of traditional reforming catalyst to flow in second kind of non-acid high-selectivity catalyst, overcome the defective of prior art so that a product stream to be provided.But do not advise CONTINUOUS REFORMER in BUSS in the document.
US-A-4,985,132 point out a kind of subregion catalystic reforming method, the prime area contains the catalyzer of the platinum-germanium on refractory inorganic oxides and contains a moving-bed system that is connected with the continuous catalyst regeneration system rapidly with catalyst area in the end.Yet, the L-zeolite component is not disclosed.
US-A-5,190,638 point out with successive catalyst regeneration mode in the moving-bed, produce the reformation that a part of reformate flows to the second reformation zone, preferably use a kind of at 0.791-0.354mPa (100-500 pound/inch
2) contain the catalyzer of acidic functionality, but the document does not have a kind of non-acidic zeolite catalyst of public use.
US-A-3,652,231 point out the regeneration of a kind of reforming catalyst in mobile post and adjustment again, but the document is not advised the reformation of dual area.
The purpose of this invention is to provide a kind of catalystic reforming method that improves the product yield structure.
Another object of the present invention is to improve the output of BTX aromatic hydrocarbons and the performance of CONTINUOUS REFORMER method.
The present invention is based on following discovery, and the combination that continuous catalytic reforming and zeolite are reformed shows that having improved the BTX aromatic production has greatly obtained outstanding improvement with this method of use with respect to prior art.
A combination that the wide region embodiment is a kind of catalystic reforming method of the present invention, by the processing hydrocarbon feed of continuous catalytic reforming success, above-mentioned continuous catalytic reforming comprises a continuous catalyst regeneration moving-bed and reforms regional at a zeolite that contains the catalyzer of being made up of non-acidic zeolite and platinum metals in the method.Preferred use a kind of catalyzer to carry out CONTINUOUS REFORMER, this catalyzer contains a refractory inorganic oxide carrier material of either, platinum metals and halogen, and this catalyzer at least can semi-continuous regeneration and is adjusted and turn back to continuous reforming reactor again.Preferred non-acidic zeolite is a L-zeolite, most preferably potassium type L-zeolite.Being preferred for platinum metals a kind of or two kinds of successive zeolitic reforming catalysts is platinum.
Preferably reform zone processing from first kind of effluent of continuous catalytic reforming and without separated free hydrogen at zeolite.
On the other hand, the present invention includes and add a zeolite and reform the zone with the turnout that enlarges existing CONTINUOUS REFORMER processing unit (plant) and/or improve the quality of products.
Fig. 1 illustrates the productive rate with the BTX-aromatic hydrocarbons of the productivity ratio integrated processes of the present invention of prior art.
This hydrocarbon feed contains alkane and cycloalkane, also can contain aromatic hydrocarbons and a small amount of gasoline boiling range alkene. Operable raw material comprises straight-run naphtha, natural gasoline, and synthetic naphtha, hot-working petroleum, Catalytically cracked gasoline, part reformed naphtha or from the raffinate that extracts aromatic hydrocarbons. The scope of distillation can Be full boiling range naphtha, its initial boiling point is generally 40-80 ℃, and final boiling point is 160-210 ℃, Perhaps in a narrow scope, has lower final boiling point. Paraffinic feed is for example former from the Middle East The naphtha of oil, its final boiling point is conducive to processing at 100-175 ℃, because this technology can be effective Ground dehydrocyclization alkane becomes aromatic hydrocarbons. The raffinate that extracts from aromatic hydrocarbons mainly contains and can be transformed into The low value C of valuable B-T-X aromatic hydrocarbons6-C
8Naphtha is that preferred available alternative hydrocarbon is former Material.
Hydrocarbon feed of the present invention contains a small amount of sulfide, generally be less than 10ppm (according to element benchmark meter), preferably prepare hydrocarbon feed from the raw material that contains impurity by traditional pre-treatment step, the for example hydrotreatment of above-mentioned pre-treatment step, hydrofinishing, or hydrodesulfurization effect are with these impurity such as sulfurous compound, nitrogen-containing compound, oxide is separately converted to H2S,NH
3And H2O, they can lead to Crossing distillation tells from hydrocarbon. A kind of catalyst as known in the art is used in preferred this conversion, and this is urged Change agent and contain a kind of inorganic oxide carrier and VI B (6) family and the VIII that are selected from the periodic table of elements (9-10) metal of family (referring to Cotton and Wilkinson, inorganic chemistry progress (Advanced Inorganic Chemistry), John Wiley﹠Sons (the 5th edition, 1988)). Except Outside traditional hydrogen was processed, pre-treatment step can also comprise and can remove sulfide and other impurity The sorbent contact only comprises that perhaps the latter carries out preliminary treatment as alternative alternative. These Sorbent can include but not limited to zinc oxide, sponge iron, and high surface sodium, high surface area alumina, Active carbon and molecular sieve. Can obtain good result with aluminium oxide-nickel sorbent. Preferred pretreatment Step provides a kind of in the prior art low sulfur content of disclosed reformer feed as wishing Hydrocarbon feed, its sulfur content for example are 1ppm-0.1ppm (100ppb).
Pre-treatment step is very low by the sulfur content in the hydrocarbon feed being down in conjunction with the reforming catalyst of relatively anti-sulphur with the sulphur sorbent, and the raw material of the reforming catalyst of anti-sulphur contact stain contains H in order to most of sulfide is transformed into2The eliminating logistics of S. Contain H2The logistics of S contacts advantageously zinc oxide or magnesian sulphur sorbent in order to remove H2S. Thereby can realize the sulfur content that 0.1ppm is following. At this In the scope of invention, pre-treatment step is included in the existing reforming method.
Each CONTINUOUS REFORMER zone and the zeolite regional one or more catalyst that contain respectively that contain of reforming Reactor. Raw material can be respectively with upper reaches, downflow mode or with the contact of radial flow pattern at each reactor In catalyst. Because existing reforming process is to operate under relatively low pressure, so radially Low pressure drop in the flow reactor is conducive to the radial flow pattern.
First the condition of reorganization comprises with zeolite reforms regional consistent pressure from 100kpa-6MPa (definitely Pressure), preferred 100kpa-1Mpa (absolute pressure). Operating pressure is 450kpa or lower the acquisition Good result. Usually the free hydrogen in containing the gas of light hydrocarbon combines with raw material, obtains Mol ratio is 0.1-10 moles of hydrogen/mole C5+ hydrocarbon. With respect to the first reforming catalyst volume Air speed is 0.2-10hr-1 Operating temperature is 400-560 ℃.
A kind of high in aromatics first logistics of CONTINUOUS REFORMER regional production. The big section of the naphtha in raw material Divide and be transformed into aromatic hydrocarbons. Alkane in raw material has been gone up substantially by isomerization, hydrocracking, take off The hydrogen cyclisation, wherein heavy paraffins is more than the amount that light paraffins changes, so the latter is in logistics In occupy the majority. C5Arene content in the+stream portions has improved with respect to the arene content in the hydrocarbon feed At least 5 (quality) %. Aromatic component depends primarily on raw material components and operating condition, and is generally main By C6-C
12Aromatic hydrocarbons forms.
In reforming reaction, owing to the catalyzer that acquires a certain degree such as sedimentary coke on particulate no longer be suitable for mechanism cause the granules of catalyst inactivation.Regeneration and adjustment again before this decaying catalyst must be reused in reforming process.
Because logical reprocessing cycle in a few days keeps the high catalyst activity near live catalyst to cause CONTINUOUS REFORMER to operate having more under the condition of intensity.The advantage of moving-bed is to keep producing, and removes or replace catalyzer simultaneously.Catalyst particles is because the one or more reactors of gravity by in moving-bed, and is sent to the cyclic regeneration zone.The regeneration of continuous catalyst is to be made by gravity in the moving-bed pattern that catalyst particles is dirty to be undertaken by the various treatment zones in regeneration container.Though catalyzer usually is set at successive by moving of various zones, be actually the semi continuous operation on the catalyst particles meaning of carrying respectively on each time point closely at interval relatively in a small amount.For example per minute one batch of material can be discharged from the bottom of conversion zone, and discharge can last 1/2 minute; Promptly flow and last 1/2 minute at one minute cycle inner catalyst particulate.Because generally with respect to batch volumes, stocking volume is bigger in reactor and regeneration zone, catalyst bed can be designed to mobile successive.
At a successive regeneration zone, in a combustion zone, catalyst particles contacts with containing hot Oxygen Flow, removes coke by oxidation.Usually catalyzer is again by the arid region, by with heat, the exsiccant air streams contact removes and anhydrates.By direct ingress of air stream cooling drying catalyzer.Preferably, catalyzer also can be in the halogenation zone that is positioned at combustion zone bottom by with contain halid gas and contact by halogenation.At last, catalyst particles reduces with hydrogen-containing gas at reduced zone, obtains the catalyst particles of adjustment again, and is transported to moving-burden bed reactor.Relevant continuous catalyst regeneration, the particularly detailed content of relevant hyperforming technology are disclosed in following, particularly at US-A-3, and 647,680; US-A-3,652,231; US-A-3 is in 692,496 and US-A-4,832,921.
Spent catalyst particulate from the CONTINUOUS REFORMER zone at first contacts with containing hot Oxygen Flow at regeneration zone, to remove at the coke that accumulates in during the reforming reaction on the catalyst surface.The coke content of spent catalyst particulate can reach 20% of catalyst weight, and still more typical is 5-7%.Coke mainly contains carbon and a small amount of hydrogen, is oxidized to carbon monoxide, carbonic acid gas, and water at 450-550 ℃ of (can reach 600 ℃) coke in regional area.The oxygen that is used for combustion of coke enters the combustion parts of regeneration zone with the form of the recycle gas that contains 0.5-1.5% volume oxygen usually.Stack gas is made of following component, and they are carbon monoxide, carbonic acid gas, and water, unreacted oxygen, chlorine, spirit of salt, Nitrous Oxide, the part of sulfur oxide and the nitrogen collected from the combustion zone is discharged as stack gas from regeneration zone.Remainder and a spot of oxygen make-up gas (be generally air, account for total tolerance about 3%) that contains are in conjunction with turning back to the combustion zone with the oxygen of supplement consumed and as recycle gas.The layout of typical combustion zone can be referring to US-A-3, and 652,231.
Because catalyst particles moves down by combustion zone and coke and is removed together, generally pass through the arrival midway " breakthrough point " in this zone, the oxygen that at this place is not conveying all has been consumed.People know; existing reforming catalyst particulate has the bigger surface-area relevant with many pores; when catalyst particles reached breakthrough point in bed, the coke that keeps at microparticle surfaces goed deep in the pore, so oxidizing reaction is carried out with speed very slowly.
In make-up gas and account for the seldom amount of stack gas and be discharged from from the water of combustion step, thereby in the circulation gas loop, form an equilibrium value.Be determined on a case-by-case basis, water concentration in circulation loop can be reduced by the air that drying is used for replenish replenishing gas, an a large amount of stack gas that is used for the moisture eliminator of gas circulation or ejects the self-circulation air-flow is installed to be reduced in the water balance value in the recycle gas loop in recycle gas loop.
Be determined on a case-by-case basis, catalyst particles directly enters drying zone from the combustion zone, and water wherein is evaporated by contacting with hot gas flow in the surface of particulate and pore.General air-flow is heated to 425-600 ℃ and be determined on a case-by-case basis gave drying before heating, so that increase the water yield that can be absorbed.Preferred drying air stream contains oxygen, more preferably oxygen content surpasses oxygen level in the air, so that the final combustion from the coke of the endoporus of catalyst particles can be finished in the arid region, and the oxygen that makes the excessive oxygen that in the arid region, do not have to consume upwards flow and be consumed by combustion reactions to replenish with the stack gas from the combustion zone.Catalyst particles is contacted with the gas that contains high oxygen concentration,, help catalyst particles to recover all active equally by improving the platinum on catalyzer or the oxidation state of other metal.Before catalyst particles leaves this zone, set the arid region and reduce the moisture content of catalyst particles to being not more than 0.01wt% (according to the weight meter of catalyzer).
After the drying step that carries out that is determined on a case-by-case basis, the preferred catalyst particulate separated region with redistribute precious metal on chloride gas contacts with the surface at catalyzer.For the gathering that reverses the precious metal that forms because of the water vapour that is exposed under the high temperature and in the combustion zone needs redistribution.Redistribution is preferably carried out at 510-540 ℃ at 425-600 ℃.The concentration of chlorine is the 0.01-0.2mol% of gas, and a large amount of oxygen have to be beneficial to and promote fast and disperse the platinum metals to obtain dispersed catalyst particulate again again completely.
Before being used for the catalysis purpose, by contacting reducing/regenerating and redistribution catalyzer with a kind of rich hydrogen reduction gas so that the precious metal on the catalyzer is become the simple substance state.Though the reduction of oxide catalyst is the basic step of most of resurfacing operation,, this step shifts to an earlier date slightly usually or carries out in reaction zone and the general environment division that no longer is considered in the regeneration zone.With pure relatively hydrogen reducing gas at 450-550 ℃, the preferred 480-510 ℃ of regeneration of carrying out highly oxidized catalyzer so that the catalyzer of adjusting again and again to be provided.
During press the system operation of device in CONTINUOUS REFORMER zone, most of catalyzer of supplying with this zone be reproduced and by as above describing first reforming catalyst of adjustment again.The part of catalyzer in zone of arrive reforming can be used as first reforming catalyst of additional supply, and overcoming especially the loss at reforming process inactivation and particulate between elementary period, but this amount is fewer, and each reprocessing cycle generally is less than 0.1%.This first reforming catalyst is the bifunctional compound, wherein contains one hydrogenation-dehydrogenation metal, and preferably the platinum group metal component preferred vector on a refractory carrier provides a kind of inorganic oxide that is used for cracking and isomerized acid position.First reforming catalyst is used for containing at raw material dehydrogenation and isomerization, cracking and the dehydrocyclization of petroleum naphtha.
The refractory first reforming catalyst carrier should be a porous, and adsorptivity is formed uniform high surface area material, this kind material inherent composition gradient not for its composition.Within the scope of the invention, the refractory carrier contains one or more: (1) refractory inorganic oxides is aluminum oxide for example, silicon-dioxide, titanium dioxide, magnesium oxide, zirconium white, chromic oxide, Thorotrast, boron oxide or its mixture; (2) clay synthetic preparation or natural generation and can be by acid-treated silicate; (3) or zeolite aluminosilicate crystal natural generation or synthetic preparation, for example be hydrogen form or at the FAU with the form of metallic cation exchange, MEL, MFI, MOR, MTW (the zeolite nomenclature IUPAC council); (4) spinel MgAl for example
2O
4, FeAl
2O
4, ZnAl
2O
4, CaAl
2O
4(5) above-mentionedly respectively organize the molectron that material forms by one or more.The refractory carrier that is preferred for first kind of reforming catalyst is an aluminum oxide, particularly preferably is γ-and η-aluminum oxide.
Alumina powder can be the arbitrary shape of the solid support material that one of skill in the art knows, and perhaps form is for example spherical, and extrudate is shaft-like, ball shape, sheet, thin slice or particle shape.Spherical particle can form by following step, by making alumina powder and peptization acid that suits and water reaction conversion lead oxide powder become alumina sol and colloidal sol and the gelifying agent mixture that generates being splashed in the oil bath, form the spherical particle of alumina gel, then carry out known wearing out, dry and calcination steps generates above-mentioned spherical particle.Preferred extrudate shape is preferably by mixing lead oxide powder and water and suitable peptizing agent, has extruding dough 500 ℃ of 45-65 quality % loss on ignitions with formation, and described peptizing agent is a nitric acid for example, acetate, materials such as aluminum nitrate.The dough that pushes generation by the suitable mould of shape and size thereafter, is used known method drying and roasting to form the extrudate particle.As available alternate mode, form spheroidal particle by extrudate by the extrudate particle of roll-in on rotating disk.Usually particle is a spheric, and diameter is 1/16-1/8 inch (1.5-3.1mm), though particle size can be greatly to 1/4 inch (6.35mm).In specific revivifier, wish that employed granules of catalyst drops in the narrow relatively size range.Preferred granules of catalyst diameter is 1/16 inch (3.1mm).
The basal component of first reforming catalyst is one or more platinum metals, preferred platinum component.Platinum can be used as a kind of compound or is present in the catalyzer as a kind of elemental metals, described compound with one or more catalyst composite in the chemically combined form of other composition oxide compound for example, sulfide, halogenide or oxyhalogenide exist.When being present in the catalyst composite with reduced state, all basically platinum can obtain optimal results.Calculate the 0.01-2 quality % of general platinum ingredients constitute catalyst composition, preferred 0.05-1 quality % according to the simple substance benchmark.
Within the scope of the invention, first reforming catalyst contains the metal promoters in order to the effect that improves preferred platinum component.These metal modifiers comprise the metal of IV A (14) family, other VIII (8-10) family metal, rhenium, indium, gallium, zinc, uranium, dysprosium, thallium and composition thereof.When containing the tin component, first reforming catalyst can obtain excellent results.The catalytically effective amount of this metal modifiers can enter in the catalyzer by any known process fusion of the prior art.
This first reforming catalyst can contain halogen component, but halogen component fluorine, chlorine, bromine or iodine or its mixture.Chlorine is preferred halogen component, and general halogen component and inorganic oxide carrier exist with bonding state.Preferred good being dispersed in the whole catalyzer of halogen component calculated according to the simple substance benchmark, and its content is the 0.2-15wt% of last catalyzer.
A kind of first reforming catalyst composition of looking the particular case existence is a zeolite, or crystalline aluminosilicate, yet preferred this catalyzer does not contain zeolite component substantially.According at US-A-4,741,820 is disclosed, and first reforming catalyst contains a kind of non-zeolite molecular sieve.
First reforming catalyst generally under 100-320 ℃ temperature dry 0.5-24 hour, then 300-550 ℃ in air atmosphere oxidation 0.5-10 hour.The catalyzer of oxidation preferably is reduced 0.5-10 hour or the longer time under 300-550 ℃ and substantially anhydrous condition.At US-A-4, the preparation and the activatory detailed content of first reforming catalyst disclosed in 677,094.
Zeolite catalyst is contained in the fixed bed reaction district or moving bed reaction district, thereby catalyzer can be discharged and adding by successive.These available alternate methods are that catalysis-regeneration of knowing with this area professional is relevant, and for example: (1) one contains half regenerating unit of fixed-bed reactor by improving temperature, last stopping device so that regeneration and reactivating catalyst keep intensity, operation; (2) a kind of reactor assembly that waves, along with the fixed-bed reactor that catalyst deactivation is wherein independent are isolated successively by manifold configuration, the catalyzer in the reactor of keeping apart is reproduced and reactivate, and other reactor keeps production status simultaneously; (3) the cyclic regeneration catalyzer of from moving-bed, discharging, reactivate and the catalyzer of replacing above-mentioned reactivate; (4) mixing system that contains half regeneration and continuous regeneration equipment in same area.Preferred embodiment of the present invention is the fixed-bed reactor in the zeolite of partly regenerating is reformed the zone and the mixing system of the moving-burden bed reactor with continuous catalyst regeneration in the CONTINUOUS REFORMER zone.
In this reforming method, preferred first reforming catalyst provides the 20-90vol% of total catalyst levels.First and the relative volume of zeolitic reforming catalyst depend on whether the target of product and this technology combine with the equipment of original use.If the actual production purpose of brand-new process unit is that advantageously, the general proportions that zeolitic reforming catalyst contains is preferably the 10-60% of catalyzer total amount with the naphthalene raw material of relatively small amount maximum production benzene and toluene.On the other hand, the zone is added into the CONTINUOUS REFORMER zone of an existence if a new zeolite is reformed, and zeolite reformation zone preferably only accounts for the relatively little ratio of catalyzer total amount so that reduce the influence of new region to existing CONTINUOUS REFORMER operation to greatest extent.The 55%-95% of this method catalyzer cumulative volume amount is provided by first reforming catalyst in the latter case.
Particularly preferred embodiment of the present invention is zeolite to be reformed to join that existing CONTINUOUS REFORMER zone promptly wherein is provided be the equipment with hyperformer of continuous catalyst regenerating function in the zone.The cyclic regeneration reformer needs more capital construction investment, relates generally to the high strength reformation and comprises that supplementary equipment therefore is used for continuous catalyst regeneration.By increasing the effective especially zeolite reformation of light paraffins zone in first logistics that the conversion CONTINUOUS REFORMER is produced, the improvement of operating for whole catalytic reforming provides approach:
Improve intensity, also claim the overall yield or the total octane value of product of aromatic hydrocarbons;
By reducing the turnout at least 5% that CONTINUOUS REFORMER intensity improves the CONTINUOUS REFORMER zone, preferably at least 10%, be determined on a case-by-case basis at least 20%, reach 30% or more in certain embodiments.This reduction intensity be by in the CONTINUOUS REFORMER zone in higher air speed, carry out under the condition of lower hydrogen to the ratio of hydrocarbon and less catalyst recirculation amount once realizing with multi-pass operations.Then, realize desired quality product by first logistics of processing from CONTINUOUS REFORMER zone in the zeolite reformation zone.
Improve selectivity, reduction CONTINUOUS REFORMER operation intensity and the remaining paraffinic hydrocarbons that optionally changes in first kind of logistics become aromatic hydrocarbons.
First logistics from the CONTINUOUS REFORMER zone enters the zeolite reformation zone that is used to finish reforming reaction, preferably follow the first logistics first being processed of free hydrogen in zeolite is reformed the zone of first logistics not separated, i.e. successive reformation zone is in identical hydrogen loop with zeolite reformation zone.Within the scope of the invention, the feed naphtha that replenishes is added in first logistics, arrives zeolite reformation zone as raw material, to obtain additional reformate.The feature that the feed naphtha that replenishes has is in the scope of those descriptions that are used for hydrocarbon feed, and it is lower boiling and best that best is is the raw material that is used for the production of the aromatic hydrocarbons lighter than the raw material that is fed to the CONTINUOUS REFORMER zone.This first logistics and look the additional feed naphtha that particular case exists contacts zeolitic reforming catalyst under second the condition of reorganization in zeolite is reformed the zone.
Obtain a kind of rich aromatic hydrocarbon product at the zeolite regional hydrocarbon feed contact zeolitic reforming catalyst of reforming, its principal reaction is the dehydrocyclization of the paraffinic hydrocarbons that keeps in first logistics.Comprise pressure from 100kpa-6MPa (absolute pressure) at zeolite of the present invention second the condition of reorganization that the zone uses of reforming, preferably from 100kpa-1MPa (absolute pressure), the pressure of last reactor exit be 450KPa or lower be particularly preferred.With enough amounts free hydrogen is supplied to zeolite reformation zone, described amount preferably is not more than 6, more preferably no more than 5 corresponding to the every mol hydrocarbon feed of ratio 0.1-10mol hydrogen.Wherein to refer in hydrocarbon or other compound be not have combined molecule H to free hydrogen
2The little hourly space velocity of liquid of the zeolitic reforming catalyst volume correspondence that contains is from 1-40hr
-1, preferably be at least 7hr
-1, be more preferably 10hr
-1Or more than.
Be defined as hydrocarbon feed, free hydrogen, the service temperature of top temperature of mixture of component of following free hydrogen arbitrarily is generally at 260-560 ℃, select the best overall result of this temperature can realize reforming CONTINUOUS REFORMER zone and zeolite the zone combines, described result is about being the aromatics yield in the purpose product with the production of chemical aromatic hydrocarbons or being the performance octane value for example of purpose with the gasoline production.The type of the hydrocarbon in raw material is also influential to the selection of temperature, and is effective especially because zeolitic reforming catalyst is used for the dehydrocyclization of light paraffins.Because endothermic heat of reaction is accompanied by the decrease of temperature that it passes catalyst bed, naphthenic hydrocarbon obtains dehydrogenation usually largely and handles in previous continuous reforming reactor.Usually inevitable inactivation raises during being operational cycle of purpose initial temperature of reaction slowly with make-up catalyst at each.The temperature of reactor in zone of reforming the reactor in CONTINUOUS REFORMER zone and zeolite preferably staggers each other, promptly is different between reactor, so that corresponding to such as the ratio of the fragrant agent of difference and the class variable productive target product of non-aromatic agent concentration.Usually the top temperature in zeolite reformation zone is lower than the top temperature in the CONTINUOUS REFORMER zone, but can be higher in the temperature in zeolite reformation zone, and this depends on the condition of catalyzer, and target product.
Zeolite reformation zone can comprise the single reactor that contains zeolitic reforming catalyst, perhaps comprises two or more parallel reactors that valve is housed well known in the art, so that carry out available alternate cyclic regeneration.Selection between one reactor and parallel recirculation reactor depends on that reactor volume and needs keep stable and high yield that can not be interrupted.Under any circumstance, the reactor in zeolite reformation zone preferably is equipped with valve and is used for throwing off from process integration, so that zeolitic reforming catalyst can be regenerated or be replaced, the CONTINUOUS REFORMER zone keeps operating simultaneously.
In the embodiment of an available replacement, within the scope of the present invention, zeolite reformation zone is contained two or more reactors and have middle heating phenomena between reactor, with elevated temperature and maintenance dehydrocyclization condition.This is very favourable, be cyclized into the dehydrogenation of aromatic hydrocarbons and simultaneous with it common naphthenic hydrocarbon because the principal reaction that takes place in zeolite reformation zone is a paraffin dehydrogenation, the thermo-negative reaction of generation can occur cooling off reactant below the reforming temperature that produces before the sufficient dehydrocyclization.
In the embodiment of another available replacement, in reforming the zone, zeolite keeps reforming temperature by additional internal heat exchange component in this zone reactor.Preferred heat exchange reactor is that radial flow is arranged and has the fluid channel of the area format that the annular volume at reactor contains.Heat exchange medium and radially the reactant flow of contact catalyst stream preferably with the passage of counter-flow arrangement by alternately occurring.A kind of coiled material is supported the thin-walled heat exchanger plate and is provided flow distribution and the mobile 1L collection chamber on the interior and neighboring of this passage.
Zeolitic reforming catalyst contains non-acidic zeolite, basic metal component and platinum group metal component.Importantly, the zeolite that is preferably LTL or L-zeolite is non-acid, because the acidity in zeolite can reduce the selectivity to the aromatic hydrocarbons of product catalyst.In order to become non-acid zeolite, non-hydrogen form has occupied almost its whole cationic exchange position.The positively charged ion that takies the exchangeable cation position preferably includes one or more basic metal, though other cationic form also can exist.Particularly preferred non-sour L-zeolite is a potassium shape L-zeolite.
For a kind of catalyzer that is used for suitable form of the present invention is provided, generalized case is combined with each other a kind of tackiness agent and L-zeolite.Prior art discloses any refractory inorganic oxide adhesive and all suits, one or more silicon-dioxide, aluminum oxide or magnesium oxide are preferred adhesive materials of the present invention, particularly preferably be non-crystal silicon-dioxide, when using from the aqueous solution, can obtain good result as the sedimentary synthetic white of the thin spheroidal particle of spy SiO 2 powder.Preferred silica binder is non-acid, and wherein sulphate content is less than 0.3 quality %, and the BET surface-area that has is from 120-160m
2/ g.
Can be by the compound L zeolite of any means of known technology and tackiness agent to form desirable catalyst shape, for example potassium shape L-zeolite and non-crystal silicon-dioxide can be mixed into a kind of uniform powdered mixture before adding peptizing agent.Add a kind of aqueous solution of sodium hydroxide that contains to form squeezable dough.The moisture content of preferred dough is that 30-50 quality % has with formation and can withstand the gratifying complete extrudate of direct incinerating.Mould by suitable shape and size pushes the dough that generates, and forms the extruding particle, and dried particles is also by known method roasting.Form spheroidal particle by aforesaid method and be used for zeolitic reforming catalyst.
A kind of alkaline components is a kind of essentially consist of zeolitic reforming catalyst.Can use one or more basic metal, comprising lithium, sodium, potassium, rubidium, caesium and composition thereof, preferably potassium.Preferred as alkali is almost occupied the tradable position of all positively charged ions of nonacid L-zeolite.At US-A-4, the alkali-metal existence of surface deposition is disclosed in 619,906.
The platinum metals is another essential characteristic of zeolitic reforming catalyst, preferred platinum component, platinum can be used as compound or is present in the catalyzer as elemental metals, described compound can be with the form of other composition chemical combination in one or more catalyst complex oxide compound for example, sulfide, halogenide or oxyhalogenide.When all basically platinum can obtain best result to go back when ortho states is present in the catalyst complex.The 0.05-5 quality % of platinum ingredients constitute catalyst complex calculates with the simple substance benchmark generally speaking, preferred 0.05-2 quality %.Within the scope of the invention, catalyzer can contain and can have other known metal component of improved action to the effect that preferred platinum component produces.This metal modifiers comprises IV A (14) family metal, other VIII (8-10) family metal, rhenium, indium, gallium, zinc, uranium, dysprosium, thallium and composition thereof.By known any means, the catalytically effective amount of this metal modifiers is incorporated in the catalyzer.
Usually final zeolitic reforming catalyst is at 100-320 ℃ of dry 0.5-24 hour, then 300-550 ℃ (preferred 350 ℃) in air atmosphere oxidation 0.5-10 hour.The catalyzer of preferred oxidation stands effect 0.5-10 hour or the longer time of substantially anhydrous reduction step at 300-550 ℃ (preferred 350 ℃).The time length of reduction step only just needs reduction platinum, to avoid the pre-inactivation of catalyzer, if can keep dry atmosphere, can be used as the device actuating section and carries out at the scene.At US-A-4, preparation and the activatory detailed content of zeolitic reforming catalyst embodiment disclosed in 619,906 and US-A-4,822,762.
The zeolite rich aromatic hydrocarbon product of regional production department in the reformation logistics that contains hydrogen and light hydrocarbon of reforming.Use techniques well known in the art and equipment, usually, the reformate stream of reforming regional from zeolite arrives separated region by condenser zone.At separated region, generally remain on 0-65 ℃, hydrogen-rich gas is separated from liquid phase, and preferably the major part of the hydrogen-rich stream body of Sheng Chenging turns back to the zone of reforming by suitable compression set circulation, and part hydrogen can be used as the other parts that pure product is used for refining of petroleum factory or chemical plant.Usually, eject the liquid phase in self-separation zone and in fractionating system processing obtain rich aromatic hydrocarbon product to regulate the concentration of light hydrocarbon.
Embodiment
Three parameters are being measured aspect reforming method and the catalyst performance particularly usefully, are used for aspect the catalyzer of dehydrocyclization of paraffinic hydrocarbons especially suitable in mensuration." activity " is to the tolerance of the ability of catalyzer conversion reaction thing under the reaction conditions of setting." selectivity " indication catalyzer obtains the ability of desired product with high yield." stability " is that catalyzer keeps its tolerance active and the time-independent ability of selectivity.
This embodiment shows that working as processing mainly contains C
6-C
8The comparative result of pilot plant test during the feed naphtha of hydrocarbon.Feed naphtha has following feature:
Proportion 0.7283
ASTMD-86,℃:IBP 75
50％ 100
EP 137
Volume % paraffinic hydrocarbons 62.0
Naphthenic hydrocarbon 28.5
Aromatic hydrocarbons 9.5
Simultaneous test is under corresponding condition, carries out in the transformation efficiency scope of the non-aromatics in whole raw material, and the result of a plurality of regional combination technologies of the present invention and the result of known closely-related reforming process are contrasted.According to " BTX aromatic hydrocarbons " or benzene/methylbenzene/dimethylbenzene/ethylbenzene (representing basic aromatic hydrocarbons intermediate) and " C
8The productive rate of aromatic hydrocarbons or dimethylbenzene+ethylbenzene (generally it being regarded as target aromatic hydrocarbons intermediate, in order to determine the size of new aromatic hydrocarbons title complex) is determined the result,
Embodiment 1
According to the purposes of the known catalyst A above-mentioned C of middle device test processing that reforms
6-C
8Raw material, cyclic regeneration catalyzer contain the platinum of 0.29 quality % on chlorinated aluminas and the tin of 0.30 quality %, and working pressure is 450kpa, and the little hourly space velocity of liquid is 2.5Hr
-1, be 6 to supply with molecular hydrogens to the mol ratio of raw material with hydrogen.Transformation temperature is 45-77 quality % so that make the transformation efficiency scope of non-aromatics.The transformation efficiency boiling range fraction B TX aromatics yield of this comparative example is plotted among Fig. 1.
Embodiment 2
Process above-mentioned C according to the present invention
6-C
8The reform middle device test of the multizone process integration of raw material.Describe among catalyst A such as the embodiment 1, packed into before catalyst B, catalyst B contains the platinum of 0.82 quality % on the L-of bonding silicon-dioxide zeolite, and catalyst A is 75/25 to the volume ratio of catalyst B.
Petroleum naphtha is being loaded in the reactor in the flow operation down, successively contact catalyst A and catalyst B.Working pressure is 450kpa, and the little hourly space velocity of total liquid is 2.5Hr with respect to catalyst mixture
1, be 4.5 to supply with hydrogen with hydrogen to the mol ratio of raw material, the transformation efficiency that transformation temperature obtains non-aromatics is 50-87 quality %.
Its result is plotted among Fig. 1, and the result of catalyst A in itself and the Comparative Examples 1 is compared, and the result shows that this catalyst mixture has improved aromatics yield significantly, is better than comparative catalyst A.
Embodiment 3
The yield structure of comparative catalyst A and united catalyst A/B of the present invention is at raw material (C
5The analysis octane value of+product is respectively 99.5 and 98.5) in the equivalent transformation efficiency of non-aromatics be to compare under 74% the condition, this yield structure is selected from the transformation efficiency scope of embodiment I and embodiment 2, is represented as productive rate (quality) % with respect to raw material.
Catalyst A catalyst A/B
Benzene 9.5 13.0
Toluene 25.0 31.0
C
8Aromatic hydrocarbons 25.0 22.0
BTX aromatic hydrocarbons total amount 59.5 66.0
Hydrogen 3.6 4.0
C
5+ product 89.4 91.2
United catalyst of the present invention proves that the productive rate of its aromatic hydrocarbons is higher than comparative example more than 10%, and higher hydrogen productive rate and higher C
5+ productive rate.
Embodiment 4
Another advantage of integrated processes of the present invention is to change zeolite reformation zone into and then more effectively utilize the CONTINUOUS REFORMER zone to implement the present invention by the final section with reaction.This advantage is effective especially in the situation in existing CONTINUOUS REFORMER zone that can the cyclic regeneration catalyzer, and described continuous catalyst regeneration can not be satisfied the needs that gasoline or aromatic hydrocarbons are constantly increased.By the present invention, except transformation efficiency is lowered, also improved the throughput of raw material in this zone, and can not increase the cycle rate and the regeneration rate of catalyzer.Realize simultaneously that by only adding reactor in the zeolite reformation zone of in same hydrogen loop, containing basically higher turnout keeps total transformation efficiency of process integration.
By the embodiment that draws by above-mentioned middle device test this embodiment is described, more only have the CONTINUOUS REFORMER zone " initially " situation and increased the zeolite zone of reforming in the present invention, thereby improved the situation (initial value is annual 1,000,000 tonne) of processing unit (plant) turnout.
Initial invention
Turnout 10
3Ton/year 1,000 1,300
The transformation efficiency of non-aromatics, quality %
*74 65
Catalyst recirculation basic 0.9 * substantially
Hydrogen/raw material, mole 6.0 4.5
The little hourly space velocity of liquid, hr
-1*2.5 3.3
Productive rate, 10
3Ton/year:
C
5+ product 894 1185
Toluene 250 403
C
8Aromatic hydrocarbons 250 286
BTX aromatic hydrocarbons total amount 595 858
*In the CONTINUOUS REFORMER zone
The air speed in zeolite reformation zone is 10hr
-1Usually, catalyst volume and gas circulation are the limiting parameters of turnout in the hydrotreater.The liquid production amount usually can improve 20-30% or more (when almost not having the waterpower deoppilation).Therefore, according to explanation the above embodiment of the present invention, increase comprises the zeolite reformation zone of the reactor that contains non-acidic zeolite catalyst and makes possible small-scale with miscellaneous equipment and improve the production 44% that can improve BTX aromatic hydrocarbons
Claims (9)
1. one kind is used for basic method of carrying out distillatory catalytic reforming feed naphtha in 40-210 ℃ of scope, be included in and contain regenerated difunctionality reforming catalyst particulate CONTINUOUS REFORMER zone, in the presence of the free hydrogen with under first the condition of reorganization, contact feed naphtha and flow out logistics to produce original first, above-mentioned catalyzer contains platinum group metal component, halogen component and refractory inorganic oxides, the first above-mentioned the condition of reorganization comprises that pressure is 100kpa-1Mpa, and the little hourly space velocity of liquid is 0.2-10hr
-1, hydrogen is to C
5The mol ratio of+hydrocarbon is 0.1-10, temperature is 400-560 ℃, above-mentioned original first flows out the granules of catalyst that logistics contains the inactivation of a BTX aromatic hydrocarbons and a fundamental quantity, at least semi-continuously remove the granules of catalyst of de-inactivation from the CONTINUOUS REFORMER zone, with cyclic regeneration in containing oxygen containing gas zone and the reduced zone that contains hydrogen-containing gas contact in proper order to the small part particle to obtain the granules of catalyst of re-adjustment, its further feature is circulation raising at least 5% (volume) with the CONTINUOUS REFORMER zone, meanwhile, improve air speed, reduce the mol ratio (its scope at 0.1-6) of hydrogen to hydrocarbon, and do not increase granules of catalyst with respect to the inactivation of fundamental quantity to obtain improved first logistics from the CONTINUOUS REFORMER zone, non-separation of hydrogen is to obtain to contain the rich aromatic hydrocarbon product that has more 10%BTX than the first initial logistics at least with contact improved first logistics under second the condition of reorganization in the zeolite that contains zeolitic reforming catalyst is reformed the zone, above-mentioned zeolitic reforming catalyst contains non-acidic zeolite, one alkaline components and platinum group metal component, the second above-mentioned the condition of reorganization comprises that pressure is 100kPa-6MPa, and the little hourly space velocity of liquid is 1-40hr
-1With temperature be 260-560 ℃.
2. the process of claim 1 wherein that each CONTINUOUS REFORMER zone and zeolite reform regional pressure at 100kPa-1MPa.
3. the process of claim 1 wherein that the pressure in each CONTINUOUS REFORMER zone and zeolite reformation zone is 450kPa or lower.
4. the process of claim 1 wherein in the CONTINUOUS REFORMER zone and the mol ratio of hydrocarbon to be not more than 5 in order to the hydrogen that obtains improved first logistics.
5. the process of claim 1 wherein that the little hourly space velocity of liquid in zeolite reformation zone is to be at least 7hr
-1
6. the process of claim 1 wherein that the air speed in zeolite reformation zone is to be at least 10hr
-1
7. each method among the claim 1-6, wherein non-acidic zeolite contains platinum shape L zeolite.
8. each method among the claim 1-6, wherein the alkaline components of zeolitic reforming catalyst contains the potassium component.
9. each method among the claim 1-8, wherein the platinum group metal component of zeolitic reforming catalyst contains the platinum component.
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| Application Number | Priority Date | Filing Date | Title |
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| CN97114124A CN1108353C (en) | 1997-11-03 | 1997-11-03 | Continuous catalytic reforming combined with zeolitic reforming for increased BTX yield |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97114124A CN1108353C (en) | 1997-11-03 | 1997-11-03 | Continuous catalytic reforming combined with zeolitic reforming for increased BTX yield |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103857646A (en) * | 2011-12-15 | 2014-06-11 | 环球油品公司 | Integrated hydrogenation/dehydrogenation reactor in a catalytic reforming process configuration for improved aromatics production |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4645586A (en) * | 1983-06-03 | 1987-02-24 | Chevron Research Company | Reforming process |
| US5190638A (en) * | 1991-12-09 | 1993-03-02 | Exxon Research And Engineering Company | Moving bed/fixed bed two stage catalytic reforming |
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| CN103857646A (en) * | 2011-12-15 | 2014-06-11 | 环球油品公司 | Integrated hydrogenation/dehydrogenation reactor in a catalytic reforming process configuration for improved aromatics production |
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