CN100338189C - Method for preparing reforming catalyst in platinum, stannum series - Google Patents

Method for preparing reforming catalyst in platinum, stannum series Download PDF

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CN100338189C
CN100338189C CNB2004100379315A CN200410037931A CN100338189C CN 100338189 C CN100338189 C CN 100338189C CN B2004100379315 A CNB2004100379315 A CN B2004100379315A CN 200410037931 A CN200410037931 A CN 200410037931A CN 100338189 C CN100338189 C CN 100338189C
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carrier
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CN1696253A (en
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马爱增
潘锦程
杨森年
刘辰
方大伟
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Abstract

The present invention relates to a preparation method of reforming catalysts of platinum and tin. The catalyst comprises high temperature-resistant inorganic oxide carriers and the active components with the following contents by using the carriers as a calculation reference: 0.01 to 5.0 wt% of metal of a group VIII, 0.01 to 5.0 wt% of the metal of a group IVA, 0 to 10.0 wt% of lanthanide series metal, and 0.1 to 10.0 wt% of halogen. The method comprises the steps that firstly, the high temperature-resistant inorganic oxide carriers of the metal of the group IVA are prepared, so that the content of the metal of the group IVA in the carriers is 50 to 70% of the content of the metal of the group IVA in the catalyst; metal compounds of the group IVA and immersion liquid which comprises or does not contain lanthanide metal compounds are prepared; the carriers with the metal of the group IVA are dipped, and the immersion liquid contains monadic mineral acid of which the concentration is 2 to 15 wt% by using the carriers as the calculation reference; after immersion, drying and roasting are carried out; then, the immersion liquid containing the metal compounds of the group VIII is prepared, the carriers are dipped, and finally, the carriers are dried and roasted. The catalyst prepared by the method of the present invention has low content of carbon deposits and high activity and arene selectivity.

Description

A kind of platinum, tin are the preparation method of reforming catalyst
Technical field
The present invention is the preparation method for a kind of dual-function reforming catalyst, specifically, is that a kind of platinum, tin are the preparation method of reforming catalyst.
Background technology
Catalytic reforming is one of important production technique of refining of petroleum, and its main purpose is to produce stop bracket gasoline, broad-spectrum aromatic hydrocarbons and cheap hydrogen.Reforming reaction need have the dual-function catalyst of isomerization acid function and hydrogenation-dehydrogenation functionality.The acid function of catalyzer is generally provided by the acid inorganic oxide of porous such as alumina supporter and halogen, and hydrogenation-dehydrogenation functionality is then provided by VIII family metal constituent element, and other metal such as Sn or Re are usually used in improving the above-mentioned functions of catalyzer.
In catforming process, there are several competing reactions to take place simultaneously, these reactions comprise that cyclohexane dehydrogenation becomes aromatic hydrocarbons, alkyl cyclopentane dehydroisomerization to turn to aromatic hydrocarbons, the naphthenic hydrocarbon dehydrocyclization becomes aromatic hydrocarbons, paraffinic hydrocarbons hydrocracking to become the light hydrocarbon product outside the gasoline boiling range, the isomerization of taking off alkyl and paraffinic hydrocarbons of alkylbenzene.In above these reactions,, unfavorable for the yield of gasoline because hydrocracking produces light hydrocarbon gas; And the coking reaction can be accelerated the deactivation rate of catalyzer, and frequent catalyst regeneration can increase the running expense of device.Thereby the catalytic reforming catalyst and the technology of exploitation highly selective, low carbon distribution speed are the directions that people make great efforts always.
Preparation platinum, tin are that the reforming catalyst usual method is once to introduce required metal component in carrier, and the metal component of introducing also contains rare earth metal usually except that VIII family metal and IVA family metal.USP3,915,845 disclosed catalyzer comprise VIII family metal, IVA family metal, halogen and lanthanon, and wherein the atomic ratio of lanthanon and VIII family metal is 0.1～1.25: 1, and preferred lanthanon is Nd, La or Ce.
USP6,059,960 discloses the reforming catalyst of a kind of VIII of containing family metal, IVA family metal and lanthanide series metal, and lanthanide series metal wherein is Yb, Eu or Sm, and 50% lanthanide series metal exists with+divalent oxide form.
The disclosed multimetal reforming catalyst of EP0901814A1 contains VIII family metal, IVA family metal and Eu, and wherein 50% Eu exists with EuO, and the Eu/Pt atomic ratio is at least 1.3.
The multimetal reforming catalyst of the described platiniferous of CN1150169A, tin adopts stanniferous alumina supporter preparation, and the tin component is once introduced when preparing carriers.The multimetal reforming catalyst of the disclosed platiniferous of CN1384175A, tin also is to introduce IVA family metal earlier in the preparing carriers process, and then introduces Eu, Ce, VIII family metal and halogen by pickling process.When this catalyzer is used for catforming process, can increase the liquid yield of reformate, and reduce catalyst carbon deposition speed.
Summary of the invention
The purpose of this invention is to provide a kind of platinum, tin is the preparation method of reforming catalyst, the catalyst carbon deposition speed of this method preparation is low, activity stability good and selectivity is high.
Reforming catalyst provided by the invention comprises the high-temperature inorganic oxide carrier and is the following active ingredient of content of calculating benchmark with the carrier; 0.01 the VIII family metal of～5.0 quality %, the IVA family metal of 0.01～5.0 quality %, the lanthanide series metal of 0～10.0 quality % and the halogen of 0.1～10.0 quality %, this catalyzer prepares by the following method:
(1) preparation contains the high-temperature inorganic oxide carrier of IVA family metal, the content that makes IVA family metal in the carrier be in the catalyzer IVA family metal content 50～70%,
(2) the preparation steeping fluid that contains IVA family metallic compound and contain or do not contain lanthanide metal compound, the carrier of dipping (1) step preparation, containing in the steeping fluid with the carrier is that the concentration of calculating benchmark is the monobasic mineral acid of 2～15 quality %, dipping after drying, roasting,
(3) preparation contains the steeping fluid of VIII family metallic compound, the carrier of dipping (2) step preparation, dry then, roasting.
The inventive method preparation earlier contains the carrier of IVA family metal, in this carrier, introduce IVA family metal and other catalytic active component for the second time again by dipping method, the catalyzer carbon accumulation resisting ability that makes is once introduced the catalyzer that IVA family metal makes and is increased in carrier, thereby activity of such catalysts and selectivity all can keep higher level in the long time.
Embodiment
The present invention's preparation earlier contains the carrier of IVA family metal, and then in the carrier that contains IVA family metal, introduce for the second time a part of IVA family metal with pickling process, and then in carrier, introduce VIII family metal component and make catalyzer, preferable methods is before introducing IVA family metal for the second time, introduces the lanthanide series metal component afterwards or simultaneously and make the catalyzer that contains lanthanide series metal.In the steeping fluid of in the carrier that contains IVA family metal, introducing IVA family metal and the preparation of introducing lanthanide series metal for the second time, should contain an amount of monobasic mineral acid, so that described metal component is uniformly distributed in the carrier.
The material that normally a kind of porous of high-temperature inorganic oxide carrier described in the catalyzer of the present invention has adsorptivity, its specific surface area is 30～500 meters 2/ gram, preferred 100～500 meters 2/ gram, apparent bulk density is 0.4～1.0 grams per milliliter, mean pore size is that 20～300 , pore volume are 0.2～1 milliliter/gram.
The composition of porous carrier materials material should be uniformly, and is infusible under the condition of using.The meaning that term " is formed evenly " is meant that carrier is not stratified, does not have intrinsic component concentrations gradient.If carrier is the mixture of two or more refractory material, the relative quantity of these materials is constant or uniform on whole carrier so.High-temperature inorganic oxide of the present invention comprises:
(1) refractory inorganic oxide: aluminum oxide, magnesium oxide, chromic oxide, B 2O 3, TiO 2, ThO 2, ZnO 2, ZrO 2, silica-alumina, silicon oxide-magnesium oxide, chromic oxide-aluminum oxide, Al 2O 3-B 2O 3, SiO 2-ZrO 2
(2) various potteries, alumina, bauxite;
(3) SiO 2Or silica gel, silicon carbide, synthetic or naturally occurring various silicate and clay, these silicate and clay can with or without acid treatment;
(4) crystalline silico-alumino oxide compound: X-zeolite, Y-zeolite, mordenite, beta-zeolite, Ω-zeolite or L-zeolite, described zeolite can be Hydrogen or sodium type, preferred non-acid zeolite can have one or more basic metal to occupy cationic commutative position in non-acid type crystalline silico-alumino zeolite;
(5) non-zeolite molecular sieve, for example aluminophosphates or silicoaluminophosphates;
Preferred inorganic oxide is Al among the present invention 2O 3, its crystal habit can be γ-Al 2O 3, η-Al 2O 3Or θ-Al 2O 3, more preferably γ-Al 2O 3Or η-Al 2O 3, γ-Al most preferably 2O 3
Al 2O 3Carrier can be made into Any shape known to those of skill in the art or type, as ball-type, excellent type, ball, bead, sheet, granular, bar shaped etc.Preferred support shapes is a ball-type.Al 2O 3Ball type carrier can prepare with conventional oil ammonia column method, deep fat post method method.
VIII family metal is a main active component in the catalyzer of the present invention, comprises Pt, Pd, Ru, Rh, Ir, Os or their mixture, the preferred Pt of VIII family metal.VIII family metal can for example oxide compound, sulfide, halogenide, oxyhalogenation thing etc. exist with the form of compound in catalyzer, also can exist in chemically combined mode, can also exist with the metal simple-substance form with one or more other component in the catalyzer.Usually VIII family metal disperses in catalyzer equably, but the form that also can the centre concentration from the surface to the granules of catalyst decays is gradually disperseed.Preferred 0.05～2.0 quality % of VIII family metal content in the catalyzer.
Another main ingredient in the catalyzer of the present invention is an IVA family metal component, preferred Ge and Sn.Existence such as IVA family metal component can metal simple-substance, compound such as oxide compound, sulfide, halogenide, oxyhalogenation thing also can exist with other component in carrier, catalyzer combination with physics or chemistry.In finished catalyst, the most of preferred form with oxidation state of IVA family metal exists.IVA family metal content is in preferred 0.05～2.0 quality % of element, more preferably 0.1～2.0 quality % in the catalyzer.
Lanthanide series metal is a kind of preferred main ingredient of catalyzer of the present invention.Lanthanide series metal comprises La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tm, Dy, Ho, Er, Tm, Yb, Lu, the mixture of preferred europium, cerium or europium and cerium.Usually, the lanthanide series metal component can exist with form in catalyzer in any catalysis, as metal simple-substance, oxide compound, oxyhydroxide, halogenide, oxyhalogenation thing, aluminate, also can exist with chemically combined form with one or more other components of catalyzer.Preferred 0.05～2.0 quality % of the content of lanthanide series metal in the catalyzer, more preferably 0.2～2.0 quality %, when described lanthanide series metal was the mixture of europium and cerium, europium/cerium atom ratio was 0.1～10: 1, preferred 0.2～4.0: 1.The atomic ratio of lanthanide series metal and VIII family metal was at least preferred 0.1～20 0.01: 1 in the described catalyzer: 1, more preferably 0.2～5: 1, and lanthanide series metal comprises the mixture of single metal or two kinds of metals.
Also comprise halogen in the catalyzer of the present invention, preferred chlorine is so that catalyzer keeps certain acidity, preferred 0.5～5.0 quality % of content of halogen.
The inventive method (1) step can be introduced IVA family metal component with its precipitation, its gel or with the method for solid support material ion-exchange with porous carrier materials, preferably adopts cogelled method preparation to contain the carrier of IVA family metal.The gamma-aluminium oxide carrier of preferred preparation stanniferous or germanium, its preparation method is: in acidated aluminium hydrate powder, add urea, tin compound or germanium compound, kerosene and poly alkyl alcohol vinylchlorid ether, drip ball, drying, roasting then, add urea, kerosene and fatty alcohol-polyoxyethylene ether and aluminium hydrate powder ratio be respectively 20～40 quality %, 0～40 quality %, 2～6 quality %.
Used aluminium hydrate powder preferably adopts the high purity aluminium oxide that the aluminum alkoxide hydrolysis makes during preparation.Tin compound or germanium compound are selected the compound of the colloidal sol that can form solubility or dispersibility for use, as its muriate, oxide compound, oxyhydroxide or oxychlorination thing, wherein preferred tin protochloride of tin compound or tin tetrachloride, the preferred germanium dioxide of germanium compound, germanium tetrachloride or tetraethoxy germanium.
The inventive method (2) adopts pickling process to introduce IVA family metal component for the second time in the step, selectively also can introduce the lanthanide series metal component.The preferred method introducing IVA family's metal component and the lanthanide series metal component of dipping altogether of adopting, the steeping fluid that promptly is used for flooding contains solubility IVA family's metal component and lanthanide series metal.Also can adopt step impregnation method to prepare carrier, promptly be made into the carrier of steeping fluid dipping (1) step preparation earlier with IVA family metallic compound, and then, all carry out drying, roasting behind each dipping with the steeping fluid impregnated carrier that lanthanide metal compound is prepared.
The preferred tin of IVA family metallic compound that the preparation steeping fluid is used or the soluble compound of germanium, muriate, oxide compound or alkoxide as tin or germanium, as tin protobromide, tin protochloride, tin tetrachloride, tin tetrachloride pentahydrate, germanium dioxide, the tetrem alkoxide of germanium, germanium tetrachloride, preferred tin tetrachloride or germanium tetrachloride.
Be used to prepare nitrate, muriate, fluorochemical, Organoalkyl thing, oxyhydroxide or the oxide compound of the preferred lanthanide series metal of lanthanide metal compound of steeping fluid, the muriate of preferred europium and/or cerium is as Europium trichloride, cerous chlorate.
Above-mentioned each soaked carrier maturing temperature is 450～700 ℃, preferred 550～650 ℃, and in roasting process, preferably there is less water to exist, water suitable content in the roasting air or oxygen is 1～5 quality %.
Also contain a certain amount of monobasic mineral acid in described (2) step steeping fluid, example hydrochloric acid, nitric acid, oxalic acid, toxilic acid or citric acid, preferred hydrochloric acid.Preferred 3～10 quality % of amount that contain mineral acid in the steeping fluid.
(3) step of the inventive method is to introduce VIII family metal in carrier, and preferred VIII family metal is Pt, Ir, Pd or Rh.Preparation steeping fluid VIII family metal is its water-soluble cpds or title complex, as Platinic chloride, ammonium choroplatinate, bromoplatinic acid, tri-chlorination platinum, Tetrachloroplatinum hydrate, dichloride two chloroformyl platinum, dinitrobenzene diamino platinum tetranitro sodium platinate (II) (Sodium tetranitroplatinate (II)); The acid of chlorine palladium, 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, Trichlororhodium hydrate, rhodium nitrate, chlordene rhodium acid sodium (Sodium hexachlororhodate (III)), hexanitro-rhodium acid sodium (Sodium hexanitrorhodate (III)); Chloro-iridic acid, tribromide iridium, iridochloride, iridic chloride, hexanitro-iridium acid sodium (Sodium hexanitroridate (III)), potassium hexachloroiridate or sodium iridichloride, oxalic acid rhodium potassium.Preferred Platinic chloride, ammonium chloroplatinate, bromoplatinic acid, tri-chlorination platinum or Tetrachloroplatinum.For the introducing that further helps halogen with make each metal component uniform distribution on whole solid support material, steeping fluid should add HCl or nitric acid.
(3) after the carrier drying of step dipping VIII family metallic compound, preferably in the air or oxygen atmosphere, carry out water chlorine and handle the H when water chlorine is handled at 450～700 ℃ 2The O/HCl mol ratio is 1～200: 1, preferred 5～100: 1, and the time is 0.5～20 hour, preferred 0.5～8 hour.
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.
The catalyzer of the inventive method preparation need reduce before use, so that VIII family metal component is reduced into the metallic state of respective element, and guarantees to be evenly distributed on the whole inorganic oxide carrier.Reduction is carried out under substantially anhydrous condition, and the reducing gas of using is hydrogen or CO, and water should be less than 20ppm in the reducing gas.Reduction temperature is that 315～650 ℃, time are 0.5～10 hour.
The catalyzer of the inventive method preparation is suitable for catalytic reforming reaction.Reforming reaction pressure is 100KPa～7MPa, preferred 350KPa～2.5MPa; Temperature is 315～600 ℃, preferred 425～565 ℃; Hydrogen/hydrocarbon feed volume ratio 200～2000, preferred 500～1000; Volume space velocity is 0.1～10 hour during feeding liquid -1, preferred 1～5 hour -1
The preferred boiling range of raw material that is used for reforming reaction is 40～220 ℃ a full boiling range gasoline, as straight-run spirit, natural gasoline, synthetic gasoline etc., and also can admixture heat or the petroleum naphtha or the dehydrogenation petroleum naphtha of catalytically cracked gasoline cut.If the purpose of reforming is production benzene, toluene and dimethylbenzene one or more, the raw material boiling range of Shi Yonging is preferred 60～150 ℃ so.As required, the mixture that is rich in straight-chain paraffin that also can add pure hydrocarbon in the raw material or reclaim by extraction element, as raffinating oil or straight-chain paraffin that aromatic hydrocarbons extracts, this is also highly beneficial for producing aromatic hydrocarbons.
The catalyzer of the present invention's preparation preferably uses under no sulphur environment.Can use conventional method to handle the feed naphtha that adds the reforming reaction district.For example, raw material can be carried out adsorption treatment, catalytic treatment or handle with both cooperations.Adsorption treatment can adopt the SiO of molecular sieve, high surface area 2-Al 2O 3, the sulphur compound in the absorption raw materials such as crystal aluminosilicate, activated carbon.Catalysis treatment method generally adopts methods such as hydrofining, hydrotreatment, hydrogenating desulfurization to remove sulphur contained in the raw material, and makes alkene contained in the raw material saturated.
Below by example in detail the present invention, but the present invention is not limited to this.
Example 1
Preparation contains γ-Al of Sn 2O 3Carrier.
Method by example among the CN1150169A 1 prepares carrier, gets 100 gram SB aluminium hydrate powder (Germany, Condea company produces) and an amount of deionized waters, is 2.0 Gu make liquid/mass ratio, stirs and makes its pulp.The nitric acid that adds 1: 1 (volume ratio), its add-on is 7.5 milliliters/100 gram SB powder, the hydrochloric acid soln that adds the tin protochloride of 30 gram urea and predetermined amount simultaneously, the content of controlling Sn in the solution respectively is 0.30 quality %, 0.40 quality %, 0.50 quality % (serving as to calculate benchmark with the butt aluminum oxide all), stirred 1 hour, add 30 gram kerosene and 3 gram fatty alcohol-polyoxyethylene ether stirrings 1 hour then, in oil ammonia column, drip ball forming afterwards.Wet bulb solidified in ammoniacal liquor 1 hour, filters then, and with deionized water flushing 2～3 times, 60 ℃ of dryings 6 hours, 120 ℃ of dryings 10 hours, 600 ℃ of roastings 4 hours obtain containing γ-Al of Sn respectively 2O 3Carrier S A-1, SA-2 and SA-3, its Sn content are followed successively by 0.30 quality %, 0.41 quality %, 0.52 quality % (serving as to calculate benchmark with the butt aluminum oxide all).
Example 2
The spherical catalyst that contains Pt, Sn with the inventive method preparation.
(1) get 100 gram carrier S A-1, be made into the steeping fluid dipping 0.5 hour with tin protochloride and hydrochloric acid, Sn content is that 0.11 quality %, cl content are 10 quality % (are the calculating benchmark with the butt aluminum oxide) in the steeping fluid, Gu liquid/mass ratio is 1.8 during dipping.With the 60 ℃ of dryings of solid 6 hours behind the dipping, 120 ℃ of dryings 10 hours, 650 ℃ of roastings 4 hours in the air that contains 3 quality % water vapour then, carrier S A-4, its Sn content is 0.41 quality % (serves as to calculate benchmark with the butt aluminum oxide).
(2) with above-mentioned make contain Sn carrier S A-4, with the solution impregnation that Platinic chloride and hydrochloric acid are made into, Pt content is that 0.35 quality %, cl content are 1.4 quality % (serve as to calculate benchmark with the butt aluminum oxide) in the steeping fluid, Gu the liquid/mass ratio of dipping is 1.8.With the 60 ℃ of dryings of solid 6 hours behind the dipping, 120 ℃ of dryings 6 hours are at 510 ℃, H 2The O/HCl molecular ratio be under 60: 1 the condition in air activation treatment 6 hours, catalyst A, its composition sees Table 1, active component content is the content with respect to the butt aluminum oxide in the table 1.
Example 3
The spherical catalyst that contains Pt, Sn, Ce, Eu with the step impregnation method preparation.
(1) gets 100 gram carrier S A-4, be made into the steeping fluid dipping 12 hours with Europium trichloride, cerous chlorate and hydrochloric acid, Eu content is that 0.17 quality %, Ce content are that 0.10 quality %, cl content are 5.0 quality % (serving as to calculate benchmark with the butt aluminum oxide all) in the steeping fluid, Gu liquid/mass ratio is 1.6 during dipping.To flood back solid 60 ℃ of dryings 6 hours, 120 ℃ of dryings 10 hours, 600 ℃ of roastings are 4 hours in the air that contains 3 quality % water vapour, obtain containing the carrier of Sn, Eu and Ce.
(2) carrier that will contain Sn and Eu, Ce floods with containing Platinic chloride and hydrochloric acid soln by the method in 2 (2) steps of example, makes catalyzer C behind the water chlorine activation, and its composition sees Table 1.
Example 4
Contain the carrier of Sn by the method preparation in example 2 (1) step, Sn content is 0.22 quality % in the steeping fluid of preparation that different is, makes that tin content is 0.52 quality % among the carrier S A-5.
Get 100 gram carrier S A-5, in SA-5, introduces Eu and Ce makes the carrier that contains Sn, Eu and Ce by the method in example 3 (1) step, get this carrier, flood with containing Platinic chloride and hydrochloric acid soln by the method that example 2 (2) goes on foot, make catalyzer D behind the water chlorine activation, its composition sees Table 1.
Example 5
Adopt the co-impregnation preparation to contain the spherical catalyst of Pt, Sn, Ce, Eu.
Get the carrier S A-1 that 100 gram examples 1 make, steeping fluid with tin protochloride, Europium trichloride, cerous chlorate and hydrochloric acid preparation flooded 0.5 hour, Sn content is that 0.11 quality %, Eu content are that 0.17 quality %, Ce content are that 0.10 quality %, cl content are 5.0 quality % (serving as to calculate benchmark with the butt aluminum oxide all) in the steeping fluid, Gu the liquid/mass ratio during dipping is 1.8.To flood 60 ℃ of dryings of back solid 6 hours, 120 ℃ of dryings 10 hours, 650 ℃ of roastings 4 hours in the air that contains 2 quality % water vapour then obtain the Al of Sn content 0.41 quality %, Eu content 0.17 quality %, Ce content 0.10 quality % (serves as to calculate benchmark with the butt aluminum oxide) 2O 3Carrier.
Above-mentioned carrier is flooded with containing Platinic chloride and hydrochloric acid soln by the method in 2 (2) steps of example, make catalyzer E behind the water chlorine activation, its composition sees Table 1.
Example 6～9
Method by example 5 prepares catalyzer, contains the HCl of different concns in the steeping fluid of preparation that different is, HCl concentration (with respect to the butt aluminum oxide) and the catalyzer composition that makes see Table 1 in the steeping fluid that each example uses.
Comparative Examples 1
Get the carrier S A-2 that 100 grams contain Sn, flood with containing Platinic chloride and hydrochloric acid soln by the method in 2 (2) steps of example, make catalyzer X-2 behind the water chlorine activation, its composition sees Table 1.
Comparative Examples 2
Get 100 grams and contain the carrier S A-2 of Sn, prepare catalyzer X-5 by the method for example 3, its composition sees Table 1.
Comparative Examples 3
Get 100 grams and contain the carrier S A-3 of Sn, prepare catalyzer X-6 by the method for example 3, its composition sees Table 1.
Comparative Examples 4
Method by example 5 prepares catalyzer, and different is not contain HCl in the steeping fluid of preparing, and the composition of the catalyzer J that makes sees Table 1.
Example 10
This example is estimated catalyzer of the present invention and comparative catalyst's reactivity worth and activity stability.
The catalyzer of filling 28.0 grams in fixed-bed reactor, 500 ℃ are reduced with hydrogen.With boiling range is that 70～150 ℃ virgin naphtha is a raw material, and feedstock property sees Table 2.At 0.70MPa, 500 ℃, hydrogen/oil volume than 800: 1, feed volume air speed 2 hours -1Condition under react, evaluation result sees Table 3.
As shown in Table 3, catalyzer with the inventive method preparation, compare with comparative catalyst with same composition, under the situation that liquid is received, the virtue product is suitable substantially with the product octane value, carbon distribution comparison has reduced about 32% than catalyzer, show that the catalyzer of the inventive method preparation has activity stability preferably.
The reaction result of comparative catalyst J shows in the table 3, and when introducing active ingredient Sn, Eu, Ce in the stanniferous carrier, the not hydrochloric catalyzer that makes carbon distribution in reforming reaction obviously increases in the steeping fluid.
Table 1
Instance number The catalyzer numbering HCl concentration in the steeping fluid, quality % Catalyzer is formed, quality %
Pt Sn Eu Ce Cl
2 A 10 0.35 0.41 - - 1.16
3 C 5.0 0.35 0.41 0.17 0.10 1.18
4 D 5.0 0.35 0.52 0.17 0.10 1.18
5 E 10 0.35 0.41 0.17 0.10 1.20
6 F 10 0.35 0.41 0.17 0.10 1.16
7 G 5 0.35 0.41 0.17 0.10 1.18
8 H 3 0.35 0.41 0.17 0.10 1.20
9 I 2 0.35 0.41 0.17 0.10 1.22
Comparative Examples 1 X-2 0.35 0.41 - - 1.20
Comparative Examples 2 X-5 0.35 0.41 0.17 0.10 1.20
Comparative Examples 3 X-6 0.35 0.52 0.17 0.10 1.23
Comparative Examples 4 J 0 0.35 0.41 0.17 0.10 1.22
Table 2
Density (20 ℃), grams per milliliter Boiling range, ℃ initial boiling point/50%/final boiling point Form quality % paraffinic hydrocarbons/naphthenic hydrocarbon/aromatic hydrocarbons Arene underwater content, quality %
0.7274 86/109/151 55.70/41.38/2.92 41.59
Table 3
Catalyzer Liquid is received, quality % Virtue contains, quality % Virtue produces, quality % Research octane number (RON) Carbon distribution, quality %
A 85.27 80.16 68.35 102.7 3.3
C 84.46 79.99 67.55 102.1 3.0
D 84.01 79.61 66.88 101.8 2.9
E 84.38 79.92 67.43 102.1 3.0
F 84.49 79.65 67.29 3.3
G 84.97 79.07 67.17 3.2
H 84.74 79.27 67.16 3.3
I 84.69 79.12 67.00 3.7
X-2 85.35 79.92 68.21 102.5 4.7
X-5 84.30 79.91 67.36 102.0 4.5
X-6 83.32 79.09 65.89 100.9 4.4
J 83.50 77.84 64.99 4.5

Claims (10)

1, a kind of platinum, tin are the preparation method of reforming catalyst, and described catalyzer comprises the high-temperature inorganic oxide carrier and is the following active ingredient of content of calculating benchmark with the carrier; 0.01 the VIII family metal of～5.0 quality %, the IVA family metal of 0.01～5.0 quality %, the lanthanide series metal of 0～10.0 quality % and the halogen of 0.1～10.0 quality % is characterized in that this catalyzer prepares by the following method:
(1) preparation contains the high-temperature inorganic oxide carrier of IVA family metal, the content that makes IVA family metal in the carrier be in the catalyzer IVA family metal content 50～70%,
(2) the preparation steeping fluid that contains IVA family metallic compound and contain or do not contain lanthanide metal compound, the carrier of dipping (1) step preparation, containing in the steeping fluid with the carrier is that the concentration of calculating benchmark is the monobasic mineral acid of 2～15 quality %, dipping after drying, roasting,
(3) preparation contains the steeping fluid of VIII family metallic compound, the carrier of dipping (2) step preparation, dry then, roasting.
2, in accordance with the method for claim 1, it is characterized in that containing in the described catalyzer VIII family metal of 0.05～2.0 quality %, the IVA family metal of 0.05～2.0 quality %, the lanthanide series metal of 0.05～2.0 quality % and the halogen of 0.5～5.0 quality %.
3, according to claim 1 or 2 described methods, it is characterized in that described high-temperature inorganic oxide is an aluminum oxide, VIII family metal is selected from platinum, IVA family metal is selected from tin or germanium, halogen is selected from chlorine, described lanthanide series metal is selected from the mixture of europium, cerium or europium and cerium, and when described lanthanide series metal was the mixture of europium and cerium, europium/cerium atom ratio was 0.1～10: 1.
4,, it is characterized in that the high-temperature inorganic oxide of (1) step described IVA of containing family metal is the stanniferous of the cogelled method preparation of employing or the gama-alumina of germanium according to claim 1 or 2 described methods.
5, in accordance with the method for claim 4, the gama-alumina that it is characterized in that stanniferous or germanium adopts following method preparation: in acidated aluminium hydrate powder, add tin compound or germanium compound, urea, kerosene and fatty alcohol-polyoxyethylene ether, drip ball, drying, roasting then, add urea, kerosene and fatty alcohol-polyoxyethylene ether and aluminium hydrate powder ratio be respectively 20～40 quality %, 0～40 quality %, 2～6 quality %.
6, in accordance with the method for claim 5, it is characterized in that described tin compound is selected from tin protochloride or tin tetrachloride, germanium compound is selected from germanium dioxide, germanium tetrachloride or tetraethoxy germanium.
7, in accordance with the method for claim 1, it is characterized in that adopting step impregnation method to prepare carrier in (2) step, be made into the carrier of steeping fluid dipping (1) step preparation earlier with IVA family metallic compound, and then, all carry out drying, roasting behind each dipping with the steeping fluid impregnated carrier that lanthanide metal compound is prepared.
8, in accordance with the method for claim 1, it is characterized in that IVA family metallic compound is selected from the muriate of tin or germanium, lanthanide metal compound is selected from the muriate of europium and/or cerium, and VIII family metallic compound is selected from Platinic chloride, ammonium chloroplatinate, bromoplatinic acid, tri-chlorination platinum or Tetrachloroplatinum.
9, in accordance with the method for claim 1, the maturing temperature after it is characterized in that flooding is 450～700 ℃, and the monobasic mineral acid that contains in the described steeping fluid of (2) step is a hydrochloric acid.
10, in accordance with the method for claim 1, it is characterized in that the carrier drying of (3) step dipping VIII family metallic compound after, described roasting is to carry out water chlorine at 450～700 ℃ in the air or oxygen atmosphere to handle the H when water chlorine is handled 2The O/HCl molecular ratio is 5～100: 1, and the time is 0.5～20 hour.
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CN101850997B (en) * 2009-03-31 2012-07-18 中国石油化工股份有限公司 Method for preparing spherical alumina
FR2947465B1 (en) * 2009-07-01 2012-05-11 Inst Francais Du Petrole MULTI-METALLIC CATALYST WITH OPTIMIZED SITE PROXIMITY
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CN104511291B (en) * 2013-09-27 2017-07-14 中国石油天然气股份有限公司 Large-aperture high-bulk-density continuous reforming catalyst and preparation and application thereof
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CN109201051B (en) * 2017-07-05 2021-08-06 中国石油化工股份有限公司 Preparation method of multi-metal continuous reforming catalyst
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FR3074063B1 (en) * 2017-11-30 2019-11-01 IFP Energies Nouvelles MULTI-METALLIC CATALYST DOPED BY PHOSPHORUS AND YTTERBIUM
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6153090A (en) * 1997-10-31 2000-11-28 Institut Francais Du Petrole Catalytic hydroreforming process
CN1393514A (en) * 2001-06-29 2003-01-29 中国石油化工股份有限公司 Dual-function reforming catalyst containing Pt and Sn and its preparing process

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6153090A (en) * 1997-10-31 2000-11-28 Institut Francais Du Petrole Catalytic hydroreforming process
CN1393514A (en) * 2001-06-29 2003-01-29 中国石油化工股份有限公司 Dual-function reforming catalyst containing Pt and Sn and its preparing process

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