CN1210880A - Selective bifunctional multimetallic hydrocarbon conversion catalytic composite and process for use thereof - Google Patents
Selective bifunctional multimetallic hydrocarbon conversion catalytic composite and process for use thereof Download PDFInfo
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- CN1210880A CN1210880A CN 97120660 CN97120660A CN1210880A CN 1210880 A CN1210880 A CN 1210880A CN 97120660 CN97120660 CN 97120660 CN 97120660 A CN97120660 A CN 97120660A CN 1210880 A CN1210880 A CN 1210880A
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Abstract
A novel catalyst and the use thereof in a hydrocarbon conversion process is disclosed. The catalyst comprises a refractory inorganic oxide, platinum-group metal. Group IVA (IUPAC14) metal, and europium in a specified ratio. Utilization of this catalyst in the conversion of hydrocarbons, especially in reforming, results in signilicantly improved selecticity to the disired gasoline or aromatic products.
Description
Theme of the present invention is in finished catalyst, is combined into the dual-function catalyst composition and its application in hydrocarbon conversion reactions of the novelty of feature with the metallographic phase more than three kinds or three kinds of specific concentrations.In many application facet, particularly aspect oil and petrochemical complex, use catalyzer widely, with the very wide hydrocarbon conversion reactions of promotion scope with hydrogenation-dehydrogenation functionality and two kinds of functions of cracking function.The cracking function relates generally to usually as heavy metal components, the acid action material of the porous adsorptivity refractory oxide type of the support of VIII family (IUPAC8-10) metal or carrier for example, and described heavy metal components mainly plays hydrogenation-dehydrogenation functionality.Other metal that is chemical combination or element state can influence the one or both of cracking and hydrogenation-dehydrogenation functionality.
On the other hand, the present invention comprises and comes from improving one's methods of new catalyst purposes.Utilize these dual-function catalysts, to promote various hydrocarbon conversion reactions, for example dehydrogenation, hydrogenation, hydrocracking, hydrogenolysis, isomerization, desulfurization, cyclisation, alkylation, polymerization, cracking and hygrogenating isomerization reaction.Particularly, utilize catalyzer of the present invention, improved reforming method, improved selectivity gasoline and aromatic hydrocarbon product.
The catalysis bulk wight relates to many competition processes or response procedures.These comprise that cyclohexane dehydrogenation becomes aromatic hydrocarbons, alkyl cyclopentane dehydroisomerization to change into aromatic hydrocarbons, and the cyclic hydrocarbon dehydrocyclization becomes aromatic hydrocarbons, paraffinic hydrocarbons hydrocracking to become gasoline boiling range outer light hydrocarbon product, the dealkylation of alkylbenzene and the isomerization of paraffinic hydrocarbons.Some reaction in these reactions takes place in reforming process, and for example hydrocracking produces light paraffins gas, and the productive rate of gasoline boiling range product is had injurious effects.Therefore, the improvement of process is to react this target towards these of the more high yield of the gasoline fraction that improves the given octane value of influence in catalytic reforming.
Important key is that dual-function catalyst demonstrates the initial ability of effectively carrying out its specific function and this two aspect of life-span of the satisfaction of carrying out these specific functions.Measure concrete catalyzer and how carry out its purpose function under concrete hydrocarbon conversion reaction situation, employed in the art parameter is active, selectivity and stability.In reforming reaction, these parameter-definitions are as follows: (1) activity is under specified stringent condition, measure catalyzer the hydrocarbon reaction thing is changed into the ability of product, stringent condition is the combination of expression reaction conditions, and reaction conditions is: temperature, pressure, duration of contact and hydrogen partial pressure.Activity generally is to be appointed as pentane and the heavy hydrocarbon (" C that is obtained by certain raw material under given stringent condition
+ 5") octane value of product stream, otherwise or be appointed as and realize the desired temperature of given octane value.(2) selectivity refers under specific activity value, the petrochemicals aromatic hydrocarbons or the C that obtain from given raw material
+ 5The yield percentage of gasoline product.(3) stability is meant that time per unit or per unit handle the active or rate of change optionally of raw material.Activity stability generally is to realize given C
+ 5The rate of change of the service temperature of product octane value time per unit or unit raw material is measured, and the low rate of temperature variation is corresponding to good activity stability, because catalytic reforming unit is operated under more stable product octane value usually.Selectivity and stability is with time per unit or per unit raw material C
+ 5The changing down of product or aromatic production is measured.
The scheme of improving the reforming catalyst performance is to prepare by gasoline again, then extensively removes the delead antiknock dope, promotes to reduce the vehicle noxious emission.The method such as the catalytic reforming that improve quality of gasoline must be with high-level efficiency and greater flexibility operations, to satisfy the requirement of these variations.For making each component of gasoline be fit to these needs, avoid the lesser value product losses simultaneously, it is more important that selectivity of catalyst is just becoming.So the subject matter that the investigator faces in the present technique field is to develop more high-selectivity catalyst, keeps the effective active and the stability of catalyzer simultaneously.
Art technology is instructed the multimetallic catalyst of various feed naphtha catalytic reforming.Great majority wherein comprise has selected platinum metals, rhodium and IV A family (IUPAC14) metal.
US-A-3915845 number the conversion of carrying out hydro carbons with a kind of catalyzer is disclosed, described catalyzer comprise a kind of pt family metal, IV A family metal, halogen and with the atomic ratio of pt family metal be the lanthanon of 0.1-1.25.Preferred lanthanon is La, Ce and particularly Nd.A kind of catalyzer that is used for the U.S. catalytic hydroprocessing of hydrocarbon is disclosed for US-A-4039477 number, described catalyzer comprises a kind of refractory metal oxide, pt family metal, Sn and is selected from least a metal among Y, Th, U, Pr, Ce, La, Nd, Sm, Dy and the Gd, obtained favourable result during for lower ratio at the metal pair pt of back.Instructed for US-A5254518 number and a kind ofly comprised VIII family precious metal, IV B family oxide compound and at amorphous SiO
2-Al
2O
3On be loaded with rare earth oxide, be preferably the catalyzer of Nd or Y.
The purpose of this invention is to provide a kind of optionally new catalyst of the hydrocarbon conversion that improved.Further purpose of the present invention has provided a kind of optionally reforming method of gasoline or aromatic product that improved.
The present invention particularly comes from such discovery, promptly is stated from halogenation Al
2O
3On the catalyzer that contains pt, Sn, Eu in hydrocarbon reformation reaction, demonstrated aromizing to the cracked remunerative rate.
Main embodiment of the present invention is a kind ofly to comprise that refractory inorganic oxide, IV A family (IUPAC14) metal, Pt family metal and La are the catalyzer of metal.La is that the atomic ratio of metal and Pt family metal preferably is at least 1.3, more preferably more than 1.5 or 1.5 and most preferably be 2-5.Catalyzer also preferably preferably includes halogen, particularly chlorine.In preferred embodiments, refractory inorganic oxide is Al
2O
3, Pt family metal is that Pt and IV A family (IUPAC14) metal are Sn, Pt family metal is that Pt and La are that metal is selected from least a of Eu and Yb.Catalyzer very preferably comprises at Al
2O
3Sn on the carrier, Pt and major part are the Eu of EuO.
Moreover the present invention is a method of utilizing the hydrocarbon feed of catalyzer of the present invention to transform.Preferred hydrocarbon conversion reaction is to utilize catalyzer of the present invention to make the feed naphtha catalytic reforming to improve the reaction of gasoline and/or aromatic production.Conversion reaction comprises that more preferably dehydrocyclization is to improve the reaction of aromatic production.Best feed naphtha comprises C
6-C
8Hydro carbons, in catalytic reforming unit, its produces in benzene, toluene and dimethylbenzene one or more.
The comparison of cracking and aromizing output when Fig. 1 represents to use catalyzer of the present invention and prior art catalyst treatment stone brain raw material.
When Fig. 2 represented to handle feed naphtha, prior art and catalyzer of the present invention were reformed and are optionally compared.
Fig. 3 represents that three kinds contain the catalyzer of Eu and the comparative catalyst C that does not contain Eu
+ 5Comparison with aromatic production.
Fig. 4 represents to contain the funtcional relationship of relative reactivity and the selectivity and the Eu content of Eu catalyzer.
Therefore, main embodiment of the present invention is a kind of a kind of infusible inorganic oxide carrier that comprises, at least a metal of periodic table of elements IV A (IUPAC14) family (referring to Cotton andWilkinson, Advanced Inorganic Chemistry, John Wiley﹠amp; Sons (FifthEdition, 1988)], a kind of Pt family's metal and a kind of La are the catalyzer of metal.
The refractory inorganic oxide carrier used in the present invention normally surface-area of porous adsorptivity is 25-500m
2The high surface area carrier of/g.Porous carrier materials also should be uniformly aspect composition, and with respect to being infusible under the employed condition of hydrocarbon conversion reaction process.The meaning of term " form evenly " is that carrier is not stratified, do not have its form in intrinsic component concentrations gradient and composition be fully uniformly.Therefore, if this carrier is the mixture of two or more refractory material, the relative quantity of these materials is constant and uniform on whole carrier so.Be included in solid support material general in the difunctional hydrocarbon conversion catalyst within the scope of the present invention, for example: (1) difficult alkane inorganic oxide, for example aluminum oxide, magnesium oxide, TiO
2, ZrO
2, chromic oxide, ZnO, ThO
2, B
2O
3, silica-alumina, silicon oxide-magnesium oxide, chromic oxide-aluminum oxide, Al
2O
3-B
2O
3, SiO
2-ZrO
2Deng; (2) pottery, china clay, bauxite; (3) SiO
2Or silica gel, silicon carbide, clay and synthetic preparation or naturally occurring silicate, it is available or without acid treatment, for example U.S. atlapulgite, diatomite, Fuller's earth, kaolin or (U.S.) diatomite; (4) crystalline zeolite aluminosilicate, for example X-zeolite, Y-zeolite, mordenite, beta-zeolite, Ω-zeolite or L-zeolite, or Hydrogen or most preferably non-acid type, wherein one or more basic metal occupy the commutative position of positively charged ion; (5) non-zeolite molecular sieve, for example aluminophosphates or phosphorus silicon plumbite; (6) combination of one or more materials of one or more of these groups.
The infusibility solid support material preferably includes one or more inorganic oxides, wherein is used for the preferred Al of refractory inorganic oxide of the present invention
2O
3Suitable Al
2O
3Material is crystalline Al
2O
3, be commonly referred to as γ-Al
2O
3, η-Al
2O
3And θ-Al
2O
3, γ-Al wherein
2O
3Or η-Al
2O
3Obtained best result.Preferred refractory inorganic oxide will have the apparent bulk density of 0.3-1.0g/cc, and to have mean pore size be 20-300A
0, pore volume is that 0.1-1cc/g and surface-area are 100-500m
2The surface property of/g.
With regard to Al
2O
3Be preferred infusible inorganic oxide and opinion, particularly preferred Al
2O
3Be in US-A-3852190 and US-A-4012313, to be characterized by at those of the by product of the high alcohol synthesis reaction of the Ziegler of the conduct described in the US-A-2892858.For simplicity, this Al
2O
3" Ziegler Al hereinafter referred to as
2O
3".Now, Ziegler Al
2O
3Be to be purchased from Vista Chemical Company, trade mark is " Catapal ", or is purchased from Condea Chemie GmbH, and trade mark is " pural ".This material is the false boehmite of extreme high purity, at high temperature after the calcining, verifiedly obtains highly purified γ-Al
2O
3By the well-known method of catalystic material forming field professional, Al
2O
3Powder can be made any desirable shape of solid support material known to those skilled in the art or type, and is for example spherical, clavate, ball, bead, sheet, granular, extrudate and similar shape.
Support of the catalyst preferred shape of the present invention is spherical.Al
2O
3Ball can be made continuously by well-known oil drop method, and this method comprises: prepare Al by any means of instructing in this area
2O
3The water-sol preferably prepares with metallic aluminium and hydrochloric acid reaction; The water-sol and suitable jelling agent merging will be made; Splash in the oil bath of keeping at high temperature with the mixture that will generate.The droplet of mixture remains in the oil bath, till they solidify and generate hydrogel spheres may.Then, hydrogel spheres may is discharged from oil bath continuously, and carries out special aging drying treatment usually in oil and ammonia solution, further improves their physical property.Then, the aging mistake that makes and the particle of gelling washing back is dry and carry out 1-20 hour calcining step under 450-700 ℃ temperature under 150 ℃-205 ℃ lesser temps.This processing makes Al
2O
3The water-sol changes into corresponding γ-Al
2O
3US-A-2620314 provides other details, is incorporated herein reference.
The another kind of shape of solid support material is cylindrical extrudate, preferably passes through Al
2O
3Powder and water and suitable peptizing agent such as HCl mix the dough that can extrude up to generation and prepare.Form water yield loss on ignition (LOI) when 500 ℃ of calcinings that dough added, be enough to reach 45-65 quality %, and be preferably 55 weight %.The speed that acid adds generally is enough to the Al that provides used in the mixture of 2-7 quality %
2O
3Powder is non-volatile, is preferably 3-4 quality %.The dough that obtains extrudes formation extrudate particle by the mould of suitable size.These particles are under 260 ℃-427 ℃ temperature dry 0.1-5 hour then, generate the extrudate particle.It is that 0.6-1g/ml and surface-area are 150-280m that preferred refractory inorganic oxide mainly comprises apparent bulk density
2/ g (preferred 185-235m
2/ g is when pore volume is 0.3-0.8ml/g) pure Ziegler Al
2O
3
IV A family (IUPAC14) metal component is the chief component of catalyzer of the present invention.About IV A family (IUPAC14) metal, preferred especially Ge and Sn.Existence such as this component can metallic element, compound such as oxide compound, sulfide, halogenide, oxychlorination thing, or to exist with other component of porous carrier materials and/or catalyst composition form with the composition of physics or chemistry.In finished catalyst, the major portion of IV A family (IUPAC14) metal preferably exists with the oxidation state of above-mentioned metallic element.In metallic element, the optimum amount of IV A family (IUPAC14) metal component is to be enough to make contain 0.01-5 quality % metal in the finished catalyst that makes, and is preferably 0.1-2 quality % metal.
IV A family (IUPAC14) metal component can any suitable mode be introduced in the catalyzer, to obtain uniform distribution, for example by with the porous carrier materials co-precipitation, carry out ion-exchange with solid support material, in catalyst preparation process, at a certain step impregnated carrier material.A kind of method that IV A family (IUPAC14) metal component is introduced catalyst composition comprises the decomposable compound of the solubility of utilizing IV A family (IUPAC14) metal, metal is full of and is dispersed in whole porous carrier materials.IV A family (IUPAC14) metal component can be before other component be added to solid support material, simultaneously or afterwards the impregnated carrier material.Like this, IV A family (IUPAC14) metal component is by solid support material and suitable metal salt or soluble compound for example tin protobromide, tin protochloride, tin tetrachloride, tin tetrachloride pentahydrate; Or germanium dioxide, the tetrem alkoxide of germanium, GeCl
4Or the aqueous solution of compound such as lead nitrate, lead acetate, lead chlorate is added on the solid support material.Particularly preferably be and utilize IV A family (IUPAC14) metal chloride, for example SnCl
4, GeCl
4Or lead chlorate, because it is easy to introduce metal component and at least one a spot of preferred halogen component in a step.At particularly preferred aforesaid Al
2O
3In the peptization course, when cooperating, just obtained the uniform dispersion thing of IV A family (IUPAC14) metal component according to the present invention with hydrogenchloride.In another embodiment, be in the inorganic oxide adhesive peptization course, with organometallic compound such as trimethyltin chloride with dimethyl tin dichloride is introduced catalyzer and most preferably at Al
2O
3At HCl or HNO
3Introduce in the peptization course.
Another chief component of catalyzer is a Pt family metal component.This component comprises Pt, Pd, Rn, Rh, Ir, Os or their mixture, and wherein Pt is preferred.Pt family metal in the finished catalyst composition can with for example existence such as oxide compound, sulfide, halogenide, oxyhalogenation thing of compound of one or more other component of catalyst composition, or exist with the metallic element form.When this component all be basically with element state exist and this component be evenly dispersed in obtain in the solid support material best as a result the time.This component is catalytically effective amount existence arbitrarily in the finished catalyst composition; With the element is that benchmark calculates, and finished catalyst generally comprises the Pt family metal of 0.01-2 quality %.When catalyzer comprises the Pt of 0.05-1 quality %, obtained excellent results.
Pt family metal component can any suitable mode, and for example co-precipitation, ion-exchange or dipping are introduced porous carrier materials.The preferred method of preparation catalyzer comprises the decomposable compound of the solubility of using the Pt metal, with mode impregnated carrier material more equably.For example, this component can be added on the carrier by carrier and Platinic chloride or chloro-iridic acid or chlorine palladium aqueous acid are mixed.Also can adopt other water-soluble cpds or the title complex of Pt family metal in dipping solution, they comprise ammonium chloroplatinate, bromoplatinic acid, tri-chlorination platinum, the Tetrachloroplatinum hydrate, dichloride two chloroformyl platinum, dinitrobenzene diamino platinum, tetranitro sodium platinate (II) (Sodium tetranitroplatinate (II)), Palladous chloride, Palladous nitrate, palladous sulfate, diamino palladium oxyhydroxide (diamminepalladium (II) hydroxide), chlorine four ammonia palladiums (tetrammine pallaclium (II) chloride), chlorine six ammonia palladiums, rhodium carbonyl chloride, the Trichlororhodium hydrate, rhodium nitrate, chlordene rhodium acid sodium (Sodium hexachlororhodate (III), hexanitro-rhodium acid sodium (Sodium hexanitrorhodate (III)), tribromide iridium, iridochloride, iridic chloride, hexanitro-iridium acid sodium (Sodium hexanitroridate (III)), potassium hexachloroiridate or sodium iridichloride, oxalic acid rhodium potassium etc.The preferred muriatic compound that uses Pt, Ir, Rh or Pd, the hydrate of Platinic chloride, chloro-iridic acid or acid of chlorine palladium or Trichlororhodium for example is because help introducing the Pt family's metal component and the preferred halogen component of a small amount of at least in a step.For the introducing that further helps halogen component with make each metal component uniform distribution on whole solid support material, HCl or similarly acid generally also add dipping solution.In addition, the impregnated carrier material is usually preferably after its calcining, so that make the wash-out danger of valuable Pt family metal reduce to minimum.
Usually, Pt family metal component disperses in catalyzer equably.Pt family metal homodisperse situation is measured by scanning transmission electron microscope (STEM), and each concentration of metal and catalyst metal total content are compared.In another scheme, one or more Pt family metal components can exist as the described upper layer component of US-A-4677094, and the content of this patent documentation is incorporated herein reference." upper layer " is the layer of catalyst particles on adjacent particles surface, decays gradually in the center of upper layer concentration of metal from the surface to the granules of catalyst.
Lanthanide series metal is another main ingredient of catalyzer of the present invention.Lanthanide series metal comprises La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu.Favourable element is to generate stable those elements of+2 ionic, i.e. Sm, Eu and Yb (CRC Handbook of Chemistry and Physics 75
ThEdition 1994-1995, CRC Press, Inc.), wherein preferred Yb and Eu, and Eu is most preferred.Usually, the group of the lanthanides component can exist with form in catalyst composition in any catalysis, metallic element for example, compound such as oxide compound, oxyhydroxide, halogenide, oxyhalogenation thing, aluminate, or the form that cooperates with one or more other component chemical of catalyzer exists.Though do not plan the present invention is carried out such restriction, but, it is believed that when group of the lanthanides component whole basically group of the lanthanides component in catalyst composition be oxidation state with above-mentioned metal, when for example oxide compound, oxyhalogenation thing or their mixture of halogenide exist, obtained best result, for reaching this purpose, in the preparation of catalyst composition of the present invention, preferred described subsequently oxidation and the reduction step used.In a particularly preferred scheme, select preparation process and condition, to realize that most of form (i.e. group of the lanthanides component more than 50%) of the stable favourable group of the lanthanides component of+2 ionic that generates is as SmO, EuO and/or YbO.Be that (by lanthanum atomic standard) exists with+2 oxide compounds more than 80% best, for example, preferred EuO.Because the last reduction step of catalyzer can be finished in reformer on the spot, therefore catalyzer of the present invention is being made or all have a ratio of this oxide compound before its use of reforming process.
Can the catalysis effective any amount of lanthanum component is introduced catalyzer, when in the catalyzer in the element being benchmark lanthanum component when being 0.05-5 quality %, has obtained good result.When being that basic calculation lanthanide series metal component is 0.2-2 quality % with the element, obtained best result usually.The atomic ratio of preferred lanthanide series metal component and Pt family metal was at least 1.3: 1 in this catalyzer, be preferably 1.5: 1 or more than, be preferably 2: 1 to 5: 1 especially.
In any suitable mode known in the art, for example by with the co-precipitation of porous carrier materials, altogether gelling or coextrusion, with the ion-exchange of the solid support material of gelling, or after porous carrier materials drying and calcining, before or its during, the dipping porous carrier materials is incorporated into the group of the lanthanides component in the catalyst composition.Introduce and all universal methods of metal component that distribute simultaneously in the catalyzer plan all to comprise within the scope of the invention with desirable mode, but do not want the special methods of employed introducing as essential feature of the present invention.The preferred method of using produces lanthanum component part dispersive method uniformly, is within the scope of the invention though generate the dispersive method of uneven lanthanum component.
A kind of proper method of the lanthanum component being introduced catalyst composition is included in preferred solid support material Al
2O
3Preparation process in corresponding hydrous oxide or oxyhalogenation thing form gelling or co-precipitation lanthanum component altogether.This method generally comprises the lanthanum compound of the colloidal sol of suitable solubility colloidal sol or dispersibility such as lanthanum trichloride, lanthanum-oxides etc. is added Al
2O
3The water-sol will contain the water-sol of lanthanum then and suitable jelling agent mixes and it is medium that the mixture that makes is splashed into an oil bath, and it is described at length to be explained as follows literary composition.Alternatively, lanthanum compound can be added in the jelling agent.After the gelling material of air drying and calcining generation, obtain Al
2O
3Material with lanthanum-oxides and/or oxychlorination thing intimately admixing.
The preferred method that the lanthanide series metal component is introduced catalyst composition comprises the impregnating porous carrier solution material that utilizes group of the lanthanides solubility decomposable compound.Usually in this impregnation steps used solvent be according to dissolving institute's lanthanide series compound that requires and maintenance it in solution up to being uniformly distributed in whole solid support material not other component to solid support material or catalyzer have the ability of disadvantageous effect to select.The suitable solvent comprises alcohols, ethers, acids etc., wherein preferably uses acidic aqueous solution.Therefore, the acidic solution by compounds such as carrier and suitable lanthanide metal salt, title complex or compound such as nitrate, muriate, fluorochemical, Organoalkyl thing, oxyhydroxide, oxide compounds mixes the lanthanide series metal component is added on the solid support material.The suitable acids that is used for dipping solution is: mineral acid such as HCl, HNO
3Deng, strongly-acid organic acid such as oxalic acid, toxilic acid, citric acid etc.The lanthanide series metal component can be before Pt family metal component, simultaneously or be impregnated into carrier afterwards.
As lanthanide series metal component equally distributed alternative method in carrier, the lanthanide series metal of upper layer can any suitable mode be introduced granules of catalyst, to realize from the surface of granules of catalyst to the reduction of central metal gradient.Near this compound decomposition and on granules of catalyst surface or disengage the metallic compound impregnated carrier of metal it when preferably, contacting with carrier with metallic compound.Do not limit other method of the present invention and comprise that utilization cooperates or do not infiltrate the metallic compound of granules of catalyst inside with carrier.An example is many ligands, for example carboxylic acid or contain amino, contain thiol, the phosphorus base or can with other the metallic compound of polar group of the strong Cheng Jian of oxide carrier.Alternatively, the lanthanide series metal component also can be introduced catalyzer by the spraying dipping.
Catalyzer can also comprise the mixture of other component or these components, is used alone as or is used as together catalyst modifier, to improve activity of such catalysts, selectivity or stability.The properties-correcting agent of some known catalyzer comprises Rh, In, Co, Ni, Fe, W, Mo, Cr, Bi, Sb, Zn, Cd and Cu.These components of catalytically effective amount can any suitable way be added in the solid support material during solid support material preparation back or preparation, or before other component is introduced, while or join in the catalyst composition afterwards.
Catalyzer transforms scheme especially for hydrocarbon of the present invention, and the selective component that comprises the catalyzer in dehydrogenation, dehydrocyclization or the hydrogenation reaction is basic metal or alkaline earth metal component.More precisely, this selective component is to be selected from by basic metal--Cs, Rb, K, and in the group that the compound of the compound of Na and Li--and alkaline-earth metal--Ca, Sr, Ba and Mg is formed.Usually, when having constituted the 0.01-5 quality % of composition in this component of element in the catalyst composition, in these schemes, obtained good result.This selective basic metal or alkaline earth metal component can be introduced in the catalyst composition with any known mode, wherein preferred aqueous solution dipping with suitable water-soluble decomposable compound.
As mentioned above, in catalyst preparation step of the present invention, must adopt at least one oxidation step.Realize that the condition that oxidation step adopted is the such condition of corresponding oxide form that selection all changes into metal components all in the catalyst composition them basically.Oxidation step takes place under 370 ℃ of-600 ℃ of temperature usually.The oxygen atmosphere that is adopted generally includes air.Usually, oxidation step will carry out more than 0.5-10 hour or 10 hours during, be the needed time of corresponding oxide form that all metal components is changed into substantially they during accurate.Certainly, this time changes with the oxygen level of oxidizing temperature that is adopted and the atmosphere that adopted.
Except oxidation step, in the Preparation of catalysts step, also can adopt the halogen regulating step.As mentioned above, the halogen regulating step can be difunctional service.At first, the halogen regulating step can help the homodisperse of IV A (IUPAC14) family metal and the homodisperse of other metal component.In addition, the halogen regulating step can be used as the institute's required amount introducing finished catalyst method for compositions with halogen.The halogen regulating step adopts halogen or halogen-containing compound in air or oxygen atmosphere.Comprise chlorine owing to be used to introduce the preferred halogen of catalyst composition, employed preferred halogen or halogen contained compound are the precursors of Cl, HCl or these compounds during the halogen regulating step so.In carrying out the halogen regulating step, catalyst composition contacts under 370 ℃-600 ℃ high temperature with halogen or halide-containing in air or oxygen atmosphere.In contact procedure, there is also a desire for water and exist, to help adjusting.Specifically, when the halogenic ingredient of catalyzer comprises chlorine, the preferred H that uses
2The mol ratio of O and HCl is 5: 1-100: 1.The time length of halogenation step is generally 0.5-5 hour or longer.Because conditional likelihood, the halogen regulating step can carry out during oxidation step.In addition, the halogen regulating step can be before or after oxidation step, as prepares the employed concrete grammar of catalyzer of the present invention and carry out desired.No matter employed accurate halogen regulating step how, the content of halogen should be to comprise enough halogens in the finished catalyst, by element, is the 0.1-10 quality % of finished catalyst.
In Preparation of Catalyst, also need to adopt reduction step.Reduction step be used for Pt family metal component basically Restore All become the metallic state of respective element and guarantee evenly and make this component in the fine distribution of whole refractory inorganic oxide.Reduction step is preferably carried out in substantially anhydrous environment.The preferably pure substantially and exsiccant hydrogen of reducing gas (promptly less than 20ppmv water).But, other reducing gas such as CO, N
2Deng also adopting.Usually, reducing gas and the catalyst composition of oxidation are to comprise that reduction temperature is to contact under the condition of 315 ℃-650 ℃, 0.5-10 hour or the time durations more than 10 hours, effectively reduction basically all Pt families metal group be divided into the metallic state of element.Reduction step can be carried out before catalyst composition is packed the hydrocarbon zone of transformation into, or carries out on the spot when the hydrocarbon conversion process process begins to carry out.But, if adopt this technology of back, must carry out suitable preventive measures, as predrying hydrocarbon conversion unit, make it anhydrous basically and should adopt anhydrous basically hydrogenous reducing gas.
Catalyst composition can carry out the prevulcanized step.Optional sulphur component can be introduced catalyzer with any known method.
Catalyzer of the present invention is particularly useful as hydrocarbon conversion catalyst.The hydrocarbon that will be transformed contacts with catalyzer under the hydrocarbon conversion condition, and described conversion condition comprises 40-300 ℃ temperature, and the pressure (101.3KPa-20.26MPa) and the liquid hourly space velocity of normal pressure-200 bar absolute pressure are 0.1-100hr
-1Catalyzer is particularly suitable for the catalytic reforming of gasoline-range raw material, and also can be used for dehydrocyclization, the isomerization of aliphatic and aromatic hydrocarbons, dehydrogenation, hydrocracking, disproportionation, dealkylation, alkylation, transalkylation, Oligomerisation and other hydrocarbon conversion reaction.
In preferred catalytic reforming scheme, after hydrocarbon feed and the hydrogen-rich gas preheating, add the reforming reaction district that generally comprises two to five tandem reactors.Suitable heating unit is set to compensate the clean heat that absorbs of reaction in each reactor between reactor.Reactant contacts with catalyzer with upper reaches, mode dirty or radial flow in each reactor, wherein the mode of preferred runoff.Catalyzer is a fixed bed system, or moving-bed system preferred and that continuous catalyst regenerating interrelates.The method of other of the reactivation of catalyst of inactivation all is that those skilled in the art is well-known, comprise half regenerative operation, in half regenerative operation, all install regeneration and the reactivate that catalyzer is carried out in shut-down operation, or the operation of shift-converter, in this operation, reactor and system disconnect, regenerate and reactivate, and other reactor is kept production.The cyclic regeneration of the preferred catalyzer that is connected with the moving-bed system especially is disclosed in US-A-3647680; US-A-3652231; Among US-A-3692496 and the US-A-4832291, all these patent documentations all are incorporated herein reference.
To the disengaging zone, this disengaging zone maintains 0 ℃-65 ℃ to the effluent of catalytic reforming zone usually by refrigerating unit, and hydrogen rich gas is commonly referred in " unsettled reformate " and separates from liquid stream.The hydrogen stream of Sheng Chenging is by suitable pressurizing device then, and circulation turns back to reformer section.Liquid phase from the disengaging zone is generally discharged, and handles in fractionating system, so that regulate the concentration of butane, controls the volatility of the reformate front end that generates thus.
Applied operational condition comprises the pressure that is chosen in 100KPa-7MPa (definitely) scope in the reforming process process of the present invention.Under low pressure obtain good especially result, promptly under 350-2500Kpa pressure, obtained good especially result.Reforming temperature is preferably 425 ℃-565 ℃ in 315 ℃-600 ℃ scope.Well-known just as the technician in the reformation technical field, temperature begins to be chosen in this wide scope, thinks that mainly the desired octane of reformate and the raw material of adding and the feature of catalyzer have functional relation.Usually, at run duration, temperature increases at leisure, to compensate expected deactivation, to provide the product of stablizing octane value.Supply with enough hydrogen,, when every mol hydrocarbon feed uses 2-10mol hydrogen, obtained best result so that the 1-20mol hydrogen/hydrocarbon feed mol that enters reformer section to be provided.Equally, be selected from 0.1-10hr in the employed liquid hourly space velocity of reformer section (LHSV)
-1, preferred 1-5hr
-1
Add the feed naphtha that comprise naphthenic hydrocarbon and paraffinic hydrocarbons of the preferred boiling point of hydrocarbon feed of this reforming system in gasoline-range.Preferred raw material is the petroleum naphtha of mainly being made up of naphthenic hydrocarbon and paraffinic hydrocarbons, but in many cases, also has aromatic hydrocarbons.A this preferred class comprises straight-run spirit, natural gasoline, synthetic gasoline etc.As a yes-no decision, very advantageously be the gasoline that adds heat or catalytic cracking, the petroleum naphtha of part reformation or the petroleum naphtha of dehydrogenation.Also can use the mixture of the petroleum naphtha of straight run and pressure gasoline scope.The reinforced raw material of the petroleum naphtha of gasoline-range is that to have initial ASTM D-86 boiling point be that 40-80 ℃ and end point are 160-220 ℃ full boiling range gasoline, or be selected from its cut, this generally is a high boiling fraction, be commonly referred to heavy naphtha for example boiling point be 100-200 ℃ petroleum naphtha.If the purpose of reforming is to produce one or more of benzene, toluene and dimethylbenzene, the scope of boiling point in principle or be essentially 60-150 ℃ so.In some cases, add pure hydrocarbon or the hydrocarbon mixture that reclaims by extraction element-raffinate that extracts of aromatic hydrocarbons or that straight-chain paraffin-it will be converted to aromatic hydrocarbons is also favourable for example.
Usually, preferably under anhydrous basically environment, utilize the present invention.Realize that in reformer section the key of this condition is that control adds the raw material of reformer section and the water yield in the hydrogen stream.The total amount that enters the water of zone of transformation when any source keeps during preferably less than 20ppm (in the water equivalent in the raw material), obtaining best result less than 50ppm usually.In general, this just can realize by the water of controlling carefully in raw material and the hydrogen stream.Raw material can for example have high optionally conventional solid sorbent material, for example the crystalline silico-aluminate of sodium or calcium, silicon gel, active A l to water by utilizing suitable drying installation known in the art
2O
3, molecular sieve, anhydrous CaSO
4, high surface area sorbent materials such as sodium carry out drying.Equally, the water-content in the raw material can be by fractional column or is similarly carried out suitable stripping in the device and operate and regulate.In some cases, can use adsorption dry and stripping drying to match, advantageously realize from raw material, almost completely removing and anhydrate.Preferably, raw material drying arrives the analog value less than the 20ppm of water equivalent.
The water-content that preferably enters the hydrogen stream of hydrocarbon zone of transformation remains on 10-20ppmv or less than this value.In the case, if the water-content of hydrogen stream at this more than scope, this can realize by hydrogen stream and the siccative that is fit to such as above-mentioned those are contacted under general drying conditions.
The present invention preferably implements to use under no sulphur environment.Can use any control device known in the art to handle the feed naphtha that adds the reforming reaction district.For example, raw material can carry out adsorption treatment, catalytic treatment, or their processing of matching.Adsorption treatment can adopt the SiO of molecular sieve, high surface area
2-Al
2O
3, carbonaceous molecular sieve, silicon metal plumbite, gac, contain the composition of high surface area metal, for example contain the composition of the high surface area of Ni or Cu etc.Preferred these raw materials are removed the pollutent of the sulphur, nitrogen and the generation water that contain substantially, and are made alkene contained in the raw material saturated by pretreatment processs such as for example hydrofining of conventional catalyst pretreatment process, hydrotreatment, hydrogenating desulfurizations.Catalytic treatment can be adopted the prescription of traditional sulphur reducing catalyst known in the art, and described prescription comprises the refractory inorganic oxide carrier that contains the metal in the group that is selected from periodictable VI-B (6) family, II-B (12) family and VIII family (IUPAC8-10) composition.
A scheme of the present invention is included under the condition of catalytic dehydrogenation cyclisation, the method that feed naphtha transforms.Specifically, preferred petroleum naphtha comprises C
6-C
8Non-aromatics.The dehydrocyclization condition comprises that pressure is 100KPa-4MPa (definitely), and preferred pressure is 200KPa-1.5MPa, and temperature is that 350 ℃-650 ℃ and liquid hourly space velocity are 0.1-10hr
-1Preferably, hydrogen can be used as thinner.When existing, hydrogen can 0.2-10molH
2The rate loop of/mol hydrocarbon feed.
The feed naphtha of preferred another dehydrocyclization method scheme comprises a high proportion of paraffinic hydrocarbons, because of the purpose of dehydrocyclization method is that paraffin conversion is become aromatic hydrocarbons.Because C
6-C
8The high value of aromatic hydrocarbons, therefore, also preferred feed naphtha comprises C
6-C
8Paraffinic hydrocarbons.But, do not get rid of this selection, promptly feed naphtha removes C
6-C
8Paraffinic hydrocarbons is outer can to comprise naphthenic hydrocarbon, aromatic hydrocarbons and alkene.Embodiment 1
Comprise and be loaded in Al
2O
3The prior art spherical catalyst of Pt on the carrier and Sn is by general technology preparation, is used as the comparative catalyst who compares with catalyzer of the present invention.According to prior art Sn is introduced Al
2O
3Colloidal sol contains the Al of Sn
2O
3Colloidal sol is made oil droplet and is generated the 1.6mm ball, is 10% and in 650 ℃ of calcinings down with its steam-treated to be dried to LOI.Ball type carrier floods with the Platinic chloride that contains HCl then, has obtained containing the finished catalyst of 0.38 quality %Pt.Dry impregnated catalyzer, and under 525 ℃, after the oxychlorination, under 565 ℃, reduce with pure hydrogen in air with 2MHCl.
The comparative catalyst's called after catalyzer X that makes, approximately by following forming (quality %):
Pt: 0.38
Sn:0.3 embodiment II
Preparation comprises Pt, Yb and Sn is loaded in Al
2O
3On spherical catalyst so that feature of the present invention to be described.Sn introduces Al by prior art
2O
3Colloidal sol contains the Al of Sn
2O
3Colloidal sol is made oil droplet and is generated the 1.6mm ball, is 10% and in 650 ℃ of calcinings down with its steam-treated to be dried to LOI.Ball type carrier floods with the nitric acid that contains 3.5% ytterbium nitrate then, and solution is 1: 1 with the carrier ratio, contains 1.1%Yb in the finished catalyst that makes.After the composition water steam drying that obtains is 10% to LOI, calcine with 3% water vapor down at 650 ℃.The calcined composition that makes contains 0.38 quality %Pt with the HCl dipping that contains Platinic chloride in the finished catalyst that obtains.Dry impregnated catalyzer, and with 2MHCl in air after carrying out oxychlorination under 525 ℃, reduce down at 565 ℃ with pure hydrogen.
The finished catalyst called after catalyst A that contains Yb, approximately by following forming (quality %):
Yb: 1.1
Pt: 0.38
Sn: 0.3
In the mode identical with containing the Yb catalyzer, preparation contains other catalyzer of La, Sm and Dy.The content of La series elements is as follows in the finished catalyst, and wherein each catalyzer and catalyst A have essentially identical Sn and Pt content.
Catalyst B 0.9 quality %La
Catalyzer C 1.0 quality %Sm
Catalyzer D 1.1 quality %Dy embodiment III
Carry out pilot plant test, the catalyzer of catalyzer more of the present invention and prior art in the reforming process process to the selectivity of aromatic hydrocarbons.Test is to be undertaken by following condition, and promptly the pressure of reformed naphtha is that 0.8MPa (definitely), liquid hourly space velocity are 3hr on catalyzer
-1And H
2/ hydrocarbon mol ratio is 8.By changing the scope of temperature studies transformation efficiency, obtain the data point under 502 ℃, 512 ℃, 522 ℃ and 532 ℃ of temperature.The petroleum naphtha of comparison test is the petroleum naphtha that the hydrotreatment oil obtains, and described petroleum naphtha is the petroleum naphtha of Mid-continent (North America) crude oil from paraffin, and described crude oil has following feature:
Proportion: 0.737
Distillation
ASTMD-86℃
IBP: 87
10％: 97
50％: 116
90％: 140
EP: 159
Quality % paraffin series: 60
Naphthenic hydrocarbon: 27
Aromatic hydrocarbons: 13
Figure l shows aromatics yield and the C of catalyst A, B, C, D and X
+ 5The result of productive rate.Aromatics yield is defined as benzene, toluene, C
8Aromatic hydrocarbons and C
+ 9The quality % of aromatics yield.Therefore, the high aromatics yield main object of catalytic reforming normally.Relative C
+ 5The high aromatics yield of productive rate is a kind of expression of highly selective.Catalyst A of the present invention, B, C and D show at identical C
+ 5Under the productive rate, the high 2-3% of aromatics yield.The embodiment IV
Carry out pilot plant test, relatively selectivity and the activity of feed naphtha reforming catalyst C and X.Used identical in used petroleum naphtha and the embodiment III in the comparison test.The condition of each test basis comprises that pressure is 0.8MPa (definitely), liquid hourly space velocity 3hr
-1And H
2/ hydrocarbon ratio is 8.By changing the scope of temperature studies transformation efficiency, under 502 ℃, 512 ℃, 522 ℃ and 532 ℃ of each temperature, several data points have been obtained.The transformation efficiency of paraffinic hydrocarbon and naphthenic hydrocarbon is than the high 2-4% of catalyzer X, still with C under each temperature
+ 5It is high that the catalysts selective C that the productive rate of product is represented wants in whole conversion range.Fig. 2 shows the figure of selectivity and transformation efficiency relation.The embodiment V
Levying preparation with the commentaries on classics of the present invention's description comprises pt and Eu and Sn and is loaded in Al
2O
3On 3 spherical catalysts so that feature of the present invention to be described.Sn introduces spherical Al by the described prior art of embodiment II
2O
3Carrier.Ball type carrier floods with the nitric acid that contains 3.5% europium nitrate then, and solution is 1: 1 with the carrier ratio during dipping, has obtained three kinds of different finished catalysts of europium content.The composition water steam drying that generates is 10% back and calcines in 650 ℃ of 3% water vapor to LOI.The calcined composition usefulness that obtains contains the salt acid dipping of Platinic chloride, obtains the finished catalyst of 0.38 quality %Pt.Dry impregnated catalyzer after the oxychlorination, is used pure H down at 565 ℃ with 2MHCl down at 525 ℃ in air
2Reduction.Finished catalyst called after E, the F and the G that contain Eu, and approximately by following forming (quality %):
Catalyzer E F G
Eu 0.30 0.51 1.1
Pt 0.37 0.37 0.38
Sn 0.3 0.3 0.3 embodiment VI
Catalyzer G carries out the comparison test with the catalyzer X of prior art, to confirm existing according to determination by reduction EuO.Program control temperature is realized reduction process, uses to contain 5mol%H
2Ar, be raised to 600 ℃ with the speed of 10 ℃ of per minutes from room temperature.The H that catalyzer G consumes
2Surpass catalyzer X33 μ mol/g, this just shows the Eu more than 90%
+ 3Be reduced into Eu
+ 2The embodiment VII
Carry out pilot plant test, relatively the selectivity and the activity of the reformation of catalyzer E, F and G and catalyzer X feed naphtha.
Used identical of the petroleum naphtha of comparison test and embodiment III.
The condition of reorganization of each test comprises that pressure is that 0.8MPa (definitely), liquid hourly space velocity are 3hr
-1And H
2/ hydrocarbon ratio is 8.By changing temperature studies transformation efficiency scope, obtain several data points under each temperature of 502 ℃, 512 ℃, 522 ℃ and 532 ℃.Compare transformation efficiency (paraffinic hydrocarbon and naphthenic hydrocarbon), C
+ 5The productive rate of product and aromatics yield all use following quality % to represent:
502℃ X E F G
Transformation efficiency 79.5 75.6 70.1 58.9
C
+ 5Productive rate 89.5 91.6 92.9 96.2
Aromatics yield 65.8 65.1 61.5 52.2
512℃ X E F G
Transformation efficiency 84.7 81.2 76.9 65.3
C
+ 5Productive rate 88.1 90.0 91.7 95.2
Aromatics yield 68.8 68.4 66.6 58.3
522℃ X E F G
Transformation efficiency 88.1 85.2 82.3 70.8
C
+ 5Productive rate 86.7 88.8 90.3 94.0
Aromatics yield 70.0 70.3 69.6 62.9
523℃ X E F G
Transformation efficiency 91.6 89.2 86.6 75.5
C
+ 5Productive rate 85.2 87.4 88.9 92.6
Aromatics yield 71.5 72.0 71.9 66.6
Fig. 3 shows aromatics yield and the C that is marked and drawed by above-mentioned value
+ 5The graph of a relation of productive rate shows that catalyzer of the present invention is at identical C
+ 5Aromatics yield is higher under the productive rate.
Go out activity and optionally concern and be illustrated in Fig. 4 from above-mentioned value association.
Activity is to be benchmark with catalyzer X, each temperature is pressed transformation efficiency reduce % and calculate, and the Eu/Pt atomic ratio of each catalyzer is drawn.Selectivity is to be used in C
+ 5In the common scope of productive rate, the variation of the aromatics yield between the catalyzer removes C
+ 5Productive rate is measured, promptly with C
+ 5Productive rate % represents the mean change Δ of aromatics yield.In Fig. 4, mark with C
5 +When productive rate % represented the mean change Δ of aromatics yield, catalyzer G represented with milder line to the extended line of high Eu/Pt.Because the line of the line of catalyzer G and other catalyzer of Fig. 3 is only seldom overlapping.
Fig. 4 shows, transformation efficiency with the raising of catalyzer Eu content for example Eu/Pt between 1 and 2, quicken to reduce.At Eu/Pt is 2 when above, and it is higher that slope becomes.On the other hand, selectivity and the relation of Eu/Pt ratio are more near linear relation.Though selectivity and active relative importance are depended in the selection of Eu/Pt ratio, very high ratio will cause the serious loss of activity with respect to the selectivity advantage.
Claims (8)
1, a kind of catalyst composition, comprise a kind of refractory inorganic oxide carrier, contain 0.01-5 quality % IV A family (IUPAC14) metal component in element, in 0.01-2 quality %Pt family's metal component of element with in the 0.05-5 quality %Eu component of element, wherein the Eu more than 50% exists with EuO.
2, by the catalyst composition of claim 1, wherein refractory inorganic oxide comprises Al
2O
3
3, by the catalyst composition of claim 1 or 2, wherein Pt family metal component comprises the Pt component.
4, by each the catalyst composition of claim 1-3, wherein IV A family (IUPAC14) metal component comprises the Sn component.
5, by each the catalyst composition of claim 1-4, wherein the atomic ratio of Eu and Pt family metal is at least 1.3.
6, by each the catalyst composition of claim 1-5, also comprise halogen component.
7, by the catalyst composition of claim 6, wherein halogen component comprises the chlorine component.
8, a kind of method of feed naphtha catalytic reforming, this method are included in and comprise 425 ℃-565 ℃ temperature, the pressure of 350-2500Kpa (gauge pressure), and liquid hourly space velocity is 1-5hr
-1And H
2/ hydrocarbon feed mol ratio is under the condition of reorganization of 2-10, and raw material is contacted with the catalyst composition of each definition of claim 1-7.
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| CN97120660A CN1075106C (en) | 1997-09-08 | 1997-09-08 | Selective bifunctional multimetallic hydrocarbon conversion catalytic composite and process for use thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1091135C (en) * | 1999-09-29 | 2002-09-18 | 中国石油化工集团公司 | Hydrogenating catalyst for heavy oil and its preparing process |
| US6780814B2 (en) | 2001-04-28 | 2004-08-24 | China Petroleum & Chemical Corporation | Multimetallic reforming catalyst comprising platinum and tin, the preparation and the application thereof |
| CN101987298B (en) * | 2009-08-07 | 2012-08-08 | 中国石油天然气股份有限公司 | Metal-modified eutectic zeolite catalyst with EUO (Europium Oxide) structure as well as preparation method and application thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3915845A (en) * | 1973-12-06 | 1975-10-28 | Universal Oil Prod Co | Hydrocarbon conversion with a multimetallic catalytic composite |
| US4003826A (en) * | 1973-12-06 | 1977-01-18 | Uop Inc. | Hydrocarbon conversion with an acidic multimetallic catalytic composite |
| FR2280426A1 (en) * | 1974-07-30 | 1976-02-27 | Raffinage Cie Francaise | HYDROCARBON HYDROTREATMENT CATALYSTS AND APPLICATION OF SUCH CATALYSTS |
| US4677094A (en) * | 1986-09-22 | 1987-06-30 | Uop Inc. | Trimetallic reforming catalyst |
-
1997
- 1997-09-08 CN CN97120660A patent/CN1075106C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1091135C (en) * | 1999-09-29 | 2002-09-18 | 中国石油化工集团公司 | Hydrogenating catalyst for heavy oil and its preparing process |
| US6780814B2 (en) | 2001-04-28 | 2004-08-24 | China Petroleum & Chemical Corporation | Multimetallic reforming catalyst comprising platinum and tin, the preparation and the application thereof |
| CN101987298B (en) * | 2009-08-07 | 2012-08-08 | 中国石油天然气股份有限公司 | Metal-modified eutectic zeolite catalyst with EUO (Europium Oxide) structure as well as preparation method and application thereof |
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