CN1229310C - Improved method for producing saturated low polymer - Google Patents
Improved method for producing saturated low polymer Download PDFInfo
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- CN1229310C CN1229310C CN 98124646 CN98124646A CN1229310C CN 1229310 C CN1229310 C CN 1229310C CN 98124646 CN98124646 CN 98124646 CN 98124646 A CN98124646 A CN 98124646A CN 1229310 C CN1229310 C CN 1229310C
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Abstract
The present invention relates to a method for preparing saturated oligomer by using the oligomerization of light olefin to prepare heavy olefin and saturating the heavy olefin. In the method, heavy paraffin hydrocarbons are circulated to an oligomerization zone for improvement; the recirculation of the heavy paraffin hydrocarbon improves the oligomerization selectivity of a C8 paraffin hydrocarbon product and reduces catalyst pollution; the pollution-reduced catalyst can be used for controlling the oligomerization zone under the condition of lower pressure, and is favorable for the combination with a dehydrogenization zone for producing light olefin airflows.
Description
The present invention relates generally to produce hydro carbons in the gasoline boiling range scope by the saturation of the oligomeric of light olefin and the heavier alkene that generates.
The demand that light hydrocarbon is converted into high-octane motor spirit exists always.The same propylene of Trimethylmethane, butylene and amylene are carried out alkylation, are commonly referred to the HF alkylation as catalyzer with hydrofluoric acid (HF), a kind of method of extremely successful production high-octane motor fuel is provided.Although existing very long safety in production history, fears are entertained that recently hydrofluoric acid calamitous possibility that discharges from HF alkylated reaction equipment, and this impels people that the improvement and the replacement of the HF alkylation production method of motor spirit are studied.A kind of known replacement method is to make the similar alkylation of catalyzer with sulfuric acid.Although use sulfuric acid perhaps can reduce some hazard level, use the vitriolic method still to be counted as to have same danger, and it be favourable to be not so good as HF alkylation economy because of using HF acid to bring.Therefore still need seek the alternative method of HF alkylation.
Some other is known and has realized in conjunction with the method for producing motor spirit with light olefin Trimethylmethane, but it is expensive to produce the gasoline products of same quality or installation and operation.A kind of alternative method promptly is with dehydrogenation of isobutane, then with the gained olefin oligomerization, produces the hydro carbons in the gasoline boiling range scope.To hang down motor spirit that olefin oligomerization becomes higher molecular weight for people know with solid phosphoric acid, and its use is early than HF alkylation-see US-A-2526966.Such oligomerization process is also referred to as the catalyzing and condensing of gained motor spirit and superimposed, and described motor spirit often is called polymerization gasoline.
People also know, come saturation alkene by the oligomeric olefin stream that makes is carried out hydrogenation.GB-A-2186287 discloses and has passed through C
4Cut dehydrogenation and oligomeric production can be chosen the jet fuel that is hydrogenated to premium motor fuel wantonly.US-A-4678645 discloses jet fuel, diesel-fuel and lubricating substance that hydrotreatment makes by dehydrogenation and oligomeric light paraffins.Yet for by the oligomeric gasoline fraction that makes, hydrotreatment is always not useful, and can reduce octane value, but people know that when isooctene was saturated to octane-iso, this processing was useful especially.
The objective of the invention is to improve the combine operations of oligomerization zones and saturation region.Another object of the present invention is to provide the improved associating of oligomerization zones and saturation region, this associating and dehydrogenation zone bound energy provide an attractive alkylating method of alternative HF.
The present invention by the saturated oligopolymer of a recirculation part to oligomerization zones, thereby realize the oligomeric of light olefin and the saturation of the oligopolymer that obtains between associating.The pollution that the oligomerization zones that is recycled to saturated oligopolymer will suppress in the oligomerization zones catalyzer that the deposition owing to coke causes has also shockingly improved the C of oligomerization zones to higher octane simultaneously
8The selectivity of isomer.Reduce pollution by recirculation heavy paraffin from saturated oligomeric effluent, can prolong in the oligomerization zones life of catalyst or can under lower pressure, operate oligomerization zones.
When oligomerization zones and saturation region and when being used to provide the dehydrogenation zone associating of light olefin charging, the operation under lower pressure is useful especially.When the working pressure of oligomerization zones reduced, the dehydrogenated operation under the general low pressure can more effectively be united oligomerization zones.The working pressure scope is 136～1136kPa (5 to 150psig) in the dehydrogenation reactor, and the routine operating pressure of general oligomerization zones will be about 3550kPa (500psig) usually above 2170kPa (300psig).Recirculation by saturated oligopolymer reduces pollution, and oligomerization zones pressure can be brought down below 2170kPa (300psig) always.Operating pressure difference between dehydrogenation zone and the oligomerization zones can be contracted to less than 1034kPa (150psig), has eliminated the needs of any twin-stage compression between the zone simultaneously.Therefore have benefited from such recirculation, a kind of dehydrogenation of associating, the setting oligomeric and saturation region have not only improved selectivity, and have reduced process cost.
In main embodiment of the present invention, correspondingly provide a kind of method of producing saturated oligomer.This method with under the oligomeric condition, comprise C
3To C
5The oligomerization zones charging of alkene contacts with oligomerisation catalyst under oligomeric condition, and it is 93 ℃ to 260 ℃ (200 °F to 500 °F) that described oligomeric condition generally comprises temperature, and pressure is that 790 to 6996kPa (100 to 1000psig) and LHSV are 0.5 to 5 hour
-1Contain C
8The recirculation stream of paraffinic hydrocarbons also contacts with catalyzer.Oligomeric condition is effectively for the oligomeric outflow logistics of producing, and contains C in the oligomeric outflow logistics
7Heavier alkene and the paraffinic hydrocarbons that reclaims from oligomerization zones.At least a portion contacts come alkene in saturation oligomeric effluent by the saturation region and under saturation conditions with saturation catalyst from the effluent of oligomerization zones and hydrogen-containing gas streams.The saturation region that at least a portion comprises the paraffinic hydrocarbons with at least 8 carbon atoms flow out logistics as described recirculation stream by described oligomerization zones, reclaim a part simultaneously and contain C
8The saturation region that reaches than heavy paraffin flows out logistics.
More specifically in embodiment, provide a kind of method of producing the motor spirit product by the incoming flow that contains Trimethylmethane in the present invention.Dehydrogenation zone is passed through in the incoming flow that this method will contain Trimethylmethane, and incoming flow is contacted with dehydrogenation catalyst under dehydrogenation condition at dehydrogenation zone, described dehydrogenation condition generally comprises: temperature is 510 to 649 ℃ (950 to 1200 °F), and pressure is that 136 to 1136kPa (5 to 150psig) and LHSV are 0.5～50 hour
-1, recover hydrogen and contain C from dehydrogenation zone simultaneously
4The dehydrogenation effluent of isoolefine.After from hydrogen purity is the dehydrogenation zone effluent of 70～95 moles of %, isolating hydrogen stream, with the resistates of dehydrogenation zone effluent as containing C
4The liquid-phase feed stream of alkene is delivered to oligomerization zones.In oligomerization zones with oligomerization zones charging and the recirculation stream that contains the alkane warp in typical oligomeric condition: comprise that temperature is 93～260 ℃ (200～500 °F), pressure be 790～6996kPa (100～1000psig) and LHSV be 0.5～5 hour
-1Contact with the solid oligomerisation catalyst down, contain C to produce effectively
7And the oligomeric effluent of higher isoolefine.To deliver to the saturation region without separating together with hydrogen stream from the effluent of oligomerization zones.Under saturation conditions, in the saturation region, oligomerization zones effluent and hydrogen are contacted with saturation catalyst, come saturated alkene in oligomeric effluent.At least a portion saturation region is flowed out logistics deliver to the disengaging zone, reclaim and contain C
8Reach saturated logistics than heavy paraffin.The saturated logistics that at least a portion reclaims is delivered to described oligomerization zones as described recirculation stream.
Accompanying drawing is a process flow diagram of the present invention, has wherein indicated main technique district and relevant pipeline and equipment.
Main operational zone in the invention process process is the oligomerization district.Be used for suitable oligomerization zones of the present invention many forms are arranged.Oligomerization process is known many titles, as catalyzing and condensing and catalytic polymerization.The known catalysts of reacting like this comprises that note makes the solid phosphoric acid catalyst and the homogeneous catalyst of SPA catalyzer, as at US-A-3906053, and the boron trifluoride of describing among US-A-3916019 and the US-A-3981941.
Preferred oligomerization catalyst is solid phosphoric acid (SPA) catalyzer.Previously mentioned SPA catalyzer refers to and contains phosphorated acid as ortho-phosphoric acid, tetra-sodium or four phosphoric acid (tetraphosphoric acid) solid catalyst as main component.This catalyzer normally mixes by the solid carrier that phosphorated is sour and siliceous, forms wet soup compound and forms.This soup compound can pass through roasting, and crushing then produces granules of catalyst, and wherein soup compound can be through extruding or pellet and make more uniform catalyst particle before roasting.Carrier is preferably natural porous material, as diatomite (kieselguhr), kaolin, diatomite (infusorial earth) and diatomite (diatomaceous earth).Can be with a small amount of different additive, as mineral talc, Fuller's earth and comprise that the iron containing compounds of ferric oxide is added in the carrier, to increase its intensity and hardness.Carrier and additive preferably amount to and account for 15～30% of catalyzer, and all the other are the phosphoric acid additive.Additive can account for the 3-20% of whole solid support material.With respect to the change of forming, remain feasible as phosphorus acid content is low.Relevant SPA catalyzer is formed and the further details of preparation can be from US-A-3050472, obtains among US-A-3050473 and the US-A3132109.
Among the present invention, the oligomerization district preferably carries out under certain temperature and pressure, so as to increase its outflow condition and downstream saturated reaction district inlet entry condition, with and the compatibility of the outflow condition of entry condition and upstream dehydrogenation reaction zone.The preferred range in oligomerization district is generally 93～260 ℃ (200～500 °F), more typically is 149～232 ℃ (300～450 °F), wherein some catalyzer is preferably 149～204 ℃ (300～4000 °F) especially.Usually (100～1000psig), when using the present invention to reduce the working pressure of oligomerization zones, more general range is 790～3549kPa (100～500psig) to pressure range in the oligomerization district at 790～6990kPa.When enforcement was of the present invention, for the SPA catalyzer, particularly preferred working pressure scope was 790～2170kPa (100～300psig).Have now found that, service temperature is remained on a narrow scope promptly selectivity can be guided into the more C of production in 149～171 ℃ (300～340 °F)
8Isomer.
The charging in oligomerization district generally comprises C
3～C
5Alkene and paraffinic hydrocarbons.Steam or water can be fed in the reactor,, be used for the hydration of preferred SPA catalyzer to keep low water-content.The source of alkene charging is generally from the partially recycled light gas stream of the gas delivery of FCC method, from the C of steam cracking and coker tail gas
4The effluent of air-flow or dehydrogenation zone.Olefin feed stream is characterised in that, C
4The total concn of alkene is at least 10% (weight).In the major part operation, olefin feed stream contains C
4Alkene, but it can contain all or a large amount of C
3Alkene.Contain the C that concentration is at least 30% (weight) in the general alkene charging
3～C
5Alkene, C in the preferred alkene charging
4Concentration of olefin is at least 30% (weight), more preferably is at least 50% (weight).Olefin feed stream preferably comprises at least 20% (weight), the more preferably iso-butylene of at least 30% (weight).The iso-butylene preferred content accounts for 33% of whole butylene at least.Olefin(e) centent mainly comprises the branched-chain alkene that contains a large amount of iso-butylenes in the preferred charging.By in the charging of oligomerization zones of the present invention, keeping the iso-butylene of high density, promoted the reaction of positive amylene and propylene.At least the alkene that contains 50% (weight) iso-butylene in the charging of oligomerization zones distributes and can promote amylene to become the high-octane rating isomer with oligomeric acrylamide.When a large amount of propylene is present in the charging of oligomerization zones, can increase the octane value of product by improving in the butene component of the charging percentage composition of iso-butylene.When a large amount of propylene entered oligomerization zones, butene component preferably comprised 100% iso-butylene.
In the invention process process, the heavy paraffin component contacts with catalyzer together with common oligomerization zones charging.The heavy paraffin component contains the hydrocarbon with at least 8 carbon atoms and maximum 20 carbon atoms, preferably contains C
8～C
12Paraffinic hydrocarbons.Adding the heavy paraffin logistics will provide a large amount of heavy paraffins in oligomerization zones, be the C of 20% (weight) with the output minimum quantity in the outflow logistics of reactor preferably
8And heavy paraffin more, more typically at the inlet of each catalyst bed C with output at least 25% (weight)
8Reach more heavy paraffin.Preferred especially C
8Paraffinic hydrocarbons, it preferably contains minimum 5% (weight) in first catalytic bed, to the C of 50% (weight) mass rate nearly
8Paraffinic hydrocarbons is by the oligomerization district.
The heavy paraffin component can enter reaction together with charging, or is injected into to the oligomerization district in the mid-way.Different catalyst beds preferably is contained in the reactor of one or more gardens tubular, vertical orientation, and incoming flow preferably enters the top of reactor.Catalyzer preferably is installed in the fixed bed in the oligomerization zones that is known as the chamber reactor structure.Generally, chamber reactor contains 5 catalyst beds of having an appointment.In chamber reactor, reactant flows through a series of large diameter catalyst beds.Hydro carbons by the recirculation relative inertness serves as the temperature that heat sink is further controlled reactant.That oligomerization zones is injected in the middle of being equipped with usually and accepting, in order to a plurality of catalyst beds of control from the quenching material of the temperature of thermopositive reaction.Inject logistics as the centre, can obtain many benefits by adding heavy paraffin, wherein middle injection logistics also helps this reaction as the quenching logistics.
By adding the heavy paraffin logistics, the ratio of paraffinic hydrocarbons and alkene is 1: 1 to 5: 1 in the parallel feeding of oligomerization zones.Paraffinic hydrocarbons concentration is at least 50% (weight) in the general oligomerization zones charging, preferably is at least 70% (weight).The alkene of high per-cent reacts together with iso-butylene one in the oligomerization district in the feed stream.Olefin conversion is generally 80～99%.Contain C in the main oligopolymer
7+ alkene.
The oligomeric effluent of the heavy alkene that will contain unreacted heavy paraffin and obtain passes through saturating reactor.Suitable saturating reactor can substantially fully saturated all alkene from saturating reactor.From the effluent of oligomerization zones preferably without separating or reclaiming lighting end and directly deliver to the saturation region.The operation of oligomerization reactor under lower pressure makes the polymerization effluent directly to be sent in the hydrogenator.Exothermicity generally will make the saturation region operate under the temperature higher than oligomerization zones, and like this, cooling fluid in the oligomeric effluent and paraffinic hydrocarbons will provide additional heat sink material, be used for the release of saturated reaction district heat.
Before entering the saturation region, oligomeric effluent at first mixes with hydrogen-containing gas streams.This air-flow should contain the hydrogen of 50% (weight) at least.Density of hydrogen preferably is higher than 75% (weight) in the hydrogen-containing gas streams.Can be from dehydrogenation zone recover hydrogen, be used for providing most of hydrogen of input saturation region, the essential hydrogen of remainder is provided by the external air source of hydrogen as a supplement, or when dehydrogenation zone did not exist, external air source can provide all essential hydrogen.The preferred highly purified hydrogen hydrogen as a supplement that adopts enters the total purity of hydrogen of saturation region with raising, thereby reduces the volume of light hydrocarbon.These light hydrocarbons are normally unwanted, because their existence has unnecessarily increased the flow volume by the saturated reaction district, and their higher relatively vapour pressures will increase the loss of potential hydrocarbon in the downstream separation section.Yet have united dehydrogenation, oligomeric and saturated preferred the present invention is provided with and can conveniently uses the tripping device that can allow the low-purity hydrogen stream.
The hydrogen make-up air-flow is mixed by a certain percentage with oligomeric effluent, and wherein the proportional range of hydrogen and hydrocarbon is 0.1 to 2, and more preferably scope is 0.15 to 0.30.
The preferred saturating reactor of the present invention can substantially fully saturated all unsaturated hydrocarbons.The condition of hydrogen treatment zone generally comprises, and temperature range is 93～316 ℃ (200～600 °F), and pressure is that (100～700psig), liquid hourly space velocity is 1～20 hour to 791～4928kPa
-1Selecting preferred reaction conditions to keep the hydrocarbon charging is vapor phase.Hydrotreatment equipment is operation at a certain temperature usually, so that can carry out heat exchange by the effluent with hydrotreater, makes the blended feed stream rise to the temperature of saturated reaction.In this manner, the heat in the oligomeric and hydrogenation operation of any input preferably provides by the sealing heat exchanger in the inlet logistics in oligomerization district.
Preferred hydrotreating reactor contains the fixed bed of hydrotreating catalyst.Can be used for composite catalyst of the present invention and comprise traditional hydrotreating catalyst.Have now found that clay is particularly useful with the mixture that is selected from the aluminiferous metallic element of VIII and group vib in the periodic table of elements.VIII family element comprises iron, cobalt, nickel, ruthenium, rhenium, palladium, osmium, iridium and platinum, wherein preferred especially cobalt and nickel.The group vib metal is made up of chromium, molybdenum and tungsten, wherein preferred especially molybdenum and tungsten.Metal component is loaded on the porous solid support material.Solid support material can comprise aluminum oxide, clay or silicon-dioxide.Useful especially catalyzer contains the mixture of the molybdenum of the cobalt of 2～5% (weight) or nickel metal and 5～15% (weight) for those on alumina supporter.Weight metal percentage ratio exists with metallic state by them and calculates.General commercial catalyst comprises the alumina base mixture of sphere or extruding, and the ratio in above-mentioned suggestion on the aluminum oxide is impregnated with Co-Mo or Ni-Mo.Other useful catalysts composition is included in the nickel of 15～20% on the aluminum oxide (weight).The ABD value of commercial catalyst is generally 0.5～0.9g/ milliliter, and surface-area is 150～250m
2/ g.Usually, metal content is high more in the catalyzer, and catalyst activity is strong more.
The effluent in the district of self-saturation in the future separates, so that the heavy paraffin recirculation stream to be provided.The heavy paraffin component also comprises the hydrocarbon resultant.The separation of recirculation stream can be carried out in a simple separator, wherein saturated effluent is carried out roughing out, so that heavier feeds and any cooling material that cycles through the saturation region enough, that be used to be circulated to oligomerization zones to be provided.Recirculation is also included within the side logistics of the product of light matter material after separating in the main separator.
The effluent in saturated reaction district preferably enters in the quenching separator.The quenching separator is with a high proportion of C
4Reach the lower boiling material and from the effluent of saturation region, separate, the C with relative higher concentration is provided
8Reach quenching logistics than heavy hydrocarbon.From saturated reaction district effluent, reclaim the material of higher molecular weight, help the associating in oligomerization district and saturated reaction district.C
8The recirculation that reaches than heavy hydrocarbon provides non-reacted logistics, and it makes in the oligomerization district, kept strength of fluid under lower pressure.
Oligomerization zones operation under the lower pressure that use the present invention obtains also can be used for uniting valuably the dehydrogenation zone of oligomerization zones upstream.The charging of general dehydrogenation zone comprises light paraffin stream.Preferred material is rich in C
4Paraffinic hydrocarbons, and contain the Trimethylmethane of high per-cent.(term used herein " is rich in " to refer to and contains the logistics that its weight or meausurement percentage composition is at least 50% described component, and term " is rich in relatively " and refers to the logistics of comparing the described component with greater concn with charging, and this logistics is derived by charging and got.) charging of dehydrogenation zone more preferably contains 60～99% (weight) Trimethylmethane.The general source of incoming flow is natural butane, refining C
4Saturated air-flow reaches the butane from gas concentration unit.The Trimethylmethane air-flow can provide the source of being rich in the butane raw material from refining butane air-flow or other and obtain.The preferred dehydrogenation reaction zone of the present invention helps by using high pressure and low-conversion condition to unite dehydrogenation zone and oligomerization district.Lower transformation efficiency will reduce the deactivation of catalyzer to be used, and particularly when in conjunction with higher space velocity, will most of dehydrogenation reaction zone be operated at the regeneration requirement condition that has reduced.In addition, the elevated pressures condition especially can reduce the isolating compression needs of effluent, and can improve reaction efficiency.
Catalytic dehydrogenation method and reactor setting are to be known.Suitable method of dehydrogenating is that raw material is mixed with hydrogen-containing gas streams, and contacts with catalyzer in reaction zone.The preferred feedstock that is used for catalyzer dehydrogenation of the present invention mainly comprises Trimethylmethane, also can contain propane and pentane.The catalytic dehydrogenation method will be handled a large amount of paraffinic hydrocarbonss, thereby form olefin(e) compound.In present method, Trimethylmethane is lower to conversion for isobutene in the suitable dehydrogenation zone, and catalyst contamination speed is also relatively low.
Any suitable dehydrogenation catalyst all can be used in the inventive method.Preferred dehydrogenation reactor structure depends on the performance characteristics of catalyzer and reaction zone.Be used to operate under the low-conversion condition of dehydrogenation zone, the general yield of alkene is 10～40% (weight), is preferably 20～30% (weight).The operational condition of dehydrogenation zone preferably can make the alkene produced flow out iso-butylene in the logistics to the ratio of n-butene and propylene greater than 1.The regeneration of catalyzer can be achieved by shaking bed operation, half regenerative operation or continuous catalyst RS Regenerator Section.
Catalytic dehydrogenating reaction carries out having in the presence of the granules of catalyst usually, and wherein granules of catalyst comprises the precious metal (as platinum, iridium, rhodium and palladium) that is incorporated into one or more VIII families on porous support such as the refractory inorganic oxide.Usually preferred catalyst pack is contained in platinum group metal component, the alkaline components on the porous support.Catalyzer also can contain the promoter metal that helps to improve specificity of catalyst.The porous carrier materials of dehydrogenation catalyst preferably has 25～500m
2The adsorptivity high surface area carrier of/g surface-area.Porous carrier materials should be resistant to elevated temperatures relatively for the condition that reaction zone adopts, and can be selected from those and be usually used in solid support material in the difunctional hydrocarbon conversion catalyst.Therefore porous carrier materials can be selected from activated carbon, coke or charcoal, silicon-dioxide or silica gel, clay and comprise that those synthesize with naturally occurring, through or without the silicate of peracid treatment, as a kind of U.S. atlapulgite (attapulgus), carclazyte, diatomite (diatomaceousearth), diatomite (kieselguhr), bauxite, high-temperature inorganic oxide such as aluminum oxide, titanium dioxide, zirconium dioxide, magnesium oxide, sieve and silica-sesquioxide, aluminum oxide-boron oxide, mordenite or one or more these mixtures of material of crystalline pure aluminium silicate such as natural existence or synthetic preparation.Preferred porous carrier materials is resistant to elevated temperatures inorganic oxide, wherein can obtain the alumina supporting material that is of best result.Aluminum oxide is the most frequently used carrier.Known preferred alumina material such as γ-, η-and θ-aluminum oxide, wherein γ-and θ-aluminum oxide effect is best.Preferred catalyzer contains the θ-alumina supporter that exists with the spheroidal particle form.Be that (particle of 1/16 ") is preferred to 1.6mm, but also can be greatly to 5.6mm (1/4 ") than its grade of minor diameter relatively.
Platinum-group component can be with the oxide compound of compound form such as metal, sulfide, halogenide and oxysulfide etc. or be present in the final composite catalyst with the form in conjunction with other composition of one or more catalyzer.When nearly all platinum-group component exists with the simple substance form, it is believed that to obtain best result.Press the element benchmark and calculate, platinum-group component accounts for 0.01～2% (weight) of final composite catalyst usually.The content of platinum is preferably 0.2～1% (weight) in the catalyzer.Preferred platinum family element is a platinum, and palladium secondly.Platinum-group component can be incorporated in the composite catalyst in any suitable manner, and such mode is, for example, and with preferred solid support material co-precipitation or cogelled or by ion-exchange or impregnated carrier material.The preferred method of preparation catalyzer generally includes the solid support material that adopts water miscible decomposable platinum group metal compounds impregnation-calcination to cross.For example, platinum-group component can join in the carrier by carrier is mixed with Platinic chloride or chlorine palladium aqueous acid.A kind of sour example hydrochloric acid joins in the dipping solution usually, and this helps the distribution of platinum-group component in whole solid support material.The preferred catalytic agent material contains the chloride concentration of 0.5～3 weight percentage.
Preferred basic metal common or potassium or lithium, this depends on feed hydrocarbon.Press the element benchmark and calculate, alkali-metal concentration range is 0.1～3.5% (weight), is preferably 0.2～2.5% (weight).This composition can join in the catalyzer as an independent process or with another kind of component solution simultaneously by aforesaid method.
Dehydrogenation catalyst also can contain promoter metal.Such preferred promoter metal is a tin.The tin component should be made of the tin of 0.01～1% (weight).The atomic ratio of tin and platinum is preferably 1: 1 to 6: 1.The tin component can be incorporated in the composite catalyst with any known suitable method, thereby effectively this component is scattered in the whole solid support material in very uniform mode.Mix the preferred method of tin component, carry out co-precipitation when being included in the preferred solid support material of preparation.About the more detailed description of the interpolation of the preparation of solid support material and platinum component and tin component with reference to US-A-3745112.
The low severe degree operation of preferred dehydrogenation zone will prolong catalyst life.According to the characteristic of catalyst system and dehydrogenation zone charging, dehydrogenation reaction zone will use can be as the solid catalyst of fixed bed, half Regenerative beds or continuous catalyst RS Regenerator Section system.It is simple relatively that dehydrogenation zone actual is provided with, and comprises a reactor and a well heater.Yet the catalysis dehydrogenation reaction zone is made up of a plurality of catalyst beds.In a kind of such system, in annular bed, use catalyzer, by this bed, catalyzer moves in the gravity flowage mode.At US-A-5227566, US-A-3978150 has described the preferred method of light hydrocarbon dehydrogenation among US-A-3856662 and the US-A-3854887, and this method is applicable to the continuous dehydrogenation that carries out Trimethylmethane with successive catalyst regeneration system.
In preferred scheme, method of dehydrogenating uses moving bed reaction district and breeding blanket.When removing or more during catalyst changeout, the moving-bed system helps to keep production.In typical moving bed reaction district, the catalysis system particle of new system is passed through gravity supply response district.Take out catalyzer and be sent to the breeding blanket from the reaction zone bottom, wherein adopt the multistep renovation process that describes below to readjust catalyzer, promote the fully ability of reaction to recover it.Catalyzer takes out and the supply response district from the breeding blanket then by the different excessively regeneration step of run by gravity.In moving-bed, typical combustion zone, drying zone and being provided with of redispersion district can be referring to US-A-3653231 and US-A-5227566.
The operational condition of the preferred dehydrogenation zone of the present invention generally includes, and operating temperature range is 510～649 ℃ (950～1200 °F), wherein is preferably at least 593 ℃ (1100 °F), is preferably 610 ℃ (1130 °F) especially.High relatively working pressure has characterized the low-conversion condition of preferred dehydrogenation zone, and its scope is generally 377～1136kPa (40～150psig).The pressure of preferred dehydrogenation zone is generally 446kPa (50psig) at least, is preferably 584～860kPa (70～110psig) especially.The low-conversion condition is also allowed the low mol ratio 0.1～4 at hydrogen and hydrocarbon, more preferably from about carries out the dehydrogenation zone operation under 0.2 the condition.Dehydrogenation zone air speed scope is 0.5～50 hour
-1, usually above 10 hours
-1, typically equal about 15 hours
-1
When with the oligomerization zones of low pressure of the present invention when linked together, the low-conversion of dehydrogenation reaction zone and lower pressure also help the saving of equipment.For example a piston blower can be used for reclaiming recycle hydrogen from the dehydrogenation effluent.In the dehydrogenation zone higher pressure and with the associating of saturation region also can reduction and hydrogen supply and the relevant cost of equipment of recovery hydrogen.In dehydrogenation zone, adopt high relatively pressure also can pass through the cooling recovery 80% or the more highly purified hydrogen stream of minimum.The harmful effect that produces because a large amount of Trimethylmethane recirculation can weaken that any alkene is entrained to dehydrogenation zone is so the low-conversion of dehydrogenation zone is operated the hydrogen stream that can adopt described low-purity.In addition, supply to from the excessive hydrogen of dehydrogenation zone and to cause in primary fractionator, reclaiming excessive Trimethylmethane in the saturation region, otherwise in present method operation, will cause the unacceptable loss of this class hydrocarbon.
Below in conjunction with accompanying drawing the inventive method and different operation stepss are described.
Be rich in C
4The light hydrocarbon streams of paraffinic hydrocarbons enters deisobutanizer 10 by pipeline 12.Tower 10 also accepts to flow out from saturation region described below the recycle stock of logistics by pipeline 96.Deisobutanizer 10 provides and contains the logistics 16 of sideing stream that is useful on dehydrogenation zone feed stream Trimethylmethane.
Accompanying drawing has shown the operation of the dehydrogenation zone that has the catalyst regeneration system, and this regeneration system provides the catalyzer of having regenerated through pipeline 38 to reactor 26 and 34.Catalyzer transmission system (not indicating) is passed to catalyzer lifting conduit 46 from reactor 26 and 34 bottoms with coked catalyzer by conduit 42 and 44 respectively.Promote conduit 46 coked catalyzer is sent to breeding blanket 48.Catalyst regeneration zones 48 is repaired catalyzer by the coke burning.
Effluent 20 from dehydrogenation reaction zone contains hydrogen, butane, butylene, some light hydrocarbons and a small amount of heavy hydrocarbon at least.Make effluent from dehydrogenation reaction zone flow through interchanger 18 and be passed in the separator 52 through pipeline 20, will remove from the different heavy hydrocarbon component that flows out in the logistics by pipeline 57 through pipeline 50.Pipeline 56 will be loaded onto in the hydrogen gas segregator 54 from the steam effluent of heavy hydrocarbon separator 52, is used to reclaim hydrogen-containing gas streams, and this air communication is crossed pipeline 22 hydrogen is recycled in the charging of dehydrogenation zone.Dehydrogenation zone of the present invention can use not too pure hydrogen stream relatively.Density of hydrogen in the suitable hydrogen gas recycle air-flow of the present invention is less than 90% (weight).Acceptable density of hydrogen can be low to moderate 70% (weight), is generally about 80% (weight), and the rest part of hydrogen-containing gas streams contains C
1～C
3The C of hydrocarbon and some lower concentrations
4Hydrocarbon.If desired, thus can reduce the purity that the cut impurity of bringing in the air-flow 22 increases hydrogen stream in the dehydrogenation zone from the overhead product of separator 54 by cooling.As mentioned below, the residuum of the hydrogen-containing gas streams that reclaims from separator 54 is as the hydrogen feed of saturating reactor.
The bottoms 60 of self-separation device 54 is mixed with the air-flow 58 that contains alkene in the future, to provide parallel feeding to the oligomerization district.The olefin stream that contains by pipeline 58 deliveries provides extra alkene to the oligomerization district.The alkene that enters by pipeline 58 comprises n-butene and iso-butylene, also can comprise C
3And C
5Alkene and some paraffinic hydrocarbonss.
Opposite with the flow direction of saturation region effluent, pipeline 60 delivery blended oligomerization zones incoming flows are by interchanger 62, the charging that is used to heat oligomerization zones.The oligomeric charging of pipeline 64 delivery heating enters reactor by pipeline 68 again by airtight well heater 66.According to the present invention, contain C
8And mix with the charging that enters oligomerization zones by pipeline 69 than the heavy recirculation stream of heavy paraffin.The oligomerization zones charging is continuously by a series of multistage oligomerization reactors 70 that are divided into.Extra C
8And enter the intermediate bed position of reactor 70 by chilled distribution pipeline 72 than heavy paraffin, to cool off each intermediate reaction level.The injection of refrigerant provides heavy material of the present invention, and this also guarantees to help the flushing of catalyzer and helps higher octane C
8The selectivity of isomer.The effluent pipeline 74 that links to each other with the outlet of oligomerization reactor 70 will reclaim oligomeric effluent logistics.
The saturation region will and carry out saturatedly to the component in the not full gasoline boiling range scope from unreacted light olefin in the oligomerization zones, be used to provide high-quality alkylate stream.The placed in-line a plurality of reactors 82,86 of the general use in saturation region, its charging is by each reactor.The equal temperature controllable of this series reaction equipment.
At least a portion logistics 94 of saturation region effluent 90 turns back to described oligomerization zones 70 and described saturation region 82,86 through overcooling and as cooling liqs 72, and cooling liqs 72 provides a part of described recirculated air 69.Described oligomerization zones 70 contains a solid phosphoric acid catalyst bed, described cooling liqs 72 is injected in the described bed at least one place, mid-way.
Opposite with the effluent flow direction from the saturation region, indirect heat exchange is carried out in pipeline 84 delivery parallel feedings in interchanger 86, and the charging of warmed-up saturation region flows to first saturating reactor 82 by pipeline 87.
Preferred hydrogenation zone equipment is two-stage hydrotreating reactor system, and wherein the effluent of first saturating reactor 82 is passed to second reaction zone 86 by pipeline 85.Be the temperature that control is produced by the first reaction zone heat release, the part heavy hydrocarbon transmits by pipeline 88 as refrigerant stream and mixes with the first reaction zone effluent 85.Now saturated oligomerization district effluent transmits by heat exchanger 86 by pipeline 90, is sent to heat exchanger 62 by pipeline 91 again, before entering cooling separator 92 by pipeline 93, can reclaim the saturated reaction heat like this.
Cooling separator 92 is retrieved the saturated heavy material in self-saturation district, is used to provide liquid phase recirculation stream of the present invention.Bottoms 94 from separator 92 provides the heavy recycle stock by pipeline 69 and 72 to oligomerization zones, and provides cooling by pipeline 88 for the saturation region.The nubbin of heavier feeds returns separator top overhead product by pipeline 95, and discharges from technical process as the bottoms of deisobutanizer 10 by pipeline 102.Distillate material and any additional separator bottom effluent that provides by pipeline 95 takes out by pipeline 96 from the top of separator 92, wherein mainly comprise high-quality alkylate and unreacted butane.Being recovered in the interchanger 98 of extra heat from separator logistics 96 carried out, and is used for the temperature of preliminary rising from the dehydrogenation zone feed stream of deisobutanizer 10.
Preferred equipment of the present invention adopts deisobutanizer 10, so that distill product that contains separator overhead product stream and the preliminary production of carrying out the dehydrogenation zone incoming flow simultaneously.Preferred deisobutanizer reactor is isolated lighting end with overhead product stream 100, simultaneously as the dehydrogenation zone charging 16 of sideing stream and providing above-mentioned.This arrangement is done in the design of deisobutanizer, and the Trimethylmethane of high density is provided in the charging of dehydrogenation zone by the logistics of sideing stream.Deisobutanizer generally will provide the Trimethylmethane of 80% (weight) purity, and preferred purity is at least 95% (weight).Operating this tower can also flow 100 by overhead product isolate remaining C from the dehydrogenation zone incoming flow
4Few products.Primary fractionator also can be transmitted the saturated oligomerization zones product component as bottom effluent 102.Preferred deisobutanizer also can provide positive C
4The logistics of sideing stream is used for getting rid of unreacted butane from technical process.Side stream and can take out by pipeline 104, this cut by with heat exchanger 106 in C
4Feed stream carries out indirect heat exchange and extra heat is provided.
For describing advantage of the present invention more comprehensively, carry out following test.
Embodiment 1
The incoming flow of Trimethylmethane of iso-butylene and 69.4% (weight) that will consist of the n-butene, 17.7% (weight) of 13% (weight) contacts with about 50 milliliters of a kind of solid phosphoric acid catalysts, and this catalyzer contains the sintering mix of the phosphoric acid on silicon matrix.Catalyzer is that diameter and length are about 6.4mm (pellet of 1/4 "), they are contained in volume is that 70 milliliters 22mm is (in the stainless steel reaction container of 7/8 ").By avoiding channel with the void volume between the sand filler particles carefully.Under the pressure of 190 ℃ (374) and 3549kPa (500psig), material enters reactor and with 2 hours
-1Liquid hourly space velocity is passed through reactor.The temperature of reactor of oligomerization is up to 202 ℃ (396 °F).The sample of reactor effluent is reclaimed, distills and analyzes, to measure C
4The carbon number selectivity of conversion of olefines rate and product.Analytical results is listed in table 1.
Table 1
| Charging | Transformation efficiency (%) | The carbon number selectivity, weight/% 5-＞78 9-＞11 12＞12 | ||||
| Embodiment 1 | Just-C4 -=85 different-C4 -=91 total C4 - ＝88 | 8.4 | 56 | 5.2 | 28 | 2.4 |
| Embodiment 2 | Just-C4 -=81 different-C4 -=91 total C4 - ＝86 | 4.7 | 66.2 | 3.9 | 24.6 | 0.6 |
Embodiment 2
In order to prove the advantage of heavy paraffins recirculation, in the charging of embodiment 1, add the positive C of 25% extra (weight)
8Paraffinic hydrocarbons, and under certain operational condition, react, wherein catalyzer is with embodiment 1.The accessible top temperature of oligomerization zones is 200 ℃ (392 °F).With the sample redistillation and the analysis of reaction zone effluent, found that and contain the more C of high percent
8Alkene.Analytical results is also listed in table 1.
By comparing embodiment 1 and embodiment 2, prove at C
4Under the olefin conversion situation about equally, add C
8Paraffinic hydrocarbons makes the selectivity of reactor effluent shift to significantly and produces in demand C
8The direction of isomer, and avoided higher astoundingly and generate than the product of low carbon number isomer.
Show as this embodiment, recirculation stream of the present invention oligomeric be high-octane rating C
8The selectivity aspect of isomer has one to improve significantly.
Embodiment 3
Incoming flow and about 50 milliliters and the embodiment 1 that will consist of the Trimethylmethane of 8.4% (weight) n-butene, 21.9% (weight) iso-butylene and 69.7% (weight) contact with 2 same solid phosphoric acid catalysts.Reaction vessel and catalyzer load technology and also are same as embodiment 1 and 2.Under the pressure of 191 ℃ of (376) temperature and 3549kPa (500psig), material enters reactor and with 2 hours
-1Liquid hourly space velocity pass through reactor.The reactor top temperature of oligomerization is 206 ℃ (403 °F).With sample recovery, hydrogenation, distillation and the analysis of reactor effluent, measure C
4The carbon number selectivity of conversion of olefines rate, product and research octane number (RON) and motor-method octane number.Analytical results is listed in table 2.
Embodiment 4～6
Compare C in order to prove
8More heavy constituent reach the advantage than low operating temperature, with the positive C of 25% extra (weight)
12Paraffinic hydrocarbons joins in the charging as embodiment 3, and reacts under service temperature that reduces and air speed, and wherein catalyzer is with embodiment 3.With from adding C
12The effluent of three tests of component after to the charging distills and hydrogenation, and its transformation efficiency, selectivity and research octane number (RON) and motor-method octane number are listed in table 2 as embodiment 4-6.
Table 2
| Charging | Temperature ℃ inlet/the highest | Liquid hourly space velocity hour -1 | Transformation efficiency % | Carbon number selectivity 5-＞78 9-＞11 12＞12 | Organon rate alkane value | Motor method rate alkane value | ||||
| Embodiment 3 | 191/206 | 2 | Just-C4 -=83 different-C4 -=94 total-C4 - ＝91 | 10.5 | 51 | 6 | 30 | 2.5 | 83.3 | 84.6 |
| Embodiment 4 | 153/161 | 2 | Just-C4 -=54.5 different-C4 -=96.5 total-C4 - ＝87 | 0.8 | 87.2 | 0.3 | 11.7 | - | 101 | 95.0 |
| Embodiment 5 | 160/171 | 2 | Just-C4 -=63.7 different-C4 -=95.9 total-C4 - ＝88.7 | 1.3 | 83.1 | 0.9 | 14.7 | - | 99.7 | 94.7 |
| Embodiment 6 | 165/170 | 0.75 | Just-C4 -=83 different-C4 -=96.5 total-C4 - ＝94 | 2.3 | 75.3 | 1.6 | 20.8 | - | 97.9 | 93.2 |
All 3 tests are all carried out under the temperature that has reduced with respect to embodiment 3, by adding positive C
12Paraffinic hydrocarbons is to C
8Selectivity increases significantly.Embodiment 4 and 5 all shows, C
8The selectivity ratios embodiment 3 of isomer exceeds a lot and transformation efficiency only reduces very little.The selectivity that has improved causes the octane value of gained than not adding C
12The embodiment 3 of component is high.Embodiment 6 shows that the transformation efficiency that is higher than embodiment 3 can obtain under relative comparatively high temps and the air speed that reduces, and still keeps being significantly higher than the C of embodiment 3
8The selectivity of isomer.
Claims (10)
1, a kind of method of producing saturated oligomer, this method comprises:
A) transmission contains C
3～C
5The dehydrogenation zone charging [16] of paraffinic hydrocarbons makes it to contact with the dehydrogenation catalyst that is arranged in dehydrogenation zone [26], and this dehydrogenation zone maintains to produce effectively and comprises C
3-C
5The dehydrogenation zone of alkene flows out under the dehydrogenation condition of logistics [20];
B) transmission comprises the described C of comprising of a part
3-C
5The dehydrogenation of alkene is flowed out logistics [20] and is comprised the oligomerization zones charging [60] of the recirculation stream [69] with at least 8 carbon atom chain alkane, make it to contact with oligomerisation catalyst, this catalyzer is loaded in the oligomerization zones [70], and oligomerization zones [70] remains under the oligomeric condition that can effectively produce the outflow logistics that contains the alkene with at least 7 carbon atoms;
C) reclaim the oligomeric effluent in described district [70], wherein contain described paraffinic hydrocarbons and have the alkene of at least 7 carbon atoms;
D) be sent to the effluent [74] of small part oligomerization zones [70] and hydrogen logistics [76] to the saturation region [82,86] in, this saturation region contains the saturation catalyst under effective saturation conditions, described saturation conditions can the saturated effectively alkene in the oligomeric effluent of described part [74], and reclaim the saturation region and flow out logistics [90];
E) as described recirculation stream [69], the part [94] that will contain the described saturation region outflow logistics [90] of the paraffinic hydrocarbons with at least 8 carbon atoms is sent to described oligomerization zones [70]; And
F) recovery contains C
8And the described saturation region of heavy paraffin flows out the part [102] of logistics [90].
2, method as claimed in claim 1, wherein said oligomerization zones catalyzer is a kind of solid phosphoric acid catalyst.
3, method as claimed in claim 1, wherein said oligomerization zones is operated under the pressure less than 2170kPa.
4, method as claimed in claim 1, wherein said recirculation stream comprises C
8Or C
12Paraffinic hydrocarbons.
5, method as claimed in claim 1, wherein said oligomeric feed stream comprises C
4Alkene.
6, method as claimed in claim 1, at least a portion logistics [94] of wherein said saturation region effluent [90] turns back to described oligomerization zones [70] and described saturation region [82 through overcooling and as cooling liqs [72], 86], cooling liqs [72] provides a part of described recirculated air [69].
7, method as claimed in claim 6, wherein said oligomerization zones [70] contains a solid phosphoric acid catalyst bed, described cooling liqs [72] is injected in the described bed at least one place, mid-way.
8, method as claimed in claim 1, the operating temperature range of wherein said oligomerization zones are 149～204 ℃.
9, a kind of method of producing the motor spirit product by the incoming flow that contains Trimethylmethane [16], this method comprises:
A) transmit contain Trimethylmethane described incoming flow [16] to dehydrogenation zone [26,34], and under dehydrogenation condition, in described dehydrogenation zone, described incoming flow is contacted with dehydrogenation catalyst, this dehydrogenation condition can be produced effectively and contain hydrogen and C
4The effluent of isoolefine [20];
B) from described dehydrogenation effluent [20], isolate hydrogen stream [78], and recovery contains C from the resistates of described dehydrogenation effluent with 70～95mol% hydrogen purity
4The incoming flow of isoolefine [60] is with preparation oligomerization zones incoming flow [60];
C) recirculation stream [69] that transmits described oligomerization zones charging [60] and contain paraffinic hydrocarbons is to oligomerization zones [70], and under oligomeric condition, contact with the solid oligomerisation catalyst, this oligomeric condition can be produced the oligomeric effluent [74] that contains the isoolefine with at least 7 carbon atoms effectively;
D) transmit at least a portion in step b) separated hydrogen stream [78] and not separated effluent [74] from oligomerization zones [70] to the saturation region [82,86] in, this saturation region comprises saturation catalyst, wherein catalyzer remains under the saturation conditions of the alkene in the saturated effectively oligomeric effluent [74], and reclaims saturation region outflow logistics [90];
E) transmit the described saturation region of at least a portion and flow out logistics [90], contain the saturated logistics [94] of paraffinic hydrocarbons with recovery with at least 8 carbon atoms to the disengaging zone [92]; And
F) at least a portion logistics [69] with described saturated logistics [94] is recycled in the step c) as described recirculation stream.
10, method as claimed in claim 9, wherein the concentration of olefin of oligomerization zones incoming flow is for containing the iso-butylene of at least 30% (weight).
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|---|---|---|---|
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