CN1022420C - Catalytic composition for isomerization of paraffinic hydrocarbons - Google Patents
Catalytic composition for isomerization of paraffinic hydrocarbons Download PDFInfo
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- CN1022420C CN1022420C CN87103444A CN87103444A CN1022420C CN 1022420 C CN1022420 C CN 1022420C CN 87103444 A CN87103444 A CN 87103444A CN 87103444 A CN87103444 A CN 87103444A CN 1022420 C CN1022420 C CN 1022420C
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Abstract
The present invention relates to a composite catalyst for hydrogen type crystallization mordenite containing platinum metal components and mixing with refractory inorganic oxides. The favorable isomerization performance of hydrocarbons can be obtained, and the performance is directly obtained under the condition that the surface area of the composite catalyst is at least 580m<2>/g. The present invention also provides a new method for preparing an isomerization catalyst whose surface area is at least 580m<2>/g, and a new method for the isomerization of isomerized hydrocarbons. The new method has the excellent advantage that a material containing a sulfur compound is successfully operated, wherein the quantity of the sulfur compound accounts for 5 to 200 ppm of the weight of a hydrocarbon material measured by elemental sulfur.
Description
The present invention relates to a kind of improved composite catalyst and use the method that this composite catalyst carries out hydroisomerization.More particularly, the present invention relates to a kind of such isomerization composite catalyst, this catalyzer comprises a kind of hydrogenating function material that is selected from group VIII metal, a kind of Hydrogen crystalline aluminosilicate zeolite and a kind of refractory inorganic oxides.But this novelty composite catalyst is specially adapted to make the isomerization of the isomerization hydro carbons that is stain by sulphur.
The isomerization of lower molecular weight normal paraffin is known in the art.Because the octane value of isomerization alkanes is more much higher than its corresponding normal paraffin, so isomerization reaction is most important in petroleum industry.Because the gasoline adulterant needs a distribution with material of various boiling ranges, at C
4-C
7Isomerization alkanes in the scope is useful fusion composition.Up to the present in the practice, adopted various catalyzer to make isomerization of paraffinic hydrocarbons become the equilibrium mixture of their branched chain isomers.Friedel-crafts resemble the aluminum chloride (Friedel-Crafts) catalyzer is known to be effective isomerization catalyst.Carrier band also is used to make hydrocarbon isomerization in the precious metal on halogenated aluminum oxide or silica alumina effectively as platinum.Recently, the crystalline aluminosilicate zeolite with catalytic activity also is used to make hydrocarbon isomerization effectively.Natural and these two kinds of crystalline aluminosilicates of synthetic have been used.Comprising X type and y-type zeolite and synthetic mordenite.
Specifically, the zeolite that is called as mordenite has been subjected to very big attention.Mordenite is the natural or synthetic zeolite of crystalline aluminosilicate type: usually, their composition can be expressed as follows with terms of oxide moles:
1.0±0.2Na
2O·Al
2O
3·10±0.5SiO
2;
SiO
2Quantity also can be more.Part sodium wherein or whole sodium, also available other basic metal and/or alkaline-earth metal replace.
Usually, have been found that sodium type mordenite is ineffective especially for the isomerization of hydro carbons, when replacing whole or big portion sodium ion, can obtain more suitably h-mordenite with hydrogen ion.Mordenite changes into Hydrogen from the sodium type can be by accomplished in many ways.One of method is to adopt ion-exchange techniques, with the hydrogen ion direct replacement sodium ion in the acidic aqueous solution.Another kind method is to replace sodium ion with ammonium ion earlier, then with high temperature oxidation process ammonium type zeolite is decomposed.
The activity of hydroisomerisation catalysts and selectivity depend on multiple factor, as the Preparation of catalysts mode, whether have promotor, the quality of raw material, processing condition etc.Appropriate catalyst can be by the preparation of the method for routine: with the commodity crystalline zeolite, combine with suitable body material as h-mordenite, then add the group VIII metal element, with ordinary method it is activated.Disclose a kind of new catalyst, it has improvement greatly than the isomerization performance that catalyzer had that ordinary method makes.
Use raw catalyst of the present invention, can realize isomerization effectively the hydro carbons of high sulfur content.As what the application exemplified, when with catalyst treatment sulfur-bearing raw material of the present invention, verified it have better isomerization performance than the isomerization catalyst of routine.
Therefore, but the invention provides a kind of composite catalyst of anti-sulphur that is used to make the isomerization hydrocarbon isomerization.This composite catalyst comprises a kind of platinum-group component and the carrier that contains Hydrogen pure aluminium silicate and refractory inorganic oxides, and its basic characteristics are that the surface-area of this mixture is at least 580m
2/ g.Platinum is preferred platinum group metal, and its content is preferably the 0.15-0.5% of this mixture weight.The silicon oxide that preferred Hydrogen pure aluminium silicate has is at least 16 with the ratio of aluminum oxide, and its content is the 75-95% of this mixture weight, and it preferably should have mordenite structure.Preferred refractory inorganic oxides is an aluminum oxide, and it is selected from gama-alumina, η-aluminum oxide and composition thereof.
On the other hand, the present invention a kind ofly prepares above-mentioned composite catalyst and uses this composite catalyst and carry out the method that hydroisomerization is handled.Preparation of catalysts comprises: preparation contains the mixture of Hydrogen mordenite and refractory oxide, and the mixture that forms is contacted with the acidic aqueous solution that contains ammonium ion, platinum metals is mixed in the mixture of formation again.
The preferred isomerization process condition of using this composite catalyst comprises: 200 of temperature ranges-800 (93-427 ℃), pressure 100-1000psia(690-6895kpa gauge pressure), liquid hourly space velocity degree 0.25-5h
-1Also need hydrogeneously in the hydrocarbon material, its amount is for 0.5-5 mole H
2/ mole hydrocarbon.
Following detailed description will make general introduction of the present invention and other embodiment become clearly.
Prior art generally acknowledges that the catalyzer of hydrocarbon isomerization has ten million kind of prescription.As everyone knows, acids can be used for making the crystalline aluminosilicate powder through decationized Y sieve and dealuminzation and modification as strong inorganic acid.Ammonium compound also successfully is used for making crystalline aluminosilicate to be converted into Hydrogen from strong base and/or alkali metal cation type.
Disclose acid treatment and ammonium handled to combine and be used for the processing of pure aluminium silicate powder.United States Patent (USP) 3 475 345(Benesi) disclose a kind of usefulness three step pre-treatment with Powdered aluminosilicate zeolite, particularly sodium type synthesizing flokite changes into the method for its Hydrogen.These pre-treatment step comprise: 1) hot acid treatment, and 2) cold acid treatment, 3) handle with ammonium compound.People such as United States Patent (USP) 3 442 794(Van Helden) also disclose the aluminosilicate zeolite pre-treatment, made it change into the method for Hydrogen.Equally, preferably zeolite also is a sodium type synthesizing flokite.Disclosed this method is very similar to above-mentioned United States Patent (USP) 3 475 345, and its distinctive points is that it uses 1 respectively with any order) acid compound and 2) ammonium compound carries out two step pre-treatment.The characteristics of these two parts of bibliographys all are zeolite as before the catalyst component, to having a definite purpose just its modification that zeolite is handled, but all do not mention the importance of composite catalyst surface-area.The present invention and its dissimilarity be, in the present invention, all is to be advanced the composite catalyst that has prepared at zeolite by fusion to carry out later on to any processing of zeolite, the more important thing is that zeolite itself does not have tangible modification.
It is effective not only it to be changed into Hydrogen with the acid treatment pure aluminium silicate, and has been used as a kind of method that increases silicon oxide and the ratio of aluminum oxide.For the synthesizing flokite of sodium type, silicon oxide generally is about 10: 1 with the ratio of aluminum oxide, if handle when making it to be converted into its Hydrogen with ammonium, this ratio is constant substantially.If by United States Patent (USP) 3 597 155(Flanigen) described the mordenite powder is carried out acid treatment, then silicon oxide can increase with the ratio of aluminum oxide.It is believed that this acid treatment meeting causes the minimizing of aluminium atom on the tetrahedron skeleton, Gu and increase zeolite structured in the ratio of Siliciumatom.When the ratio of silicon oxide in the mordenite powder and aluminum oxide increased, its isomerization performance just obtained improving.As people such as United States Patent (USP) 3 507 931(Morris) described, the ratio of silicon oxide and aluminum oxide surpasses about 20: 1, and the isomerization of low-carbon (LC) hydro carbons is greatly improved.Inform also that United States Patent (USP) 4 018 711(Bertolacini) if mixed the pre-treatment mordenite powder that silicon oxide and the ratio of aluminum oxide were at least 19: 1 in composite catalyst, its isomerization performance also has improvement.These bibliographys are concrete report also, in order to reach the purpose that increases silicon oxide and the ratio of aluminum oxide, zeolite powder is adopted acid treatment separately, and the present invention then is that the crystalline aluminosilicate that will have high oxidation silicon oxidation aluminum ratio mixes in the composite catalyst.These bibliographys are not mentioned the importance of surface-area of composite catalyst or the relation of surface-area and isomerization performance yet.
A common trait of above-mentioned prior art is, at all occasions, all is crystalline aluminosilicate, and particularly sodium type synthesizing flokite carries out the pre-treatment step of acid and/or ammonium separately and makes it obtain modification, then it is incorporated in the composite catalyst.Though as the pre-treatment meeting of the described mordenite of above-mentioned bibliography improves the isomerization performance of the composite catalyst that contains this pretreated mordenite, can also do further improvement.
To help to understand the present invention with reference to the accompanying drawings.Curve in the accompanying drawing 1 shows that the isomerization performance of composite catalyst is the function of its Lang Gemiuer surface-area.This isomerization performance can be characterized by desired product, and promptly 2, the 2-dimethylbutane (2,2DMB) and Trimethylmethane (i-C
5) selectivity.
Curve in the accompanying drawing 2 shows C
+ 5Relation between research octane number (RON) of isomerization product (RON-O) and the catalyst reactor average bed temperature.In Fig. 3, the RON-O value also with C
+ 5The productive rate of isomerization product is contrasted, and the latter is to be benchmark with the fresh material, measures with its percent by volume.
Though the data that has has earlier been introduced the pre-treatment of the pure aluminium silicate component of isomerization catalyst specially, but one of purpose of the present invention provides a kind of novel composite catalyst, and it is owing to the strict treatment condition of having controlled carrier demonstrate improved isomerization performance.
According to the present invention, but a kind of composite catalyst that makes the isomerization hydrocarbon isomerization become the suitable thing of its side chain will be provided, a kind of method and a kind of technological process of using this composite catalyst to produce the high-octane rating blending compound of making this composite catalyst.
Composite catalyst of the present invention comprises a kind of platinum-group metal component, Hydrogen crystalline aluminosilicate and a kind of refractory inorganic oxides, and the surface-area of this composite catalyst is at least 580m
2/ g.We have found that, when the surface-area of composite catalyst is 580m
2/ g or when higher, its isomerization performance will have significant improvement.Obtaining this surface-area is one of purpose of embodiment of the present invention, and this will be further specified in the embodiment of back.
Mixing composite catalyst is the noble metal component of VIII family with the metal component that hydrogenation-dehydrogenation functionality is provided.The precious metal of VIII family comprises that platinum metals and palladium are metal, i.e. platinum, iridium, palladium, rhodium and ruthenium, and they are called as " platinum metals " here together.Preferred VIII family precious metal is a platinum.The consumption of the VIII family precious metal of composite catalyst of the present invention is the weight of about 0.1-5%(by composite catalyst).Particularly preferred this metal component consumption is at least 0.15%(weight), but be no more than 0.5%(weight).
Scope of the present invention also comprises: catalyzer also contains the promoter metal of effective catalytic amount.These promoter metals comprise tin, lead, germanium, cobalt, nickel, iron, tungsten, chromium, molybdenum, bismuth, indium, gallium, cadmium, zinc, uranium, copper, silver, gold, tantalum, one or more alkene earth metalss and their mixture.
Crystalline aluminosilicate of the present invention is a kind of Hydrogen silica-alumina, the lattice framework with a kind of or three-dimensional structure or ditch-pore structure.Three-dimensional pure aluminium silicate comprises synthetic and naturally occurring silica alumina, as comprises faujusites such as X type, Y type, overstable Y type.The example of ditch-pore structure crystalline aluminosilicate is L type, zeolite omega and mordenite.
Preferred pure aluminium silicate material is a kind of pure aluminium silicate material that is called the particular form of mordenite in the composite catalyst of the present invention.Though mordenite is present in nature, the synthesizing flokite commodity of various powders shape also can have been bought.These synthesizing flokites can the sodium type or these two kinds of forms of Hydrogen obtain, its silicon oxide is also had nothing in common with each other with the ratio of aluminum oxide.The preferred embodiments of the invention are, mordenite is a Hydrogen, and silicon oxide was at least 16: 1 with the ratio of aluminum oxide, and more particularly, proportional range was from 16: 1 to 60: 1.Pre-treatment step described in the above-mentioned bibliography can be used as the manufacturing that customary method is used for commodity mordenite powder usually, and this kind product can satisfy the listed requirement to raw material of the present invention.These pre-treatment step are used to increase the silicon oxide of mordenite and the ratio of aluminum oxide, and the sodium type is transformed to required Hydrogen.
Refractory inorganic oxides is mixed the preparation that is used for composite catalyst behind the Hydrogen pure aluminium silicate.Can prepare this class composite catalyst with any currently known methods in this area, comprise oil drop method and the extrusion molding known.The content of Hydrogen pure aluminium silicate can be 50 to about 99.5%(weight), be preferably 75 to about 95%(weight), the content of refractory inorganic oxides can be 0.5% to about 50%.
The inorganic oxide of preferentially selecting for use among the present invention is an aluminum oxide.This aluminum oxide preferably is selected from gama-alumina, η-aluminum oxide and composition thereof.Other inorganic refractory oxide that can consider comprises, as silica gel, silica-alumina, magnesium oxide-aluminum oxide, Zirconia-alumina etc.
Wondrous and unexpectedly have been found that between the isomerization performance and its surface-area of composite catalyst of the present invention, exist the intensive correlationship.A kind of preferred method that reaches best isomerization performance is to adopt surface-area to be at least 580m
2The composite catalyst of/g.Here the surface-area of mentioning is to adopt the Lang Gemiuer method relevant with adsorption/desorption isothermal data to measure.The Lang Gemiuer method is specially adapted to measure the high composite catalyst of crystalline aluminosilicate percentage composition.The required data of Lang Gemiuer method generally can be by the adsorption/desorption device of knowing, and particularly a kind of nitrogen adsorption/desorption device obtains.Anyly can make the finished product composite catalyst produce its surface-area to be at least 580m
2The method of/g all can be used.The method of generation high surface area composite catalyst has a variety of, for example can use the crystalline aluminosilicate powder that just has high surface area originally, perhaps a kind of high surface area component of composite catalyst is mixed with other component with vast scale.Reach and have 580m at least
2A kind of preferred method of the surface-area of/g is that the composite catalyst that will make contacts with the acidic aqueous solution that contains ammonium ion.With before the aqueous solution contacts, the catalyzer of making can first drying and/or calcining.
Adding acid can make the aqueous solution be acid.Only acid is strong inorganic acid, as H
3PO
4, H
2SO
4, HNO
3, and HCl.The preferred acid of the present invention is HCl.Certainly, the mixture of multiple acid also can be considered to use.The source that adds ammonium ion more suitable in the acidic aqueous solution is NH
4Cl, but any ammonium compound that can form ammonium ion are as NH
4OH, NH
4NO
3, (NH
4)
2SO
4, (NH
4)
3PO
4Deng all using.
The acid in the aqueous solution and the concentration of ammonium ion are not strict, and the variation range of acid concentration is 0.5M to 6M, and the scope of ammonium concentration is 0.5M to 4M.When use contains the solution of the ammonium ion of the acid of 2-5M concentration and 1-3M, can obtain good especially result.
Can expect, make the composite catalyst of making contact several different methods, but do not have a kind of superior especially with the acidic aqueous solution that contains ammonium ion.This contact method can comprise, for example the fixed bed of catalyzer contacts with the solution of static state, the fixed bed of catalyzer contacts with the solution that is stirring, and the fixed bed of catalyzer contacts with the solution of continuous flow, or any method that other can make composite catalyst and acid solution effectively contact.
The temperature of contact solution should be preferably about 50 ℃ (122 °F) to 98 ℃ (208 °F) at 25 ℃ (77 °F) to about 100 ℃ (212 °F).The required time of contact phase is depended on concentration, temperature and contact efficiency.In general, should be 0.5 hour duration of contact at least, but be no more than 4 hours, is preferably between 1-3 hour.
The result that the composite catalyst of making contacts with the acid solution that contains ammonium ion is that the surface-area that records increases.Wondrous and unexpectedly, from Magic Angle Spinning NMR(MASNMR) measure as can be known, surface-area increases to 580m
2/ g or higher, and the ratio of silicon oxide and aluminum oxide does not increase thereupon in the Hydrogen crystalline aluminosilicate.This MASNMR analytical technology as known in the art shows that in the tetrahedron skeleton of composite catalyst of the present invention, the aluminium atom does not reduce.Will illustrate that as following the present invention has 580m
2The catalyzer of/g surface-area, wondrous and demonstrate the isomerization performance that has improved unexpectedly.
Catalyzer of the present invention is used to make can the practicality especially of isomerized hydrocarbon isomerization.But the isomerization hydro carbons comprises multiple saturated hydrocarbons, and comprising paraffinic, catalyzer of the present invention also more is specially adapted to contain in each molecule the straight chain of 4 or more a plurality of carbon atoms or the hydroisomerization of the alkane of side chain slightly.Isomerization reaction can be carried out in wide temperature range, but generally is about 93 ℃ (200 °F) to 427 ℃ (800 °F).But the space velocity that per hour flows through the isomerization hydrocarbon liquids of every volume composite catalyst preferably is about the 0.25-5 volume of liquid.Reaction zone pressure is preferably about 6.9 crust (100psi) to about 69 crust (1000psi).Isomerization reaction is especially wished to have under the hydrogen existence and is carried out, but its consumption preferably is about 0.5-5 mole H to every mole of isomerization hydrocarbon
2H
2Effect mainly be to increase life of catalyst, clearly it can prevent the intermediate reaction product polymerization and be deposited on the composite catalyst.Owing to can use the hydrogen-rich gas that gets as from the petroleum naphtha catalytic reforming, so there is no need to use pure hydrogen.
More particularly, method of the present invention can be applicable to comprise naphthenic hydrocarbon and acyclic isomerization of paraffins, can be applicable to straight-chain paraffin or part branched paraffin, as normal butane, Skellysolve A, normal hexane, normal heptane, octane, 2-methylpentane, 3-methylpentane, 3-ethylpentane etc.Method of the present invention also is applicable to the mixture of paraffinic hydrocarbons and/or naphthenic hydrocarbon, comprises those hydrocarbons from natural gasoline and the acquisition of petroleum naphtha selective rectification.The example of the mixture of these paraffinic hydrocarbonss and/or naphthenic hydrocarbon comprises so-called each pentane cut, each hexane fraction and composition thereof etc.The present invention is not limited to be applied to cited saturated hydrocarbons.Each molecule also is considered as included in the scope of the present invention by the isomerization that contains up to the straight or branched stable hydrocarbon of 20 left and right sides carbon atoms.But the preferred classes of isomerization hydro carbons comprises that those each molecules are by the hydrocarbon that contains the 4-7 carbon atom.
Be applied to can contain the 1ppm-300ppm(weight of having an appointment in the straight run hydrocarbon in the inventive method) sulphur compound (by elementary sulfur).Advantage of the present invention is that the compound material that adds isomerization reaction zone can contain H
2S and/or organosulfur compound, its amount provides the elementary sulfur of about 5ppm-200ppm for giving compound material.Here said " compound material " is meant the mixture of the process-stream that will contact with isomerization catalyst., these process-streams to add the compound of isomerization reaction zone but but comprising the isomerization hydrocarbon of initiate isomerization hydrocarbon, recirculation, rich hydrogen lighter hydrocarbons, the rich hydrogen lighter hydrocarbons of recirculation and/or any other.Here said " rich hydrogen lighter hydrocarbons " are meant and contain 50%(mole at least) H
2, all the other are C
1-C
3The process-stream of hydrocarbon.The rich hydrogen lighter hydrocarbons of recirculation can obtain from the product tripping device of isomerization process usually.
When the accumulation of sulphur took place, the sulphur content in the compound material can surpass preferably the highest permission content 200ppm(weight).The accumulation of sulphur is the result of a kind of so rich hydrogen lighter hydrocarbons of recirculation, contains a certain amount of sulphur in this hydrocarbon, generally is H
2S.This H
2S is in isomerization reaction zone, forms but combine conversion by sulphur compound with the isomerization hydrocarbon phase.Therefore, because H
2The high volatile volatile of S, it just is separated with rich hydrogen lighter hydrocarbons in the product tripping device.When increasing sulphur compound changes into H in reaction zone
2During S, H in the recirculation stream
2The content of S constantly increases, and reaches and the corresponding to equilibrium level of product separator operation condition.Therefore, when recirculation stream is mixed with other process-stream when forming compound material, the total sulfur content of compound material will be increased to that to surpass the new 20%-that adds sulphur content in the material about 80%, and this depends on the temperature and pressure of separator.
Therefore, one embodiment of the present invention is to control the sulphur content of compound material in 5-150ppm(weight) about.Any control method as known in the art all can be used.Comprise catalyzed conversion, physics or chemisorption, physical sepn etc.A kind of preferred control method relates to not from the rich hydrogen lighter hydrocarbons of product tripping device recirculation.This measure can prevent the accumulation of above-mentioned sulphur.Another preferred method of controlling sulphur content in the compound material is before adding rich hydrogen lighter hydrocarbons in the compound material, the rich hydrogen lighter hydrocarbons of recirculation is carried out desulfurization handle.Adopt any known sulfur method in this area, comprise absorbing process, Catalytic processes or the two bonded technology, all can reduce or eliminate the sulphur compound in the rich hydrogen lighter hydrocarbons of recirculation.Absorbing process can adopt molecular sieve, high surface area silica-alumina, carbonaceous molecular sieve, crystal aluminosilicate, gac etc.Catalytic processes can adopt the sulfur-lowing catalyst composition of known general-purpose in this area, comprises the refractory inorganic oxide carrier material of either that contains the metal that is selected from VI B, II B, VIII family.The sulfur content of control can change, to obtain sulphur content required in the compound material.But during the content of sulphur low (5-150ppm), just do not need from the rich hydrogen lighter hydrocarbons of recirculation, not remove sulphur, in the fresh isomerization hydrocarbon because by H in the product separator liquid
2S removes, and can keep the recirculation H of enough low levelss
2S(§ 100ppm); On the contrary, but as if sulphur content height (§ 150ppm) in fresh isomerization hydrocarbon, just need desulfurization from the rich hydrogen lighter hydrocarbons of recirculation.
The purpose of enumerating following example can not be thought limitation of the scope of the invention just for the present invention is described.
Having carried out a series of experiments, to study the variation of the surface-area of isomerization composite catalyst be how to influence isomerization performance.For assess performance, five kinds of catalyzer have been prepared.In described all Preparation of catalysts of following example, raw material is the powder (deriving from the commodity LZ-M-8 of U.S. combinating carbide company) of the synthesizing flokite of Hydrogen, low sodium, part dealuminzation, hereinafter referred to as the mordenite of standard.
The embodiment I
In this example, not according to method preparation catalyzer (being called catalyst A) of the present invention.This method is to be that the mordenite and the alumina mixture of 9: 1 standard mixes with tart peptization solution and weight ratio, and extrudes by means known in the art.With the mixture drying of extruding, in oxidizing atmosphere, calcine, use the platinum solution impregnation, again calcining.The add-on of platinum is made benchmark with the weight of finished catalyst, is 0.324%(weight).The surface-area that records catalyst A is 567m
2/ g, and this surface-area is associated with its isomerization performance.This relation is illustrated in the accompanying drawing 1 with the form of curve.
The embodiment II
This routine composite catalyst is called as catalyst B, and it neither prepare by method of the present invention.In this method, the mordenite powder of standard with contain 10%(weight) HCl and 10%(weight) NH
4The ammonium ion acidic aqueous solution of Cl, 140 (60 ℃) contact 150 minutes, the weight ratio of solution and zeolite was 5: 1.The mordenite powder H that obtains
2The O washing, calcining mixes with aluminum oxide and peptization solution again.Extruding and used identical of mode that adds platinum and the catalyst A in the example I of catalyst B.Recording surface-area is 534m
2/ g, the relation of it and its isomerization performance is seen accompanying drawing 1.
The embodiment III
Catalyzer C system is by the inventive method preparation, and the mode of catalyst A is basic identical in its method for making and the example 1.Yet according to the present invention, the exsiccant extrudate contacted with the acidic aqueous solution that contains ammonium ion earlier before calcining and adding platinum.This solution contains 10%(weight) HCl and 10%(weight) NH
4Cl.Contact solution and the temperature of extruding are 140 °F (60 ℃), and the time is 120 minutes, and the weight ratio of solution and zeolite is 25: 1.Then with extrudate drying, calcining with use the platinum solution-treated, used identical of step and controlling catalyst A and B.The platinum content of catalyzer C is a 0.396%(weight), surface-area is 622m
2/ g, the relation of it and isomerization performance is shown in accompanying drawing 1.
The embodiment IV
The example II is extruded before mixture adding platinum through incinerating, in the used mode of preparation catalyzer C in the example III, carries out contacting the second time with acidic aqueous solution earlier.The mixture that makes contacts by method of the present invention with the second time of acidic aqueous solution and is undertaken.Add platinum again in mixture, making platinum content is 0.308%(weight), obtain catalyzer D.Its surface-area is 630m
2/ g, the relation of it and isomerization performance is shown in accompanying drawing 1.
The embodiment V
Catalyzer E is by the same way as preparation of catalyst A.Just the acidity of peptization reduces by 90%.Catalyzer E neither prepare by the inventive method as routine I.Its platinum content is a 0.313%(weight), surface-area is 542m
2/ g is shown in accompanying drawing 1 with the relation of isomerization performance.
The embodiment VI
The evaluation of the isomerization performance of five kinds of catalyzer that the example I is made up of the platinum of carrier band on h-mordenite gama-alumina mixture to the V, be to be placed in the flow reactor, carry out with the method for the mixture of handling the benzene contain 46% Skellysolve A, 47% normal hexane, 5.5% methylcyclopentane and 1.5% (all by weight) material.
The used operational condition of the isomerization performance of detecting catalyst A to E comprises that reactor pressure is 21.7 crust (315psia), liquid hourly space velocity degree 1.0h
-1, H
2With the mol ratio of material hydrocarbon be 1.0, temperature is 254 ℃ (490 °F)-277 ℃ (530 °F).Testing data is in 97%(weight specifically) C
+ 5Productive rate under, for iso-pentane (i-C
5) and for 2, (2, selectivity 2DMB) is used as the yardstick of weighing isomerization performance to the 2-dimethylbutane.Shown in Figure 1 to i-C
5The definition of selective value be i-C in the liquid isomerization product
5Weight fraction divided by C in the product
5The weight fraction of total hydrocarbon amount.In order to obtain 2 shown in Fig. 1, the selective value of 2DMB can be with in the liquid isomerization product 2, and the weight fraction of 2DMB is divided by acyclic C in the product
6The weight fraction of total hydrocarbon amount.
In above-mentioned example under the used isomerization test condition, for i-C
5With 2, the selectivity of 2DMB is the forward function of the finished catalyst surface-area that records.Shown in the curve of accompanying drawing 1, for i-C
5With 2, the selectivity of 2DMB increases with the increase of the surface-area that records.The catalyzer C of example III and the catalyzer D of example IV prove, they have meet the present invention's definition to i-C
5With 2, the highly selective of 2DMB, their the two measured surface-area are at least 580m
2/ g.Relatively reaching mutually of the platinum content of catalyzer C, D and comparison shows that of other three kinds of catalyzer, platinum content and isomerization performance are irrelevant, have proved that further surface-area is at least 580m
2The advantage of the composite catalyst of/g.Thereby composite catalyst of the present invention obviously can produce the catalyzer of high isomerization performance.
The example VII
Having carried out two isomerization processs tests and studies sulfide containing material and how to influence isomerization performance.First technology is called technology A, uses the isomerization catalyst that does not meet surface-area of the present invention.Carry out A item test and be for the isomerization performance when handling sulfide containing material with the conventional isomerization catalyst of prior art is described.Used catalyzer is identical with the catalyst A of example I.
Second technology is called technology B, uses catalyzer C according to the invention, i.e. the catalyzer of preparing in the example IV by the inventive method.
In flow reactor, handle the mixture contain following material, to estimate the isomerization performance of technology A and B: 6.8% butane, 20.9% Skellysolve A, 14.5% iso-pentane, 15.7% normal hexane, 19.0% isohexane, pentamethylene/hexanaphthene of 12.4% and 2.5% benzene, 8.2% C
+ 6Sulphur (being part by weight) with 133ppm.
The used operational condition of isomerization performance of estimating technology A and B comprises, reactor pressure 32.0 crust (450psig), liquid hourly space velocity degree 1.0h
-1, H
2With the mol ratio of hydrocarbon material be 2.0, temperature range 254 ℃ (490) is to 316 ℃ (600 °F).Use C
+ 5The research octane number (RON) (RON-O) of product liquid, the gentle C of average reactor catalyst bed
+ 5The weight percent productive rate measure isomerization performance.In accompanying drawing 2 and 3, illustrated as average reactor bed temperature and C
+ 5The two the RON-O value curve of function of productive rate.Technology of the present invention (technology B) is active more much higher than the isomerization process (technology A) of conventional employing prior art catalyzer.This point can obtain proof by Fig. 2, and in order to reach 78 RON-O value, temperature condition of the present invention can reduce by 32.2 ℃ (58 °F) as seen from the figure.In Fig. 3, also illustrate, at C
+ 5Productive rate is a 94%(weight) time technology B research octane number (RON) than high 4 units of technology A.
These examples clearly show that the isomerization performance of catalyzer of the present invention is better than the isomerization performance of prior art catalyzer.Comparison shows that under suitable product productive rate, the application's invention have the product octane value of higher isomerization activity and Geng Gao.Say it on the contrary, comparison shows that under suitable product octane value (as 78RON), the application's invention has higher product productive rate.
Claims (6)
- But 1, a kind of composite catalyst that is used for the isomerization hydrocarbon isomerization, it comprises platinum that accounts for 0.1-0.5% (weight) and the combination that contains the carrier of Hydrogen crystallization mordenite and refractory inorganic oxides, the surface-area of this composite catalyst is at least 580m 2/ g.
- 2, according to the composite catalyst of claim 1, wherein the silicon oxide of Hydrogen crystallization mordenite was at least 16: 1 with the ratio of aluminum oxide.
- 3, according to the composite catalyst of claim 1, wherein the content of Hydrogen crystallization mordenite is the 75-95% of composite catalyst weight.
- 4, according to the composite catalyst of claim 1, refractory inorganic oxides wherein is to be selected from gama-alumina, η-aluminum oxide and composition thereof.
- 5, a kind of preparation method of isomerization composite catalyst of claim 1 comprises the following steps:A). the mixture of preparation hydrogen mordenite and refractory inorganic oxides;B). with this mixture calcining;C). this mixture is contacted with the acidic aqueous solution that contains ammonium ion, and the condition of selection is to make the surface-area of finished product composite catalyst be at least 580m 2/ g;D). with contacted mixture calcining;E). in the calcined composite of step (d) preparation, mix a kind of platinum-group metal component.
- 6, according to the method for claim 6, its feature is that also this platinum-group metal component is a platinum, and its content is composite catalyst weight 0.15-0.5%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN87103444A CN1022420C (en) | 1987-04-29 | 1987-05-11 | Catalytic composition for isomerization of paraffinic hydrocarbons |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ZA873090A ZA873090B (en) | 1987-04-29 | 1987-04-29 | Catalytic composition for the isomerization of paraffinic hydrocarbons |
| CN87103444A CN1022420C (en) | 1987-04-29 | 1987-05-11 | Catalytic composition for isomerization of paraffinic hydrocarbons |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN87103444A CN87103444A (en) | 1988-11-30 |
| CN1022420C true CN1022420C (en) | 1993-10-13 |
Family
ID=25578836
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN87103444A Expired - Fee Related CN1022420C (en) | 1987-04-29 | 1987-05-11 | Catalytic composition for isomerization of paraffinic hydrocarbons |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPS63287556A (en) |
| CN (1) | CN1022420C (en) |
| CA (1) | CA1289934C (en) |
| DD (1) | DD266743A5 (en) |
| HU (1) | HU203988B (en) |
| ZA (1) | ZA873090B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1043740C (en) * | 1993-11-05 | 1999-06-23 | 中国石油化工总公司 | Alleyl aromatics isomerizating catalyzer |
| CN1082540C (en) * | 1999-04-16 | 2002-04-10 | 中国石油化工集团公司 | Light hydrocarbon isomerizing catalyst and its preparation |
| FR2947464B1 (en) * | 2009-07-01 | 2011-07-22 | Inst Francais Du Petrole | MULTI-METALLIC CATALYST WITH HIGH METALLIC INTERACTION |
| SG189418A1 (en) * | 2010-10-18 | 2013-05-31 | Catalytic Distillation Tech | Benzene alkylation |
| CN105709810A (en) * | 2014-12-03 | 2016-06-29 | 南京克米斯璀化工科技有限公司 | C5C6 isomerization catalyst and preparation method thereof |
| CN106732753B (en) * | 2016-11-16 | 2019-08-27 | 中国海洋石油集团有限公司 | The preparation method of temp isomerizing catalyst in a kind of C5, C6 |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3507931A (en) * | 1967-12-22 | 1970-04-21 | Texaco Inc | Isomerization of paraffinic hydrocarbons in the presence of a mordenite catalyst |
| DE3038117A1 (en) * | 1980-10-09 | 1982-05-13 | EC Erdölchemie GmbH, 5000 Köln | HYDRATED HYDROCARBON MIXTURES, METHOD FOR THE PRODUCTION THEREOF, THEIR USE AND FUELS, CONTAINING THESE HYDROGENATED HYDROCARBON MIXTURES |
| US4489216A (en) * | 1982-01-25 | 1984-12-18 | Texaco Inc. | Hydrocarbon isomerization |
-
1987
- 1987-04-29 ZA ZA873090A patent/ZA873090B/en unknown
- 1987-05-11 JP JP62115694A patent/JPS63287556A/en active Granted
- 1987-05-11 DD DD87302640A patent/DD266743A5/en not_active IP Right Cessation
- 1987-05-11 HU HU872115A patent/HU203988B/en not_active IP Right Cessation
- 1987-05-11 CA CA000536741A patent/CA1289934C/en not_active Expired - Fee Related
- 1987-05-11 CN CN87103444A patent/CN1022420C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| DD266743A5 (en) | 1989-04-12 |
| JPS63287556A (en) | 1988-11-24 |
| ZA873090B (en) | 1987-12-30 |
| HU203988B (en) | 1991-11-28 |
| HUT48484A (en) | 1989-06-28 |
| CA1289934C (en) | 1991-10-01 |
| JPH0580261B2 (en) | 1993-11-08 |
| CN87103444A (en) | 1988-11-30 |
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