CN1015101B - Catalytic composite for conversion of hydrocarbons - Google Patents
Catalytic composite for conversion of hydrocarbonsInfo
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- CN1015101B CN1015101B CN86106891A CN86106891A CN1015101B CN 1015101 B CN1015101 B CN 1015101B CN 86106891 A CN86106891 A CN 86106891A CN 86106891 A CN86106891 A CN 86106891A CN 1015101 B CN1015101 B CN 1015101B
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- zeolite
- catalyzer
- hydrocarbons
- catalyst
- present
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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
The present invention discloses a novel catalytic composite for the conversion of hydrocarbons, which comprises non-acidic zeolite, a metal component in the eighth family, which has an effective amount for catalytic action, and a silicon dioxide carrier precursor obtained by gelatinizing alkali metal silicate sol under a high pH value. The novel catalytic composite as a dehydrocyclization catalyst is especially suitable for the conversion of paraffin hydrocarbons into aromatic compounds.
Description
The object of the present invention is to provide a kind of new catalytic composition that hydrocarbons transforms and becomes aromatic hydrocarbon especially for realizing the dehydrogenation of aliphatic hydrocarbons cyclisation that is used for.Especially this new catalytic composition can make C
+ 6Paraffinic hydrocarbons is converted into the corresponding aroma hydrocarbon with high selectivity, thereby makes mass production aromatic hydrocarbon be easy to carry out.
In the past, realized the conversion of aliphatic hydrocrbon to aromatic hydrocarbon with well-known catforming process.Hydrocarbons raw material in catforming process is generally the petroleum naphtha fraction, and it contacts with the catalytic composition that contains VIII family element, to produce the reformate of high aromatic hydrocarbon content.Normally a kind of full boiling range fraction of this petroleum naphtha fraction, its initial boiling point are from 10 to about 38 ℃, and full boiling point is from about 163 to about 219 ℃.The petroleum naphtha of this full boiling range contains a large amount of C
+ 6
Paraffinic hydrocarbons and C
+ 6Naphthenic hydrocarbon.As everyone knows, these paraffinic hydrocarbonss and naphthenic hydrocarbon can be converted into aromatic hydrocarbon through various reaction mechanism.These reaction mechanism comprise dehydrogenation again after dehydrogenation, dehydrocyclization, the isomerization.Naphthenic hydrocarbon promptly is converted into aromatic hydrocarbon through dehydrogenation.Paraffinic hydrocarbons can be converted into desired aromatic hydrocarbon through dehydrocyclization, and it also isomerization may take place.Hence one can see that, and the reaction number that occurs in catalytic reforming zone is a lot, thereby general reforming catalyst must effectively just be considered to many reactions and can be applied in the reactive system of viable commercial.
Because the number of the complicacy of catforming process and reaction mechanism is various, thereby develops high special efficacy catalyzer and become current striving direction, this catalyzer only is converted into aromatic hydrocarbon with the specific reactants kind.This catalyzer is better than general reforming catalyst, goes because the latter must identify oneself with in the various reaction mechanism.According to this viewpoint, the purpose of ongoing research work is to produce a kind of catalyzer: so that paraffinic hydrocarbons, particularly have the paraffinic hydrocarbons of six or more a plurality of carbon atoms, can be converted into the corresponding aroma hydrocarbon.Can expect this catalyzer is suitable specific for final product, does not consequently almost have for what side reaction.For example hydrocracking.By this field general technology as can be known, the productive rate of raising aromatic hydrocarbon is desired.Because the aromaticity content in the gasoline in the lead content decline requirement raising gasoline and the various demands of petrochemical complex make C
6～C
8Aromatic hydrocarbons becomes the product of height requirement.Therefore, prepare a kind of catalytic composition, but the less C of its high selectivity ground conversion value
+ 6Paraffinic hydrocarbons is for being worth higher C
+ 6Aromatic hydrocarbon, this will be highly profitable.
Main purpose of the present invention is to provide a kind of catalytic composition, the manufacture method of this composition and use it and transform hydrocarbons.Another object of the present invention provides a kind of C of making
+ 6Paraffinic hydrocarbons, particularly C
6～C
8Paraffinic hydrocarbons transforms into the technological process of its corresponding aromatic hydrocarbon.
In view of the above, a summary embodiment of the present invention provides a kind of catalytic composition, this catalytic composition contains metal component of group VIII and a kind of silica-supported maternal of a kind of non-acidic zeolite, katalysis significant quantity, and this load parent is that a kind of alkali metal silicate salt sol obtains through high pH gelationization.
It is the conversion process of hydrocarbons that of the present invention another summarized embodiment, it is characterized in that it is included in contacting of a kind of hydrocarbons raw material and a kind of catalytic composition under the hydrocarbons conversion condition, this catalytic composition contains metal component of group VIII and a kind of silica-supported maternal that is obtained through high pH gelationization by the alkali metal silicate salt sol of a kind of non-acidic zeolite, katalysis significant quantity.
Another embodiment of the present invention comprises a kind of preparation method of catalytic composition, comprising combining with metal component of group VIII, non-acidic zeolite and by the silica-supported maternal that the alkali metal silicate salt sol obtains through high pH gelationization.
These and other purpose and embodiment by following can bright Liao to specific descriptions of the present invention.
Containing alkali-metal aluminosilicate is known technically.For example, the United States Patent (USP) of announcing December 19 nineteen sixty-eight 3,013,986 discloses a kind of L-zeolite of alkali metal containing.This piece document particularly points out, and the L-zeolite of potassium type or potassium/sodium type is the starting material of the best alkali-metal L-zeolite of carrier band.The document points out, thereby the dehydration molecular sieve can contact with alkali metal vapour and produces a kind of alkali-metal molecular sieve of having filled, and wherein basic metal is contained in the inside of zeolite molecular sieve.Yet the document does not disclose a kind of catalytic composition, and it contains the metal component of group VIII of non-acidic zeolite, katalysis significant quantity and the silica-supported maternal that is obtained through high pH gelationization by the alkali metal silicate salt sol.In addition, the document does not disclose this composition has any application as the hydrocarbons conversion catalyst.
The United States Patent (USP) 3 that announce April 2 nineteen sixty-eight, 376,215, a kind of hydrocarbons conversion catalyst is disclosed, this catalyzer comprise a kind of contain group VIII metal help the catalytic solid carrier, this carrier includes the zeolite of (1) a kind of refractory inorganic oxide sorbent material and (2) a kind of mordenite structure, on the zeolite deposition have an appointment 10 to about 1000ppm(weight) metal (is benchmark with zeolite weight).This metal is selected from basic metal, alkaline-earth metal and their mixture.The document points out that carrier contains a kind of zeolite and a kind of refractory oxide of mordenite form, and it has promoting catalysis.The document points out that helping the catalysis refractory oxide may be silica gel or silica-alumina, and emphasizes that aluminum oxide is best refractory oxide.In addition, the example that is obtained refractory support by gelationization only is the alumina supporter that is obtained by alumina sol, and it is a tart as everyone knows, neutralizes with ammonia usually and realizes gelationization.Hence one can see that, and the document does not disclose catalytic composition of the present invention, and at first, non-acidic zeolite of the present invention can not be thought has katalysis to the reaction of being concerned about.Yet can think that non-acidic zeolite has the effect of the VIII family catalytic metal component of improving catalytic composition, and not quicken the dehydrocyclization reaction.Secondly, the not open silica-supported maternal that obtains through high pH gelation by the alkali metal silicate salt sol of using of this document.The document is not mentioned the source of silica gel catalyst carrier disclosed herein fully.Openly do not use the available wonderful beyond thought result of catalytic composition of the present invention yet.
The United States Patent (USP) 3,755,486 that on August 28th, 1973 announced discloses a kind of making and has had a C at least
6The C of skeleton
6～C
10The process of hydrocarbons dehydrocyclization, catalyst for application are X type zeolite or y-type zeolite or the faujusites of Li, Na or K, are impregnated with 0.3 to 1.4% platinum on it.Yet this document does not have to disclose the advantage that obtains owing to the applied catalysis composition, the silica-supported maternal that this catalytic composition contains non-acidic zeolite, metal component of group VIII and obtained through high pH gelationization by alkalimetal silicate.Equally, the United States Patent (USP) 3 that on June 25th, 1974 announced, 819, the United States Patent (USP) 3,832,414 that on August 27th, 507 and 1974 announced, their disclosed method is similar in appearance to United States Patent (USP) 3,755,486, both all do not propose owing to using superiority and the purposes that the catalyzer consistent with the present invention obtains.
The United States Patent (USP) 4 that on August 1st, 1978 announced, 140,320, a kind of method of aliphatic hydrocarbon dehydrocyclization is disclosed, use a kind of L-zeolite with exchangeable cation, wherein at least 90% is alkalimetal ion, and these ions are by selecting in sodium, lithium, potassium, rubidium and the caesium, and contains a kind of by the metal that chooses in group VIII metal, tin and the germanium at least.The document does not disclose catalytic composition of the present invention, does not disclose the combination catalyst system, and the load parent system of this combination catalyst system is obtained through high pH gelationization by the alkali metal silicate salt sol.The United States Patent (USP) of announcing November 22 nineteen eighty-three 4,417,083 discloses a kind of dehydrocyclization method, and it is non-acid zeolite basically that this method is used a kind of, its aperture greater than 6.5 dusts (
), and contain a kind of metal that is selected from platinum, rhenium, iridium, tin and germanium at least.In addition, catalyzer contains sulphur and alkali metal cation.Yet this document does not openly have the catalyzer of silica-supported maternal, and silica-supported maternal needs to be obtained through high pH gelationization by the alkali metal silicate salt sol.
The United States Patent (USP) 4,416,806 that announce November 22 nineteen eighty-three, disclose another kind of paraffin dehydrogenation cyclization catalyst, wherein contained the rhenium of platinum, carboxide form, and on the silico-aluminate crystalline zeolite, contained sulphur, with alkali metal cation-exchanged to greater than 90%, its aperture greater than 6.5 dusts (
).The document fails to disclose the dehydrocyclization catalytic composition consistent with the present invention.The document briefly discloses application aluminum oxide or clay really and has made binding agent.But not having openly has trickle similar binding agent to the present invention.
The recent United States Patent (USP) of announcing on February 7th, 1,984 4,430,200 discloses a kind of hydrocarbons conversion catalyst, wherein contains supersiliceous zeolite, for example mordenite or Y zeolite, and it and basic metal have carried out the alkali exchange.The document has been pointed out a kind of silica-supported maternal, however it can not with the present invention with the alkali metal silicate salt sol through high pH gelationization and comparing of making.In addition, the document has just been announced the application of existing catalyzer in cracking process, rather than the dehydrocyclization process.
The recent United States Patent (USP) 4,448,891 that on May 15th, 1984 announced, disclose a kind of dehydrocyclization catalyst, wherein contained a kind of L-zeolite, it is dipped in pH and is at least for some time in 11 the basic solution, act at a certain temperature, to improve the time that catalyzer is kept its catalytic activity.In addition, catalyzer contains group VIII metal.Yet the document does not have the open load parent similar to the present invention.
In a word, the present technique field does not propose to transform hydrocarbons, particularly C as yet
+ 6The paraffin dehydrogenation cyclisation is the catalytic composition of aromatic hydrocarbon, contains metal component of group VIII and a kind of silica-supported maternal that is made through high pH gelationization by the alkali metal silicate salt sol of non-acidic zeolite, katalysis significant quantity in this catalytic composition.In addition, the superiority of supervening owing to this new catalyst and application thereof is not recognized in the present technique field as yet.
Reiterate tout court, the invention relates to a kind of catalytic composition, said composition contains metal component of group VIII and a kind of silica-supported maternal that is obtained through high pH gelationization by the alkali metal silicate salt sol of a kind of non-acidic zeolite, katalysis significant quantity.Secondly; The present invention is specially adapted to as C
+ 6Paraffinic hydrocarbons, particularly C
6～C
10Paraffinic hydrocarbons, the catalyzer of dehydrocyclization process.
Just as noted earlier, the principal feature of catalyzer of the present invention is that it includes non-acidic zeolite.It is all occupied by non-hydrogen cation that so-called " non-acidic zeolite " refers in this zeolite all cationic commutative positions.Preferably include alkali metal cation in these positively charged ions, also other positively charged ions can be arranged certainly.Though irrelevant with cation type on the switch, among the present invention non-acidic zeolite basically all cation positions should to be non-hydrogen cation occupied so that zeolite become all exchanged for its positively charged ion with non-acid.Existing many methods can obtain positively charged ion and go up the zeolite that is exchanged fully substantially, thereby this point be need not carefully to state.The effect of non-acidic zeolite of the present invention is to have improved the group VIII metal of katalysis, and itself is inert basically in reaction process.Therefore, non-acidic zeolite support of the present invention is a non-catalytic, basic characteristics of the present invention that Here it is.
The representative that can be applicable to non-acidic zeolite of the present invention is X-zeolite, Y-zeolite and mordenite.In an application of the invention, be the best with the L-zeolite.Certainly, all these zeolites must be non-acid forms all, as top defined.Therefore, permutable cation position should be replaced by non-hydrogen cation basically entirely.As previously mentioned, the representative positively charged ion that occupies the cationic exchange position comprises one or more alkalimetal ions, comprising lithium, sodium, potassium, rubidium and caesium.In view of the above, non-acidic zeolite of the present invention can comprise X-zeolite, Y-zeolite or the mordenite of sodium type.The non-acidic zeolite of especially preferentially selecting for use among the present invention is a potassium type L-zeolite.In addition, non-acidic zeolite of the present invention also can contain several alkalimetal ions on the cationic exchange position, for example sodium and potassium.
Except that using special non-acidic zeolite, catalyzer of the present invention also comprises the metal component of group VIII of katalysis significant quantity, comprising nickel component, rhodium component, palladium component, iridium component, platinum component or the mixture between them.Preferential especially employing is the platinum component in group VIII metal.Can believe, reach maximum catalytic efficiency for making metal component of group VIII, it should be by on the non-acidic zeolite of carrier band, rather than on the silica-supported maternal.In view of the above, preferably with the metal component of group VIII carrier band on non-acidic zeolite.Group VIII metal can be deposited on the non-acidic zeolite with any known proper method.For example, can be with platinum by suitable solution, for example rare platinum acid chloride solution impregnated on the non-acidic zeolite, then carrier band is had the non-acidic zeolite of platinum to combine with silica-supported maternal.The also available other method of metal component of group VIII, promptly ion exchange method is deposited on the non-acidic zeolite, and the group VIII metal positively charged ion will be contained in some cationic exchange positions of non-acidic zeolite this moment.After the ion-exchange, group VIII metal must carry out reduction step afterwards more earlier through low-temperature oxidation.Thereafter, carrier band the non-acidic zeolite of group VIII metal can be incorporated among the silica-supported maternal.Will describe in detail as following, non-acidic zeolite also can at first be incorporated in the silica-supported maternal, then group VIII metal is combined with zeolite and load parent selectively again, no matter uses any method, and group VIII metal optionally is deposited on the non-acidic zeolite.
Regardless of the method that deposits group VIII metal, but all should make the deposition of group VIII metal reach the katalysis significant quantity.The group VIII metal optimum content is relevant with applied group VIII metal kind in the catalyzer of the present invention usually.Yet, be deposited on the weight of the group VIII metal on the zeolite usually, be benchmark with the weight of zeolite, group VIII metal and silica-supported maternal, be advisable from 0.01 to about 5.0% approximately.
In addition, should understand when group VIII metal when the non-acidic zeolite surface elevation disperses, can reach best effects.It is the most effective when metal component of group VIII is in reduced state.The appropriate method of any reduction group VIII metal all can adopt, and wherein has many technology well-known.For example, the metal component of group VIII that is deposited on after the non-acidic zeolite can be at high temperature and appropriate reductant, as hydrogen, and contact for some time and being reduced.
Except that containing group VIII metal, also can consider in the catalyzer of the present invention to contain other metal components, so that catalyst performance improves.These metal components comprise rhenium, tin, cobalt, indium, gallium, lead, zinc, uranium, thallium, dysprosium and germanium etc.Mix into these metals and be proved improving and benefiting aspect the catalytic performance, they can be as promotor or enriching substance.In view of the above, suitably mix this improving agent and can improve catalytic performance in catalyzer of the present invention, this point surely belongs to scope of the present invention.
Except specific metal component of group VIII and with catalytic composition bonded catalysis improving agent of the present invention, another characteristics of the present invention are the silica-supported maternals that made through high pH gelationization by the alkali metal silicate salt sol.Silica-supported maternal is known technically.This load parent is widely used in petroleum industry and petrochemical industry.Especially they are applied to, the bonding molecular sieve of using in many separation and the catalytic process.Yet as hereinafter further elaboration of institute, silica-supported maternal of the present invention is to be obtained through high pH gelationization by the alkali metal silicate salt sol, and it has produced surprising and unexpected superiority in the present invention.
As well-known technology, the application of silica-supported maternal can improve the physical strength of catalyzer.Therefore, non-acidic zeolite is incorporated in the silica-supported maternal, can obtains the catalyzer that physical strength has improved.In addition, non-acidic zeolite is bondd to be generated the profile that is suitable for using in the catalytic conversion process.For example, using silica-supported maternal can be with catalyst preparation globulate of the present invention.As everyone knows, spherical catalyst can be convenient to various application.Particularly when catalyzer of the present invention is placed in the continuous moving-bed system, sphere has improved catalyzer and has been easy to locomotivity by reaction zone.Certainly, also can adopt other shapes when needed.Therefore, catalyzer of the present invention can be processed extruding slivering, saddle etc.No matter the shape of silica-supported maternal how, need to use the non-acidic zeolite of q.s in the catalyzer of the present invention.For this reason, include in the catalytic composition from about 25% to about 75%(weight) non-acidic zeolite (gross weight with zeolite and load parent is a benchmark).To contain the 50%(weight of having an appointment) catalytic composition of non-acidic zeolite is the best.In addition, the crystallite of non-acidic zeolite is evenly dispersed in the silica-supported maternal.The homodisperse of this non-acidic zeolite all improves the reactivity worth of granule strength performance and catalytic composition.
Another basic characteristics of the present invention are that silica-supported maternal is to be made through high pH pectisation by the alkali metal silicate salt sol.Should be appreciated that so-called " high pH pectisation " means that it is more than 7 or 7 that pectisation betides pH herein.This high pH gelling makes to produce two tangible benefits.At first, high pH pectisation is feasible can be blended into non-acidic zeolite in the alkali metal silicate salt sol before the gelling of load parent, and can not lose its degree of crystallinity.Just as known, zeolite is relatively more responsive to its environment pH value.Thereby the zeolite that is dispersed in the acidic sol can lose degree of crystallinity in gelation process.High pH gelationization prepares silica-supported maternal and is overcome this shortcoming owing to the present invention adopts.The present invention prepares the most convenient method of catalyzer, is before gelationization non-acidic zeolite to be dispersed in the alkali metal silicate salt sol, and the high pH value environment of gelation can be avoided the zeolite loss when preparation catalytic composition of the present invention.High pH gelation also can be avoided non-acidic zeolite is introduced in acid position, and the introducing of this acid position will cause zeolite to quicken unwanted side reaction, as cracking etc.
Be that through second advantage that high pH gelation prepares silicon skeleton parent it has produced a kind of perfect catalytic composition with the alkali metal silicate salt sol, this catalytic composition is for by C
+ 6Paraffinic hydrocarbons is produced the aromatic series hydrocarbons and is had unexpected surprising selectivity.Although this point is understood as yet fully, can believe that the silica-supported maternal that the high pH gelationization of soluble alkali metal silicate produces has been strengthened the interaction between the silicon-dioxide of non-acidic zeolite and load parent.This interaction obviously causes the modification to metal component of group VIII, like this by C
+ 6The selectivity of catalyst that alkane produces aromatic hydrocarbon just has been reinforced.In view of the above, obtain silica-supported maternal by the alkali metal silicate salt sol through high pH pectisation, this not only makes the preparation of final catalytic composition be easy to carry out, and causes catalytic composition to producing C
+ 6The selectivity that aromatic hydrocarbons is high.
As known technology, the alkali metal silicate salt sol can be used as the raw material of silica-supported maternal.Water glass (water glass) often is employed as the raw material of load parent.In addition, known have the whole bag of tricks to finish high pH gelation.Yet preferential alkali metal base hydrochlorate and the high pH gelationization technology that adopts is at United States Patent (USP) 4,537, and 866(is published on August 27th, 1985) middle proposition, its main points have been included herein.In this preferential method that adopts, lithium silicate colloidal sol is its temperature to be reached be about more than 70 or 70 ℃ by heating to cause gelationization.Thereafter, the lithium silicate colloidal sol of gelationization therefrom to remove lithium, makes gel solidify through washing thus.The SiO that the lithium silicate colloidal sol that is adopted in the present invention has
2/ Li
2The O mol ratio is the highest about 25: 1.The SiO that especially preferentially selects for use
2/ Li
2The O mol ratio was by about 4: 1 to about 8: 1.The pH of all these lithium silicate colloidal sols approximately surpasses 7, and the pH that the lithium silicate colloidal sol of preferentially selecting for use has approximately from 10 to about 11.Because lithium silicate colloidal sol can need not to adjust the pH value with jelling agent (generally being acid) by adding Thermogelling, so realize that the high pH gelationization that this paper set forth is possible.Therefore, by formerly United States Patent (USP) 4,537,866, when the method for proposition was made catalytic composition of the present invention, non-acidic zeolite need be dispersed in earlier in the lithium silicate colloidal sol, is particulate state with the machine-shaping of lithium silicate colloidal sol again.Then molded good particle is heated to temperature and surpasses about 70 ℃, so that in type particulated gelization.After this, the lithium silicate gel that contains non-acidic zeolite is therefrom removed lithium through washing step.Just solidify through this washing step gel.
Know promptly that from the general technology of this area the non-acidic zeolite that contains lithium silicate colloidal sol can be used the shaped particle of many methods.These methods comprise extrusion, spin, mold pressing etc.In all these many methods of all having known, the method for the preferential especially grain forming that adopts of the present invention is an oil drop method.The particle of colloidal sol is formed as droplet in oil drop method.Usually the moulding of these droplets is that colloidal sol is realized by suitable nozzle or by rotating-disk.Droplet falls into suspension medium afterwards, and suspension medium is generally oil.When droplet just is rendered as during by oily suspension medium spherical.The diameter of this spherical particle can be by adjust flowing out droplet nozzle diameter or/or adjust the liquid droping head vibration velocity and controlled.Along with the colloidal sol droplet that contains non-acidic zeolite passes through suspension medium, they are heated to temperature and are about 70 ℃ or higher, thereby make colloidal sol become gel.Then gel particle is collected, slaking and process water-washing step are removed lithium.Just obtain a kind of non-acidic zeolite that is incorporated in the silica-supported maternal thus, this silica-supported maternal is to be obtained through high pH gelation by alkalimetal silicate, and the preferential alkalimetal silicate that adopts is a lithium silicate.
Point out the front, preferably earlier non-acidic zeolite and silica-supported maternal is combined, and then itself and metal component of group VIII is combined again.In addition, as preceding pointing out, preferably with group VIII metal basically carrier band on non-acidic zeolite.Certainly, for reaching this optimization step, can adopt any suitable method in the present invention.Yet the preferential especially method that adopts is the selectivity ion-exchange step.Group VIII metal can mainly be deposited on the non-acidic zeolite and avoid silica-supported maternal thus.
PH makes the pH value less than 8 by the control ion exchanged soln, just can be implemented in and optionally deposit platinum on the non-acidic zeolite, and avoid silica-supported maternal.Known pH is approximately greater than 8 o'clock, and silica-supported maternal is a kind of cationite.The loading capacity of zeolite is then irrelevant with pH by contrast.Therefore, when metal component of group VIII deposit with ion exchange method and the pH of ion exchanged soln approximately greater than 8 the time, group VIII metal just might all deposit on silica-supported maternal and non-acidic zeolite.Yet, when pH value silica-supported maternal less than 8 time will lose its cation exchange capacity (CEC).So,, group VIII metal only optionally is deposited on the non-acidic zeolite basically by adopting pH approximately less than 8 cationic exchange solution.Preferably the pH value with cationic exchange solution maintains about 4 to about 8 scope.This can make group VIII metal optionally be deposited on the non-acidic zeolite, and is not deposited on the silica-supported maternal.
Regardless of the method for preparing, catalytic composition of the present invention all is specially adapted to as the hydrocarbons conversion catalyst.At this moment, the hydrocarbons raw material contacts with catalytic composition of the present invention under its conversion condition.The scope of hydrocarbons conversion condition is very wide, and it depends on specific raw material and the reaction of being carried out.Usually these conditions comprise temperature approximately from 0 to about 816 ℃, and pressure is from normal atmosphere to about 100 normal atmosphere, and the liquid hourly space velocity degree was from about 0.2 hour
-1To about 15 hours
-1(method of calculation are that the grade of the charging that per hour contacts with catalyzer is removed when the zone of transformation volume that liquid volume is contained catalyzer).In addition, the hydrocarbons conversion condition also can comprise and has thinner, as hydrogen.The mol ratio of hydrogen and hydrocarbons can be from about 0.5: 1 to about 30: 1 in this case.
The special priority application of catalyzer of the present invention is as dehydrocyclization catalyst, especially for C
6～C
8The dehydrocyclization reaction of non-aromatics.In view of the above, containing C
6～C
8The raw material of non-aromatics contacts with catalyzer of the present invention under the dehydrocyclization reaction conditions.The dehydrocyclization reaction conditions comprises pressure from being about 0 to being about 6895 kPas, and preferably from being about 0 to being about 4137 kPas, temperature is from about 427 ℃ to about 649 ℃, and the liquid hourly space velocity degree was from about 0.1 hour
-1To about 10 hours
-1The most handy hydrogen is as thinner.When having the hydrogen operation, hydrogen is about 0.1 to being about 10 to the mol ratio of hydrocarbons.
According to the present invention, the hydrocarbons raw material contacts with catalyzer of the present invention at the hydrocarbons zone of transformation.Thisly can in fixed bed system, moving-bed system, fluidised bed system, finish, or under batch operation, finish with contacting of catalyzer.Hydrocarbons raw material and want usually earlier through preheating as the hydrogen-rich gas of thinner (if required), adopt any appropriate method carry out all can so that it reaches desired temperature of reaction.Afterwards it is passed to the zone of transformation that contains catalyzer of the present invention.Zone of transformation can be one or more isolating reactors, needs therebetween to guarantee that with appropriate method each reactor inlet keeps needed invert point.Reactant can also can be undertaken by the radial flow mode by upwards flowing, flowing downward with both contacting of catalytic bed, the latter preferably, and it is very important to understand this point.In addition, when reactant contacted with catalyzer, reactant can be in liquid phase, liquid-gas mixed phase or gas phase.When reactant is in gas phase, obtained best result.
When catalyzer of the present invention is used for the dehydrocyclization process, the dehydrocyclization system will comprise the reaction zone that contains catalyzer of the present invention.As noted, this catalyzer can or be used in batch operation as fixed bed system, moving-bed system, fluidised bed system in reaction zone.Yet, just helping the viewpoint of technological operation, catalyzer of the present invention is preferably in the moving-bed system and uses.Reaction zone may be one or more isolating reactors in this system, has heating unit to betide the endothermic effect of the dehydrocyclization reaction of each catalytic bed with compensation therebetween.The hydrocarbons raw material preferably contains C
6～C
8Non-aromatics contacts to carry out the dehydrocyclization reaction with the catalyzer that moves in reaction zone.
After catalyzer of the present invention contacted, the hydrocarbons raw material was through emitting from reaction zone as going out materials flow behind the dehydrocyclization, and through apparatus for supercooling and then pass to the disengaging zone.Ejecta can be separated into various compositions in the disengaging zone according to product requirement.When hydrogen when reaction zone is used as thinner, the disengaging zone will comprise vapour-liquid equilibrium disengaging zone and fractionation zone usually.From contain the high-octane rating liquid product hydrogen-rich gas is separated, this product contains the aromatic hydrocarbons that produces in the dehydrocyclization district.After separating has at least a part of hydrogen-rich gas to be back to reaction zone again to carry out recirculation as thinner.The rest part of hydrogen-rich gas is recyclable to be used to do it.The high-octane rating liquid product that contains aromatic hydrocarbons then is sent to fractionation zone, so that aromatic hydrocarbons is separated from unconverted feed composition.Afterwards, these unconverted components are returned to reaction zone again and are reacted, and perhaps are delivered to other operations and use to do it.
The scope of applicable hydrocarbons raw material is very big in technological process of the present invention.Concrete raw material is relevant with catalyst system therefor certainly.May be applied to hydrocarbons raw material of the present invention and will comprise naphthenic hydrocarbon and paraffinic hydrocarbons, yet also have aromatic hydrocarbons and alkene in some cases.Therefore, the raw material type that can be employed comprises virgin naphtha, natural stone cerebrol, synthetic naphtha or the like.In addition, it also is favourable using virgin naphtha and pressure naphtha.Feed naphtha may be a full boiling range naphtha, and its initial boiling point is from about 10 to about 66 ℃, and its full boiling point scope perhaps may be therefrom selected fraction from about 163 ℃ to about 219 ℃.Be used for raw material of the present invention and preferably carry out pre-treatment, such as hydrofining, hydrotreatment, hydrogenating desulfurization etc., to remove impurity all sulfur-bearings, nitrogenous and that produce moisture content by habitual catalysis pretreatment method.
When catalyzer of the present invention was used as dehydrocyclization catalyst, raw materials used preferably mainly was paraffinic hydrocarbons.Yes because the purpose of dehydrocyclization process is to make paraffin conversion is aromatic hydrocarbons for this.Because C
6～C
8Aromatic hydrocarbons is very valuable, thereby the hydrocarbons raw material preferably mainly contains C
6～C
8Paraffinic hydrocarbons.Although there is this preferential, yet the hydrocarbons raw material removes C
6～C
8Paraffinic hydrocarbons also can comprise naphthenic hydrocarbon, aromatic hydrocarbons and alkene outward.
For superiority of the present invention is described more fully, some examples are proposed below.Be appreciated that following described only be as example, and can not be it as unfavorable boundary of the present invention in other broad range.
Should be pointed out that and when estimating the hydrocarbons conversion catalyst, particularly when estimating and compare the dehydrocyclization catalyst performance, three parameters are of great use arranged.First is " activity ", and it is an index of catalyzer conversion reaction thing ability under a cover reaction conditions of regulation.Second index of weighing catalyst performance is: " selectivity ", it indicates that this Catalyst Production desired product obtains the ability of high yield.The 3rd index is " stability ", and it is that catalyzer is kept its sign active and the selectivity ability in whole time range.In these examples, selectivity of catalyst will be the index of being concerned about most.Catalyzer of the present invention is to be applied in following each example as dehydrocyclization catalyst.This moment, selectivity of catalyst was to represent with the degree that the paraffinic hydrocarbons reactant is converted into aromatic hydrocarbons.
When Fig. 1 and Fig. 2 represent to produce aromatic hydrocarbons, the function relation curve of selectivity of catalyst and time.What provide among Fig. 1 is the performance curve of two kinds of catalyzer, these two kinds of catalyzer, and promptly catalyst A and B all are not catalyzer of the present invention.Fig. 2 provides is catalyzer of the present invention (catalyzer C) and is not the result of catalyzer of the present invention (catalyzer D) test.
The example I
Once produced first catalyzer of the non-acidic zeolite that contains useful silica-bonded.Yet in this example, silica-supported maternal is not obtained by high pH gelatinization process.In this catalyzer, non-acidic zeolite comprises the zeolite by potassium metathetical L-.This catalyzer is mixed by L-zeolite and silicon sol, and its quantitative relation is to make to contain 10%(weight in the final composition) silicon-dioxide and 90%(weight) L-zeolite (gross weight with silicon-dioxide and L-zeolite is a benchmark).This mixture is through dehydrating, grind and use 5% polyvinyl alcohol as the auxiliary agent extrusion molding.500 ℃ of calcinings down, through ion-exchange step platinum is deposited on it more afterwards after the extrusion molding.Used ion exchanged soln contains pt(NH
3)
4Cl
2/ KCl.After ion-exchange, with extrudate under 350 ℃ through oxidation and reduction step.Contain 0.877%(weight in the prepared catalyzer) platinum.This catalyzer is referred to as catalyst A.Though zeolite is combined on the load parent that contains silicon-dioxide, because not handled through high pH gelationization by alkalimetal silicate, the load parent of catalyst A do not obtain, so catalyst A and the present invention are inconsistent.
Implement II
Made second kind of catalyzer in this example.This catalyst pack contains a kind of agglutinating potassium type L-zeolite that do not add.As proposing in the routine I, in order to deposit the platinum component, this do not add agglutinating L-zeolite must be through ion-exchange step.After the deposition platinum component, in air, under 350 ℃, carry out oxide treatment.Again in about 350 ℃ hydrogen reduce thereafter.Contain 0.657%(weight in the gained catalyzer) platinum.This catalyzer is called as catalyst B, and it and the present invention are also inconsistent.
The example III
Catalyst A and the relevant performance of catalyst B in this example, have been measured as dehydrocyclization catalyst.Test is to carry out in having the small-scale production unit of reaction zone, is placed with tested catalyzer in the reaction zone.The condition of reaction zone is: 690 kPas of pressure, liquid hourly space velocity degree 1.0 hours
-1, 500 ℃ of import temperature of reaction.Raw material mixes with the hydrogen of capacity earlier before mutually with the catalyzer contact, and the mol ratio of hydrogen and hydrocarbons is 10.0: 1.0.Raw material is (different C
6+ different C
7+ positive C
6+ positive C
7) a kind of mixture of paraffinic hydrocarbons and a small amount of alkyl cyclopentane.
The hydrocarbons raw material contacts with the catalyzer that places reaction zone, simultaneously the effluent of reaction zone is analyzed.The experimental result of catalyst A and catalyst B provides in Fig. 1.Fig. 1 represents to produce the catalyst selectivity of aromatic hydrocarbons and the function relation curve of time, and measuring intervals of TIME is 6 hours.In this example, the gram number that selectivity of catalyst is defined as each gram aromatic hydrocarbons that charging produced multiply by 100 again.As seen from Figure 1, catalyst B produces the selectivity of aromatic hydrocarbons, except that the timed interval, all than the height of catalyst A.Therefore the not agglutinating L-zeolite that contains platinum on it will be got well for the catalyst A that the selectivity ratios that produces aromatic hydrocarbons is combined in the platiniferous L-zeolite in the silica-supported maternal.
The example IV
Make a kind of catalyzer consistent in this example with the present invention.About 300 gram potassium type L-zeolites carried out ball milling about 2 hours, the SiO of lithium silicate colloidal sol with 1382 gram lithium silicate colloidal sols
2/ Li
2The O ratio is 6, and pH is about 10.5.Colloidal sol is scattered in the oily suspension medium with droplet form afterwards.This moment, the colloidal sol droplet was about 100 ℃ of following gelationizations in temperature.The ageing in oil of these gel balls is about 2 hours then, and temperature range is from about 100 ° to 150 ℃, and pressure is about 552 kPas.The KCl solution that is 0.15 mol with 14 liters of concentration through aged bead washed 2 hours down at 95 ℃, to remove lithium.Bead is dry down at 95 ℃ afterwards.Dried bead heats gradually, reaches 610 ℃ gradually through the time chien shih temperature more than 6 hours.Then, bead was calcined 2 hours in dry air under 610 ℃ of temperature.The potassium type L-zeolite that contains of the bead of Sheng Chaning is combined in the silica-supported maternal like this, and silica-supported maternal is to be obtained through high pH gelationization by the basic metal silicon sol.It consists of 50%(weight) L-zeolite and 50%(weight) silicon-dioxide.
Bead after the calcining is again through ion-exchange, so that the platinum component is deposited on the L-zeolite.Ion exchanged soln contains 0.030 mole Pt(NH
3)
4Cl
2/ 0.90 mole KCl solution keeps pH value of solution to be lower than 8.As preceding pointing out, be lower than 8 by keeping pH value of solution, all platinum components all are deposited on the L-zeolite.Wash catalyzer then with water, and be about in temperature and carry out drying under 95 ℃.Catalyzer is about in temperature after drying and carries out oxidation under 350 ℃, and is about under 350 ℃ in temperature and reduces in hydrogen stream.Prepared catalyzer contains 0.786%(weight) platinum.This catalyzer is consistent with catalyzer of the present invention, and it is called catalyzer C.
The example V
Prepared a kind of agglutinating non-acidic zeolite catalyst that do not add, the catalyst B with routine II is identical basically for it.Yet in this example, on potassium type L-zeolite, contain 0.882%(weight approximately) platinum.Therefore the catalyst B with the example II is identical basically for this catalyzer; The catalyzer that different is in this example contains more platinum component, and it is referred to as catalyzer D.
The example VI
Do not add the relevant performance of agglutinating L-zeolite catalyst in order to measure catalyzer of the present invention with another kind of platiniferous, catalyzer C and catalyzer D are tested as dehydrocyclization catalyst.Test is to carry out in a small-scale production unit, is used for the substantially the same of test catalyst A and B in this device and the routine III, but its operating process is different.The experiment condition that is used for test catalyst C and D is: the reaction zone temperature in is 500 ℃, and the liquid hourly space velocity degree is 1.0 hours
-1, reaction zone pressure is 345 kPas.With before catalyzer contacts, hydrogen to be mixed mutually with the hydrocarbons raw material, the mol ratio of hydrogen and hydrocarbons raw material is 5: 1.The test operation process is: at first making catalyzer and charging is that 410 ℃ reaction zone contacts in temperature, and the reaction zone temperature in is 410 ℃, keeps 7 hours.Reaction zone temperature was brought up to 500 ℃ gradually through 3 hours afterwards, continued to keep 12 hour trial period again under 500 ℃ of temperature, per hour the reaction zone ejecta was once analyzed with on-line gas chromatograph during this period.
The feedstock analysis result who is used for this example is as follows:
C
3/ C
4/ C
5Paraffinic hydrocarbons 0.4%(weight)
C
6Paraffinic hydrocarbons 69.5%(weight)
C
6Naphthenic hydrocarbon 0.7%(weight)
C
7Paraffinic hydrocarbons 21.4%(weight)
C
7Naphthenic hydrocarbon 8.0%(weight)
Amount to 100.0%(weight)
Test-results provides in Fig. 2.In following discussion, the definition of the catalyst selectivity of Fig. 2 is identical with top routine III.The result is amazing and unexpected, and by Fig. 2 curve as can be seen, it is much higher that catalyzer of the present invention does not add agglutinating platiniferous L-zeolite catalyst for the selectivity ratios that produces aromatic hydrocarbons.This contradicts with observed result (as shown in Figure 1) in the top routine III.Not adding its selectivity ratios of agglutinating platiniferous L-zeolite catalyst in routine III will get well with the platiniferous L-zeolite catalyst of silica-bonded.Yet with the platiniferous L-zeolite catalyst of silica-bonded the selectivity ratios that produces aromatic hydrocarbons not being added agglutinating platiniferous L-zeolite catalyst in this example will get well.Can reach a conclusion thus: can reach surprising and unexpected result so use the present invention, be that the silica-supported maternal owing to catalyzer C is the cause that is obtained through high pH gelation by the alkali metal silicate salt sol.Though catalyst A also is a kind of and platiniferous L-zeolite catalyst silica bound, it is not compared with adding agglutinating platiniferous L-zeolite catalyst, and its selectivity is insuperior.The difference of this relative selectivity in this example and the routine III can not be thought because platinum content changes and causes, because in each case, the weight percentage that does not add platinum in the agglutinating catalyzer all is higher than the catalyzer with silica-bonded.As pointing out that preceding this non-acidic zeolite itself is a non-catalytic, its effect only is in the improvement system metal component of group VIII as catalytic elements.
Though it be unclear that the silica-supported maternal that why is obtained through high pH gelationization by the alkaline silicate salt sol combines with the platiniferous non-acidic zeolite and can improve selectivity of catalyst, but there is any to explain, promptly because high pH gelationization condition causes producing between the silicon-dioxide of load parent and the zeolite interacts, and this interaction has further improved the catalysis of platinum component, thereby the catalyst selectivity that feasible conversion paraffinic hydrocarbons is an aromatic hydroxy compound is improved.
Claims (6)
1, a kind of catalytic composition that is used for dehydrocyclization is characterized in that it comprises the metal component of group VIII of nonacid L-zeolite, katalysis significant quantity and the silica-supported maternal binding substances that is obtained through gelationization by the alkalimetal silicate melten gel under pH7 or higher pH.
2, the described catalytic composition of claim 1, its feature is that also this metal component of group VIII comprises the platinum component.
3, the described catalytic composition of claim 1, its feature are that also the L-zeolite comprises potassium type L-zeolite.
4, the described catalytic composition of claim 1, its feature are that also the load parent is obtained through gelationization under high pH by a kind of lithium silicate colloidal sol.
5, the described catalytic composition of claim 1, its feature are that also it includes from about 0.01% to about 5.0%(weight) metal component of group VIII (gross weight with zeolite, load parent and metal component of group VIII is a benchmark).
6, the described catalytic composition of claim 1 is characterized in that it contains from about 25% to about 75%(weight) non-acidic zeolite (gross weight with zeolite and load parent is a benchmark).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN86106891A CN1015101B (en) | 1984-11-05 | 1986-09-29 | Catalytic composite for conversion of hydrocarbons |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/668,102 US4623632A (en) | 1984-11-05 | 1984-11-05 | Catalytic composite for conversion of hydrocarbons and the method of preparation and use thereof |
| CN86106891A CN1015101B (en) | 1984-11-05 | 1986-09-29 | Catalytic composite for conversion of hydrocarbons |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN89107511A Division CN1017798B (en) | 1984-11-05 | 1989-09-20 | Process for the catalytic conversion of hydrocarbons |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN86106891A CN86106891A (en) | 1988-04-13 |
| CN1015101B true CN1015101B (en) | 1991-12-18 |
Family
ID=25742254
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN86106891A Expired CN1015101B (en) | 1984-11-05 | 1986-09-29 | Catalytic composite for conversion of hydrocarbons |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1015101B (en) |
-
1986
- 1986-09-29 CN CN86106891A patent/CN1015101B/en not_active Expired
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| Publication number | Publication date |
|---|---|
| CN86106891A (en) | 1988-04-13 |
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