CN1017796B - The composite catalyst that is used for olefin oligomerization - Google Patents
The composite catalyst that is used for olefin oligomerizationInfo
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- CN1017796B CN1017796B CN88101783A CN88101783A CN1017796B CN 1017796 B CN1017796 B CN 1017796B CN 88101783 A CN88101783 A CN 88101783A CN 88101783 A CN88101783 A CN 88101783A CN 1017796 B CN1017796 B CN 1017796B
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- composite catalyst
- family metal
- catalyzer
- iron
- oligomerization
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
In olefin feedstock, contain catalyst contamination thing or poisonous substance, under the situation as sulfocompound, available a kind of when having above-mentioned poisonous substance to exist, still have stability and can not subtract active catalyzer carry out oligomeric, obtain desired oligopolymer and oligopolymer configuration, this catalyzer contains porous carrier, and with a kind of iron family metal of catalytically effective amount, as iron or nickel, and a kind of metal of the non-transition of periodictable IV, as tin or germanium, dipping forms.This composite catalyst also can make up with the alkylaluminium cpd that contains catalytically effective amount, and in optimum implementation, with aluminum alkoxide that contains catalytically effective amount and/or aluminum halide compounds combination.
Description
The present invention relates to be specifically designed to olefin oligomerization with generate higher molecular weight alkene a kind of novel catalyst system-for example, the propylene selective conversion generates a kind of C
6Alkene.
The Oligomerisation of alkene is being known in the art, and these oligomerization process are to use some catalyst treatment alkene, obtain will having in chemical technology the various oligopolymer of certain purposes.In the reaction of this particular type, adaptable a kind of type catalyst comprises the metallic compound on a kind of carrier.For example, United States Patent (USP) 3,562,351 disclose the method that catalyzer on a kind of application vector carries out dimerizing olefins, this kind Preparation of catalysts is a kind of suitable carrier to be used a kind of salt solution impregnation of VIII family metal, heat-treat under inert gas atmosphere then, thermal treatment temp is to be lower than the formation metal oxide, but can form a kind of temperature of title complex on the surface of this kind solid carrier.Then this kind catalyzer is handled with a kind of organometallic compound, activated.United States Patent (USP) 3,483,269 have described a kind of oligomeric catalyzer of light alkene that is used for, and this catalyzer is to be stated from a kind of acid inorganic oxide carrier by π-allyl group halogenation nickel.If such needs are arranged, then this kind carrier can be chosen wantonly with a kind of alkylaluminium cpd and handle.United States Patent (USP) 3,592,869 have also described a kind of catalyzer that is used for olefin oligomerization.A kind of nickelous compound is contacted with a kind of olefinic compounds with a kind of alkylaluminium cpd.Mixture with gained is used to flood a kind of inorganic resistivity against fire oxide carrier then.Another patent, be United States Patent (USP) 3,644,564 have described a kind of catalyzer that is used for ethylene oligomerization, this catalyzer comprises a kind of no aluminium organic reaction product that has the nickel compound of fluorine-containing ligand, and this product is made up of a nickle atom and a kind of alkenes unsaturated compound.This kind catalyzer generally is to make on the spot.United States Patent (USP) 3,679,772 have described a kind of method by monoolefine and diolefine reaction, the used catalyst pack of this reaction contains by (1) nickel, (2) a kind of V-A family electron donor ligand, for example a kind of organic phosphine, (3) a kind of non-proton Lewis acid and (4) are a kind of itself can be a kind of lewis acidic reductive agent, all catalyzer, they all are compounded on a kind of carrier of acid silicon dioxide base.
As the situation that hereinafter will more describe in detail, can provide the product with required configuration by the oligomeric of alkene, said configuration is to exist by a kind of catalyzer of the present invention in other words about chain top set situation to handle the minimum ramose configuration that described alkene is made down.Exist in reaction feed under the situation of some impurity or toxicant, this kind catalyzer will keep it active and stable between longer-term.
The present invention relates to be used for a kind of composite catalyst of olefin oligomerization.More precisely, the present invention relates to a kind of composite catalyst and olefinic compounds, particularly alkene and carry out oligomeric a kind of method, wherein using this kind composite catalyst will make resultant is the selective oligomerization thing of this kind olefinic feed.
Term " polymerization " has quite wide connotation in chemical field.Though this term generally is meant the very high polymkeric substance of preparation molecular weight, that is molecular weight is greater than 50,000 or higher polymkeric substance, but it also can be meant the polymkeric substance of lower molecular weight, that is molecular weight is lower than 50,000 polymkeric substance, term " Oligomerisation " then with last completely different, and it is meant that the polymeric compounds molecule only contains less monomeric unit, therefore comprised dimerisation, terpolymerization or four poly-effects.
Therefore, an object of the present invention is to provide a kind of catalyzer that is used for olefin oligomerization.
A further object of the invention provides a kind of special-purpose catalyst system in the method that can be used for olefin oligomerization, thereby adopts this kind method can obtain the selective oligomerization thing.
On the one hand, one embodiment of the invention are a kind of composite catalyst, and its composition comprises the alkylaluminium cpd of catalytically effective amount and the molectron of the porous carrier of a kind of iron family metal of containing catalytically effective amount.Said iron family metal, for example nickel or iron and contain a kind of nontransition metal that belongs to periodictable IV family for example are tin or germanium.
In another embodiment of the present invention, the oligomerization process that can see alkene comprises and will contain raw material and a kind of composite catalyst of described hydrocarbon, be a kind of alkylaluminium cpd and a kind of iron family metal of containing catalytically effective amount, and a kind of molectron of the porous carrier of the nontransition metal of a kind of periodictable IV family, under the oligomerization condition, contact, and reclaim the oligopolymer of this kind generation.
In a specific embodiments of the present invention, can see in composite catalyst, a kind of molectron of the diethyl aluminum chloride that contains catalytically effective amount on the alumina supporter of a kind of nickel that contains catalytically effective amount and tin, preferably nickel wherein is to be to exist with the chlorization high tin state with aqua oxidation nickel, wherein tin.
In another specific embodiments of the present invention, can see and comprise a kind of catalyzer of use in the alkene oligomerization process, a kind of molectron of the three tert.-butoxy aluminium that this catalyzer comprises the diethyl aluminum chloride of catalytically effective amount and catalytically effective amount on the alumina supporter of a kind of a kind of nickel compound that contains catalytically effective amount and chlorization high tin, temperature in-20 ℃ to 200 ℃ scopes, and the pressure in 350 to 1000 pounds/square inch gauge (2.5 to 7 MPa) scope, butylene is handled, and reclaim generated by octene, this kind oligopolymer that methyl heptene and dimethyl hexene mixture are formed.
Other purposes of the present invention and embodiment will be included in hereinafter the detailed description.
Up to now, it all is suitable difficulty that preparation can be used for olefinic compounds polymerization or oligomeric catalyzer, because need be with the component of several expensive compounds as this composite catalyst, and simultaneously need be with some complicated method when making this catalyzer.Composite catalyst of the present invention is then completely different, and than being easier to preparation, in addition, also used than other catalyzer each component of used compound is more inexpensive.Final composite catalyst finished product of the present invention will have very high reactivity, and keep its stability in the long term.In addition, composite catalyst of the present invention will have required stability and active, because catalyzer of the present invention can still can be finished required oligomerization effectively having under the situation of impurity.And these impurity can make poisoning of catalyst or deactivation under usual conditions.
Exist in this kind raw material this catalyzer is risen subtracts active concrete impurity, includes various sulfocompounds, thion for example, hydrogen sulfide; Mercaptan, as thiomethyl alcohol, sulfur alcohol, propylmercaptan etc.; Disulphide, as dimethyl disulphide, diethyl disulphide.In addition, other make catalyzer subtract active impurity as comprising the oxygenatedchemicals of oxygen-containing organic compound, and for example alcohols comprises methyl alcohol, ethanol, propyl alcohol etc.; Ethers, as dimethyl ether, Anaesthetie Ether, methyl ethyl ether, methyl-propyl ether etc.; Aldehydes, as formaldehyde, acetaldehyde; And ketone, acetone for example, methylethylketone etc.In general, these impurity can exist by trace, for example account for the 0.1-100ppm scope of raw material.But,, therefore when these impurity exist, make this catalyzer deactivation very soon even the impurity of trace also can have adverse effect to the activity and the stability of these oligomerisation catalysts.
Now unexpected the discovery, in the present invention, new catalyst according to method preparation hereinafter described, to show the toxin immunity effect that unanticipated arrives for these impurity, therefore will make this catalyzer be used for keeping due activity when converted olefin becomes two polymkeric substance of requirement, maintenance is stable in long-term simultaneously.This catalyzer can also make the yield of product two polymkeric substance all high more a lot of than trimer tetramer, especially with C except that having these due attributes
3And C
4Alkene carries out when oligomeric.Pass through in the Oligomerisation gained dimerisation products by propylene and various n-butene, straight chain compound, promptly various n-hexylenes and various positive octene, and have only the dipolymer of a methyl substituents will account for very high percent; The oligopolymer that branch degree is higher only accounts for very small portion.With the prepared propylene dimer of method of the present invention, no matter its side chain what state all has very high-octane rating, is the blending compound of high-grade boosting of octane rating therefore.In addition, the dipolymer of various n-butenes all is the intermediate that is used to prepare excellent softening agent.
Composite catalyst of the present invention will comprise a kind of alkylaluminium cpd and a kind of a kind of composition through the incinerating porous carrier of catalytically effective amount, and carrier wherein contained a kind of a kind of hydrate of iron family metal and contains in the periodictable a kind of compound of nontransition metal in the IV family before calcining.In optimum implementation of the present invention, this iron group metal hydrate will be obtained by following compounds: the hydrate of the soluble salt of a kind of nickel, iron or cobalt, for example nickelous nitrate, nickel hydroxide, nickelous bromide, nickelous chloride, nickelous fluoride, nickelous acetate, cobaltic chloride, cobaltous acetate, cobalt chloride ammonium, cobaltous bromide, cobaltous fluoride, cobaltous perchlorate, rose vitriol, ferrous acetate, ferrous bromide or iron bromide, iron protochloride or iron(ic) chloride or the like.The compound (being meant the element of cycle the IV-A family hereinafter) that contains periodictable IV family nontransition metal will comprise the salt of these metals, and germanium chloride for example, is fluoridized germanium, germanium sulfide etc. at iodate germanium; Tin tetrabromide, tin chloride, oxychlorination tin, tin sulphate, lead acetate, lead perchlorate etc.In scope of the present invention, expect that also these metals also can its element morphology be used as a kind of component of composite catalyst of the present invention.
This kind porous carrier that floods with the hydrate of this kind iron family metal salt, to comprise inorganic, metal oxide, aluminum oxide for example, silicon-dioxide, hopcalite, alumina silica for example, aluminium oxide-zirconium oxide one magnesium oxide or the like perhaps generally is referred to as the crystal aluminosilicate of zeolite.
Constitute another component alkylaluminium cpd of this composite catalyst, for example include: alkyl aluminum halide, chlorodimethylalumiu for example, diethylaluminum chloride, chlorination dipropyl aluminium, bromination dimethyl aluminium, the bromination diethyl aluminum, bromination dipropyl aluminium, iodate dimethyl aluminium, the iodate diethyl aluminum, iodate dipropyl aluminium or the like.
A kind of optional components that can exist in composite catalyst of the present invention comprises a kind of alkoxy aluminum compound, and it will be as a kind of activator of this composite catalyst.The example of these alkoxy aluminum compounds will have general chemical formula Al(OR)
3, wherein R represents a kind of low molecular weight alkyl, its carbonatoms is about 1 to 6.Some particular instance of these alkoxy aluminum compounds will comprise aluminum methylate, aluminum ethylate, aluminium propylate, aluminium isopropoxide, three n-butoxy aluminium, three tert.-butoxy aluminium, three pentyloxy aluminium, three hexyloxy aluminium or the like.In scope of the present invention, expect when needed that also this kind composite catalyst also contains a kind of aluminum halide compounds, in order to alternative this alkoxy aluminum compound, or both and usefulness.The example of these aluminum halide compounds will comprise aluminum chloride, aluminum bromide, aluminum iodide etc.Self-evident, iron family metal listed above compound, IV-A family metallic compound, alkylaluminium cpd, and alkoxy aluminum compound, just represent this compounds can be applied to form composite catalyst of the present invention, and described invention need not be limited.
This kind oligomerisation catalyst of the present invention can prepare in such a way, even also the finished catalyst of gained possesses in the presence of this catalyzer, reaction by a kind of alkene obtains the selectivity about alkene, and the feature that needs such as the specificity of the product that so makes.This composite catalyst can be with a kind of porous carrier of aforementioned type, with the simple salt of a kind of divalence iron family metal, and for example nickelous nitrate, and a kind of IV-A family metal-salt, for example tin chloride, and preferably a kind of aqueous solution is made through dipping.Other method, this porous carrier can flood with a kind of iron family metal salt brine solution, and can IV-A family metal be added technology in this kind carrier with the known any method of those skilled in the art.For example, some colloidal sols are infiltrated up in this carrier as the colloidal sol that can prepare tin or germanium and with known sol/gel method.Which kind of situation no matter, when this porous carrier, for example aluminum oxide is after dipping, and described dipping is to carry out under room temperature and barometric point, then with this impregnated carrier heat-treat.By changing this heat treated temperature, might make the composite catalyst that obtains possess the big selectivity of this kind alkene being carried out this oligomerization gained dipolymer, compare with using other conventional oligomerisation catalysts, the amount of finding dipolymer is more than trimer and tetramer amount.The thermal treatment of impregnated carrier is preferably in about 300 ℃ to be carried out to about 450 ℃ of scopes, and optimum heat-treatment temperature range is about 340 ℃ to about 360 ℃.Contain and flood IV-A family metal or its salt, and the catalyzer base of hydrated state iron family metal salt, will bodies lost weight when heat-treating or calcine, this is owing to lose the water of hydration of this metal-salt, and form a kind of iron family metal compound of the hydrogeneous and oxygen not according to stoichiometric relation, also can be used as them is hydrates of a kind of iron family metal oxide compound and/or salt.In optimum implementation of the present invention, the water of hydration after the thermal treatment will be greater than 0.5: 1 to the molar ratio of iron family metal, preferably in about 0.5: 1 to about 6: 1 scope.Contain this kind catalyzer base with a kind of this iron family metal compound of hydrate forms, the used time is to be shorter than the required time of these water of hydration of driving away fully usually when thermal treatment.
In temperature range mentioned above, this catalyzer base and this kind iron family metal salt are heat-treated or calcined, will the bonding of this iron family metal and this catalyzer base takes place, normally by a kind of metal-oxygen-base key combination, the oxygen of this key partly is partly to be provided by the oh group that the type porous carrier surface of above describing in detail exists.
After this thermal treatment, this kind promptly handled by a kind of alkylaluminium cpd, and can be chosen wantonly with a kind of aluminum alkoxide or a kind of aluminum halide component, to make the most highly active catalyzer of a kind of tool by the impregnated catalyzer base of iron family metal salt.With this kind alkylaluminium cpd and of the processing of this kind activator to this kind base-material, also be under room temperature and barometric point, to carry out, the solution of application compound for treating these compound for treating in other words is dissolved in a kind of organic solvent, and for example the solution of benzene, toluene, various dimethylbenzene isomeries etc. carries out this processing.
Add this organic solution, otherwise or with this incinerating base-material join in this organic solution, a kind of thermopositive reaction will take place, and behind thorough mixing, with gained contain this mixture solution of impregnated web let alone to return to room temperature.Available then ordinary method is removed this kind solvent, and for example decant evaporates, and filters etc., then can be with this composite catalyst of a kind of organic solvent washing, to remove the undesirable compound part of resistates or trace.This catalyzer can be used nitrogen wash method drying then, reclaims then.In this composite catalyst finished product, the molar ratio range of this alkylaluminium cpd amount is that every mole of iron family metal has about 0.05: 1 to about 6: 1, is preferably about 0.1: 1 to about 1: 1 mole alkylaluminium cpd; The amount of this kind iron family metal in described composite catalyst is benchmark and by this composite catalyst weight in the element, is about 1% to about 20% scope, preferably about 1% to about 10% scope.In addition, also will have IV-A family metal in described composite catalyst, be benchmark and by this composite catalyst weight in the element, is to about 20% scope, preferably in about 1% to 10% scope about 0.1%.For obtaining optimal result, the weight ratio of IV-A family metal pair iron family metal is to remain on 0.1: 1 to 10: 1 scope.
As hereinafter describing in detail, by preparing a kind of catalyzer and making that each component has the molar ratio or the weight percent of scope as described above in the finished product composite catalyst, then might carry out the selective oligomerization reaction, in each oligomerization product, obtain desired isomer simultaneously containing 2 the olefin(e) compounds of having an appointment to about 6 carbon atoms.In addition, utilization has periodictable the IV-A family metal and a kind of alkoxy aluminum compound in this kind composite catalyst, just might obtain more stable composite catalyst, that is be present in the raw material in itself that above described in detail, and the type impurity that can hinder or hinder oligomerization of the present invention exists down, will not lower catalyst activity.
An example that how to prepare as composite catalyst of the present invention, it is a kind of porousness base-material with predetermined amount, aluminum oxide for example, silicon-dioxide, silicon-dioxide one aluminum oxide, silico-aluminate etc., they can be spherical, granular, bar-shaped etc., and can in a kind of suitable equipment, for example in a kind of vaporizer, be prepared from a kind of hydrate of a kind of iron family metal salt and a kind of aqueous solution of a kind of IV-A family metal-salt.This mixture can be filled a part mixing, then this equipment be heated to form the catalyzer base that needed iron family metal and IV-A family metal is flooded.This impregnated base-material can be placed a kind of heating installation then, for example a kind of tube furnace to about 250 ℃ of temperature, is used air handling with this catalyzer heat simultaneously.Finishing this heat-processed with slower speed, and after reaching specified temperature, continue to remain on this temperature for some time, can be about 2 to about 4 hours or more of a specified duration during this period of time.Then this catalyzer base being warming up to preset value calcines, and keep one section time enough again in this temperature, make the water of hydration that exists in this iron group gold salt reach the molar ratio of the water of hydration of specified amount in the salt of iron family metal, preferably there is about 0.5: 1 water of hydration of surpassing every mole of iron family metal.
After this calcination operation proceeds to this scheduled time, stop heating, and will contain have an appointment 1% to about 20%(weight) iron family metal and about 0.1% is to about 20%(weight) this catalyzer base of IV-A family metal cools off.Then this chilled base-material is mixed mutually with the solution that a kind of alkylaluminium cpd and a kind of aluminum halide/alkoxy aluminum compound are dissolved in a kind of organic solvent.As previously mentioned, the reaction of generation has exothermic character, and after these heats are dispersed, the mixture of gained filled part stir and place for some time, can be about 1 hour to about 100 hours or more of a specified duration during this period of time.At the end during this period of time, by methods such as decant, filtration, centrifugations this organic solvent is removed, and washed this solid catalyst, unreacting substance is removed fully.After the washing, this catalyzer is dry in a kind of inert gas atmosphere, for example provide this atmosphere with the nitrogen that exists, reclaim this catalyzer then.
Then can be to containing 2 alkene to about 6 carbon atoms, ethene for example, propylene, butene-1, butene-2, amylene-1, amylene-2, amylene-3 carries out oligomerization, be by in the presence of this kind catalyzer, and under the oligomerization condition, promptly comprise-20 ℃ of temperature to 200 ℃ of scopes, and the pressure of 350 to 1000 pounds/square inch gauge-be equivalent to 2.5 to 7 MPas, this kind alkene is handled.Wherein used pressure can be by the spontaneous pressure of this kind raw material, and perhaps this raw material can only provide a kind of dividing potential drop, and the rest part of described pressure is to rely on reaction zone to feed a kind of rare gas element, for example nitrogen, helium, argon or the like and reach.
Within the scope of the invention, expecting that this kind oligomerization process can be operated with a kind of batch-type or continous way carries out.For example, when adopting a kind of batch operation, a certain amount of this kind novel composite catalyst of the present invention can be placed a kind of suitable equipment, the potheater of for example a kind of rotary-type, mixed type or stirring-type.If this kind olefin feedstock is gaseous state, then with this potheater sealing, and will contain this kind alkene, or the raw material of the mixture of the alkene alkane close with carbon chain lengths feeds this reactor, till reaching desired working pressure.Then this equipment is heated to the service temperature of requirement and is retained to preset time in this temperature, this time can be about 1 hour to about 6 hours or more of a specified duration.At the end during this period of time, stop heating, treat that this equipment and contained material return to after the room temperature, excessive pressure is bled off, this potheater is opened.Reclaim from this catalyzer with ordinary method then and separate this reaction product, for example use methods such as decant, filtration, centrifugation; And when needed, carry out fractionation, and various isomers can be separated from each other, store then.On the contrary,, can after containing the reaction product recycled as such of mixture of each isomer, store, not need the various isomer components that exist in this product mixtures are separated if need.
When this kind olefin feedstock was liquid state, in this reactor of can earlier it being packed into, the rare gas element with reactor sealing and feeding aforementioned type pressurizeed then, makes it to meet the requirements of working pressure.For the rest part pressure of the working pressure that makes required oligomerization product, be to use to aforementioned similar mode to produce.
When application continous way working method is produced required oligomerization product, be that a certain amount of this kind composite catalyst is placed a kind of suitable equipment.The raw material that will contain this kind olefin(e) compound is sent in this reactor that remains on proper temperature and pressure operation condition continuously.The same with batch operation, required working pressure can lean on this kind alkene itself to provide, or by adding a kind of rare gas element of heat.With preset time by after this reactor, this reactor effluent is discharged continuously, and recyclable this reaction product and deliver to bunkerage, perhaps it is delivered to a cover distillation plant, various isomers and oligopolymer can be separated in this equipment.All unreacting olefins that from reactor effluent, reclaim, but all recirculation is back to this reactor, constitutes the part of this charge raw material.
Because this kind composite catalyst of the present invention is solid, produces the mode that the operate continuously method of the required oligopolymer of these alkene can be dissimilar and carry out.For example, in a generic operation, this catalyzer is placed this reaction zone with a kind of fixed bed, and this kind olefin feedstock is fed, make it to flow through this beds with upper reaches or downward stream mode.Another kind of operate continuously can adopt moving-bed to operate, and this methodology is passed through this reaction zone with beds and this kind raw material with mutual also stream or reflux type.Remove this kind fixed bed or moving-bed type operation part, expection also can be adopted the operation of slurries formula, particularly when this olefin feedstock is liquid state.When adopting this kind operating method, be to send in this reactor with the slurries form of this catalyzer in this kind olefin feedstock.
When using composite catalyst of the present invention, the oligopolymer example of available olefin(e) compound includes: n-butene, iso-butylene, n-hexylene, methylpentene, neohexene, positive octene, various isomery heptene, various dimethyl hexenes, positive laurylene, various isomery methyl hendecenes, various dimethyl decene or the like.As previously mentioned, mainly comprise the dipolymer of the specific olefin(e) compound that is used as this kind raw material with prepared these oligomerization products of method of the present invention, therefore, for example when with ethene during as raw material, this reaction product with major part by C
4Alkene is formed; When with propylene during as raw material, this reaction product with major part by C
6Alkene is formed; And when with butylene during as raw material, this reaction product with major part by C
8Alkene is formed.Therefore, this kind composite catalyst of the present invention can make the final product that concrete purposes is respectively arranged.
Below the purpose of each example be for illustrating this kind novel composite catalyst of the present invention, prepare the method for these composite catalysts, and a kind of method of using these composite catalysts.But self-evident, these examples only are to illustrate character of the present invention, and the present invention is not limited.
The comparison example I
With the hexahydrated aqueous solution dipping of 1/8 inch a kind of nickelous nitrate of alumina balls body and function of 250 cubic centimetres, make a kind of contrast catalyzer.Flooding in a kind of rotary evaporator that the water vapor chuck arranged, is that this mixture was rotated 0.5 hour in this equipment at ambient temperature, and this vaporizer of water steam heating lasts 2 hours then, evaporates water during this period.Then this aluminum oxide base-material through nickelous nitrate dipping is packed in the tube furnace and bubbling air stream, air is 600 cubic centimetres of per minutes by the flow of this beds.Kept 3 hours with this catalyzer temperature-elevating to 250 ℃ and in this temperature then.Then temperature is increased to 400 ℃ and kept again 2 hours in this temperature.Stop heating then, thereafter with this nickeliferous 5.5%(weight) the catalyzer base reclaim.
This kind is after the aluminum oxide cooling of dipping, activate by per 100 cubic centimetres of carriers adding, 7.3 gram diethylaluminum chlorides and the solution of 2.9 three kinds of butoxy aluminium of gram in toluene then, the activation of this kind aluminum oxide is to carry out in a glove box under nitrogen atmosphere.This activator addition method be in 15 minutes with this activator liquid being added at a slow speed in this catalyzer base, because the exothermic character of this reaction is emitted heat in adition process.After this kind activator solution finishes, stir carrying out turn with discontinuous manner in this flask is during 12 hours.At these 12 hours at the end, this kind solution decant is fallen, and wash this composite catalyst 6 times, use the 100-115 cubic centimetre at every turn with iso-pentane.Then the composite catalyst of gained is placed, treated that excessive iso-pentane evaporates and drying, keeps the nitrogen atmosphere in this glove box simultaneously.
The example I
This example is preparation a kind of composite catalyst of the present invention, method for making is that the mode of flooding this base-material with this kind aqueous solution is to similar person described in the comparison example I with the solution impregnation of a kind of 1/8 inch spheroid catalyzer base with nickelous nitrate hexahydrate and tin chloride pentahydrate.With a water vapor chuck rotary evaporator water that exists is evaporated.
The aluminum oxide base-material that will contain nickelous nitrate/tin chloride places a tube furnace that airflow is arranged, and 250 ℃ of calcinings 3 hours, subsequently 400 ℃ of calcinings 2 hours.The base-material that calcining is finished contains 4.5%(content) nickel and 1.8(weight) tin.
This catalyzer base activate be with described base-material place one in glove box erlenmeyer flask and cover with toluene, a kind of toluene solution with diethylaluminum chloride and tri sec-butoxy aluminum in 15 minutes adds at a slow speed, in case owing to this thermopositive reaction liberated heat take place overheated.The consumption of this activating compounds is that per 100 cubic centimetres of carriers restrain diethylaluminum chlorides with 2.9 gram tri sec-butoxy aluminums and 7.3.Through in 12 hours, stirring after this flask with the discontinuous manner turn, the toluene decant is fallen, wash this composite catalyst 6 times with 6 parts of iso-pentane then.Then this composite catalyst is placed and under nitrogen atmosphere, treats its drying in the glove box, become the unrestricted flow shape to it till.
The comparison example II
To be applied to a kind of oligomerization of butene feedstock by the prepared comparative catalyst of above-mentioned comparison example I, the mixture that described raw material is made up of 60% butylene and 40% normal butane, and contain 30ppm(weight) dimethyl disulphide and 45ppm(weight) methyl tertiary butyl ether.Carrying out this oligomerization and be 50 cubic centimetres of this kind catalyzer are placed an internal diameter is 1/2 inch tubular reactor.Raw material is sent into this reactor with downward stream mode, and its liquid hourly space velocity is 2.0 hours
-1, the reaction conditions that is kept simultaneously is 70 ℃ of temperature ins and 700 pounds/square inch gauge of pressure.Feed raw material to reactor and only continue 12 hours.In period, this reaction bed temperature exceeds inlet temperature never above 1.3 ℃ at this section.Oligomeric is a kind of strong exothermal reaction, and reaction the time can reach very high n-butene transformation efficiency, and the top temperature of beds is also much higher.In operation in these 12 hours, the n-butene average conversion that calculates from the n-butene of raw material and product/normal butane composition has only 10%(weight), (table I).
Only collect C very in a small amount
4Liquid.Their character sees Table 1.
By 12 hours at the end, exothermic effects in a small amount moves to this bed bottom, and this is because material toxicity makes catalyzer subtract active feature.
Table 1
C
= 8Isomer distribution (%)
The butylene selectivity
Hour transformation efficiency (%) C
= 8%(weight) positive octene methyl heptene dimethyl hexene
0-12 10.0 89.2 10.9 64.6 24.5
The example II
For illustrate this kind of the present invention with the aluminum oxide base-material with the catalyzer of nickel and tin dipping in the presence of the impurity that generally belongs to catalyzer poison, keeping stability and active usefulness, carried out operating for the second time.In this operation, this kind catalyzer of the present invention for preparing by above-mentioned example 1 places the tubular reactor similar to last example for 50 cubic centimetres.Condition used in this oligomerization is similar to employee in the comparison example II, be that raw material is 60% butylene and 40% normal butane, and contain 30ppm(weight) dimethyl disulphide and 45ppm(weight) methyl tertiary butyl ether, with this raw material with liquid hourly space velocity 2.0 hours
-1Send into this reactor, keeping temperature in simultaneously is 70 ℃, 700 pounds/square inch gauge of pressure.This reaction has been carried out 92 hours, during this period stage by stage the sampling and with gc analysis.These analytical resultss are listed in table 2:
Table 2
C
= 8Isomer distribution (%)
The butylene selectivity
Hour transformation efficiency (%) C
= 8%(weight) positive octene methyl heptene dimethyl hexene
0-12 71.0 84.4 10.4 64.7 24.9
13-24 67.4 85.8 10.6 64.9 24.5
25-36 62.5 87.3 11.5 64.5 24.0
37-48 48.9 86.6 12.0 64.7 23.3
61-72 38.1 87.2 13.4 65.0 21.6
Can see obviously that from gained result's contrast with not containing with tin be that a kind of catalyzer of IV-A family metal of example compares, use catalyzer of the present invention, stability and active aspect obtain more excellent result.
Claims (5)
1, a kind of composite catalyst that is used for olefin oligomerization, this catalyzer comprise the alkylaluminium cpd that is scattered in the porous support that contains iron group metal and periodictable IV A family metal; Described iron family metal amount is to be that benchmark calculates by element, account for 1 to 20% (weight) of described composite catalyst, alkylaluminium cpd is with alkylaluminium cpd the mol ratio of iron family metal to be represented at the amount of described composite catalyst, molar ratio range is 0.05: 1 to 6: 1, and the weight ratio of IV A family metal pair iron family metal is 0.1: 1 to 10: 1; Said catalyzer prepares by following steps: porous support be impregnated in the aqueous solution of iron family metal salt and IV A family metal-salt, the carrier of dipping is calcined in 300 ℃ to 450 ℃ temperature range, and the incinerating carrier is contacted with the solution that comprises alkylaluminium cpd.
2, according to the described composite catalyst of claim 1, it is further characterized in that described composite catalyst is to combine with a kind of alkoxy aluminum compound that contains catalytically effective amount.
3, according to claim 1 or 2 described composite catalysts, it is further characterized in that described composite catalyst is to combine with a kind of aluminum halide that contains catalytically effective amount.
4, according to the described composite catalyst of claim 1, wherein said iron family metal is iron or nickel, and wherein said IV A family metal is tin or germanium.
5, the application of the composite catalyst of claim 1-4 in producing the oligomerization process of oligomerization product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN88101783A CN1017796B (en) | 1986-03-25 | 1988-03-28 | The composite catalyst that is used for olefin oligomerization |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US84354086A | 1986-03-25 | 1986-03-25 | |
| CN88101783A CN1017796B (en) | 1986-03-25 | 1988-03-28 | The composite catalyst that is used for olefin oligomerization |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1036147A CN1036147A (en) | 1989-10-11 |
| CN1017796B true CN1017796B (en) | 1992-08-12 |
Family
ID=25742429
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN88101783A Expired CN1017796B (en) | 1986-03-25 | 1988-03-28 | The composite catalyst that is used for olefin oligomerization |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1017796B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2062642A1 (en) | 2003-05-29 | 2009-05-27 | Japan Science and Technology Agency | Catalyst for synthesizing carbon nanocoils, synthesising method of the same and synthesizing method of carbon nanocoils |
-
1988
- 1988-03-28 CN CN88101783A patent/CN1017796B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| CN1036147A (en) | 1989-10-11 |
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