CN101444732A - C9 aromatic hydrocarbon lightening catalyst and lightening method thereof - Google Patents
C9 aromatic hydrocarbon lightening catalyst and lightening method thereof Download PDFInfo
- Publication number
- CN101444732A CN101444732A CNA2007101782311A CN200710178231A CN101444732A CN 101444732 A CN101444732 A CN 101444732A CN A2007101782311 A CNA2007101782311 A CN A2007101782311A CN 200710178231 A CN200710178231 A CN 200710178231A CN 101444732 A CN101444732 A CN 101444732A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- quality
- carrier
- aromatic hydrocarbons
- metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
Abstract
The invention relates to a C9<+> aromatic hydrocarbon lightening catalyst, comprising a high-temperature-resistant inorganic oxide carrier and the following components accounted by taking the dry basis carrier as benchmark: 0.01-10.0 weight percent of hydrogenation metal, 0.01-1.0 weight percent of IVA-group metal and 0.1-5.0 weight percent of halogen; wherein, the hydrogenation metal is selected from iron, cobalt, nickel and iridium. The catalyst is used for lightening C9<+> heavy aromatic hydrocarbon. The catalyst has high lightening transformation ratio, high aromatic hydrocarbon yield and less carbon deposition; and the catalyst can effectively lower final boiling point and gum level of the heavy aromatic hydrocarbon.
Description
Technical field
The present invention is a kind of C
9 +Arenes lightening catalyst, its preparation method and lightening method specifically, are a kind ofly to contain bimetallic heavy arenes lightening catalyst, its preparation method and use this catalyst to carry out the method for heavy aromatic hydrocarbon light.
Background technology
Heavy arene is meant that generally catalytic reforming, disproportionation and isomerization reaction generate contained C in oil and the cracking of ethylene hydrogasoline
9～C
16List or bicyclic alkyl aromatic hydrocarbons.For a long time, the heavy arene resource does not obtain rationally, utilizes fully, removes to be used as solvent on a small quantity and to extract C
9, C
10Outside the monomer aromatic hydrocarbons, generally all directly mix gasoline pool and act as a fuel.But no matter from the angle of economy and environmental protection, it all is worthless that heavy arene is directly acted as a fuel.On the one hand, heavy arene can be converted into benzene, toluene and dimethylbenzene light aromatics such as (BTX); On the other hand, from environmental angle, there has been report to think in recent years and can have alleviated the pollution that vehicle exhaust causes, and thought that 90% of gasoline distillates point (T by reducing doing of gasoline
90) should be lower than or between 132 ℃～177 ℃.Therefore, heavy arene further is converted into light aromatics, from economy still be the environmental protection aspect all be favourable.
The main method of heavy aromatic hydrocarbon light is pyrolysismethod and catalytic dealkylation method at present, and the main deficiency of prior art is reaction temperature and pressure height, and air speed is low, and the commercial Application of technology is restricted.
The key reaction that heavy arenes catalytic dealkylation carries out lighting is the hydro-dealkylation reaction, and generally speaking, the aromatic hydrocarbons side chain is long more, sloughs side chain in the hydro-dealkylation reaction easily more.Thereby contained ethyl methyl benzene, diethylbenzene or dimethyl ethyl benzene in the heavy arene, n-proplbenzene, isopropylbenzene, more or less freely reacting such as methyl-propyl benzene generate benzene,toluene,xylene etc.
USP4,341,622 disclose a kind of method of utilizing the heavy reformate to produce BTX.The zeolite that this method adopts that restricted index is 1～12, silica (silica alumina ratio) is 12 or more, hang down acid activity is a catalyst, the heavy reformate is reacted under 427～540 ℃ condition, again the product separated is obtained benzene, toluene and dimethylbenzene.Contain VIII family noble metal in the described catalyst with hydro-dealkylation activity, preferred platinum, the silica alumina ratio of used zeolite is preferably greater than 200, and more preferably greater than 500, preferred zeolite is ZSM-5.The purpose of selecting the high silica alumina ratio zeolite is to reduce the acidity of zeolite, so that dimethylbenzene is not converted into other material in course of reaction.
USP5,001,296 discloses a kind of method of arenes catalytic hydro-dealkylation.The catalyst that this method is used comprises metal component and the MCM-22 zeolite that is selected from noble metal, nickel or their mixture.This catalyst can be with C
6-C
12Mononuclear aromatics takes off alkyl greater than the raw material of 50mol% and changes into light components.Described MCM-22 zeolite has advantages such as Heat stability is good and specific area be big, the MCM-22 zeolite that consists of 65wt% of its preparation, the Al of 35wt%
2O
3With the catalyst of 0.66wt% platinum, can be at 200psig, liquid hourly space velocity (LHSV) 2.5, hydrogen cycle rate 2000 gauges
3/ barrel, temperature are under 315～482 ℃ the reaction condition, with C
9 +Arene content is that the feedstock conversion of 96.8mol% is BTX.Its reactivity is with C
9 +Conversion ratio is calculated as 21.0～82.0mol%, and the BTX selectivity reaches 63.8～79.8mol%.
USP5,990,031 disclose a kind of method that zeolite takes off the alkyl activity that strengthens.This method is earlier with zeolite, preferred modenite carries out twice ammonium exchange to be handled, and then with the solution-treated zeolite that contains villiaumite, carries out ion-exchange and introduces fluorine, again with the binding agent mixed-forming after roasting obtain the zeolite of modification, introduce nickel again in the modified zeolite after moulding and make catalyst.This catalyst is used for transalkylation process tail oil and heavy reformate and has the higher alkyl activity of taking off, and shows the good selectivity to benzene and monoalkyl aromatic hydrocarbons simultaneously.
CN1048425C discloses a kind of heavy arenes lightening catalyst and lightening method.This catalyst is with the γ of the ZSM-5 zeolite of 30～70 heavy % and 30～70 heavy %-or η-Al
2O
3Be carrier, the palladium of the platinum of the rhenium of load 0.1～0.5 heavy %, the tin of 0.1～0.5 heavy % and 0.05～0.3 heavy % or 0.2～0.8 heavy % is formed.At 350～450 ℃, 0.5～3.5MPa, weight space velocity 1～5 o'clock
-1, hydrogen/hydrocarbon volume ratio is under 500～1200 the condition, this catalyst has higher activity and activity stability and lower hydrogen consumption.
CN1082539C discloses the separation method of a kind of heavy arenes lightening catalyst and lighting product.Described catalyst is made up of platinum or palladium, the zeolite with MOR structure of 20～59 heavy %, the ZSM-5 zeolite of 20～50 heavy % and the aluminium oxide of 20～40 heavy % of 0.05～0.3 heavy %.To contain C
9 +The raw material of heavy arene under 350～450 ℃, 0.5～3.5MPa condition, contact with above-mentioned catalyst, gained lighting product can obtain Organic Ingredients such as BTX and mesitylene, pseudocumene, durol through fractionation.
CN1472181A discloses a kind of heavy arenes lightening catalyst, this catalyst comprises platinum or palladium and the complex carrier of 0.01～2.0 heavy %, and described complex carrier contains the ZSM-5 zeolite of 30～70 heavy %, the modenite of 5～20 heavy % and the aluminium oxide of 10～65 heavy %.CN1472182A discloses a kind of similar catalyst, just contains the ZSM-5 zeolite of 30～70 heavy %, the β zeolite of 5～30 heavy % and the aluminium oxide of 10～65 heavy % in the complex carrier.The above-mentioned catalyst of complex carrier that contains is compared with the catalyst that the carrier that only contains ZSM-5 zeolite and aluminium oxide makes, and is used for heavy aromatics lighting reaction, can not only improve C
9 +The conversion ratio of aromatic hydrocarbons can also improve the productive rate of benzene and dimethylbenzene simultaneously, and have stronger anti-carbon deposition ability.
CN200580009162 discloses the method that a kind of polycyclic aromatic hydrocarbon is catalytically conveted to dimethylbenzene, the used catalyst carrier of this method is selected from modenite, mazzite, β zeolite, ZSM-11, ZSM-12, ZSM-22, ZSM-23, MFI and topological zeolite, NES topology zeolite, EU-1, MAPO-36, MAPSO-31, SAPO-11, SAPO-41 and silica-alumina and their mixture, and metal component is selected from platinum, palladium, nickel, tin, lead, iridium, germanium, rhenium or their combination.This catalyst can be used for handling the feed stream that contains high boiling substance, also can to a certain degree reduce the final boiling point (ASTM D2887 simulation distil gas chromatography determination) of the 99.5wt% of feed stream when generating dimethylbenzene.
Summary of the invention
The purpose of this invention is to provide a kind of C
9 +The catalyst of arene light formation and preparation method, this catalyst has higher activity and light aromatics productive rate.
Another object of the present invention provides uses above-mentioned catalyst to C
9 +Aromatic hydrocarbons carries out the method for lighting.
C provided by the invention
9 +Arenes lightening catalyst comprises the high-temperature inorganic oxide carrier and is the following component of content that benchmark calculates with the butt carrier:
Hydrogenation metal 0.01～10.0 quality %
IVA family metal 0.01～1.0 quality %
Halogen 0.1～5.0 quality %
Described hydrogenation metal chosen from Fe, cobalt, chromium, nickel or iridium.
Do not contain molecular sieve in the catalyst carrier provided by the invention, and use second metal component of hydrogenation metal component and modification, make catalyst C
9 +Aromatic hydrocarbons activity of conversion height, hydrogenation open loop side reaction is few, and the aromatic ring loss is little, xylene content height in the BTX product, catalyst carbon deposition speed is low.Catalyst of the present invention is with C
9 +When aromatic hydrocarbons is converted into BTX, can also significantly reduce the gum level in the raw material, thereby reduce the final boiling point (by the final boiling point of the 99.5wt% of ASTM D2887 simulation distil gas chromatography determination) of raw material to a certain extent.
The specific embodiment
Using high-temperature inorganic oxide to be carrier in the catalyst of the present invention, is active metal component with hydrogenation metal and IVA family metal.With the catalyst that contains molecular sieve and the high-temperature inorganic oxide that only uses a kind of hydrogenation activity component as the catalyst of carrier relatively, catalyst of the present invention has higher C in the heavy aromatic hydrocarbon light reaction
9 +Heavy aromatics conversion ratio and benzene, toluene and dimethylbenzene yield, aromatic hydrogenation open loop side reaction is few, the arenes selectivity height, and the coke deposit rate on the catalyst is lower in the course of reaction.
Preferred each constituent content of catalyst of the present invention is as follows:
Hydrogenation metal 0.1～5.0 quality %
IVA family metal 0.05～0.5 quality %
Halogen 0.1～3.0 quality %
More preferably 0.1～2.5 quality % of hydrogenation metal constituent element content in the described catalyst, IVA family tenor is 0.1～0.3 quality % more preferably, and content of halogen is 0.1～2.0 quality % more preferably.The preferred iridium of described hydrogenation metal, chromium or nickel, preferred tin of IVA family metal or lead, the preferred chlorine of halogen.
High-temperature inorganic oxide carrier of the present invention should have uniform composition and have suitable refractoriness under the service condition of hydrocarbon conversion process." form uniformly " and refer to that high-temperature inorganic oxide is that intrinsic component not stratified, its composition does not have concentration gradient and complete uniformity on forming.Therefore, if carrier is the mixture by two or more refractory materials, then the relative amount of these materials will be a steady state value and be uniformly distributed in whole carrier.High-temperature inorganic oxide is selected from aluminium oxide, titanium dioxide, zirconium dioxide, chromium oxide, zinc oxide, magnesia, thorium oxide, boron oxide, silica-alumina, aluminium oxide-boron oxide or silica-zirconia, preferred aluminium oxide.The crystalline phase of described aluminium oxide can be γ, η or θ, preferred γ phase
Described carrier can be any required shape, as sphere, sheet, ingot shape, bar shaped, powder, graininess etc., and preferred sphere or bar shaped.
Catalyst provided by the invention can be used immersion process for preparing, and the method for dipping can adopt step impregnation or common dipping, preferred step impregnation method.
The method that described branch dipping prepare catalyst comprises that with containing IVA family solution of metal compound be high-temperature inorganic oxide behind the maceration extract dip forming, again with hydrogenation metal compound solution dipping, carries out the processing of water chlorine activation after the drying after drying, the roasting.Liquid/solid volume during dipping is than preferred 1.0～3.0:1, preferred 20～40 ℃ of dipping temperature.Filter or the rotation evaporate to dryness dipping back, the gained solid is dry back in 400～600 ℃ in 100～200 ℃, be that blowing air was handled 1～20 hour under the condition of 500～2000:1 in gas/agent volume ratio, preferred 2～8 hours, the gained solid floods the hydrogenation metal constituent element again, solid is carried out the water chlorine activation handle after 100～200 ℃ of dryings.
The method that described altogether dipping prepare catalyst comprises that with the solution that contains IVA family metallic compound and hydrogenation metal compound be high-temperature inorganic oxide behind the maceration extract dip forming, carries out the water chlorine activation after the drying and handles.Liquid/solid volume during dipping is than preferred 1.0～3.0:1, preferred 20～40 ℃ of dipping temperature.Filter the dipping back, solid is carried out the water chlorine activation handle after 100～200 ℃ of dryings.
Chloracid, nitrate, sulfate or the phosphate of the described chloride that is used to prepare the preferred hydrogenation metal of compound that contains hydrogenation metal of maceration extract, oxide, oxychlorination thing, described metal.Preferred chloride, nitrate and contain the acid of described metal and chlorine.Chloride, nitrate or its chloracid of preferred iridium, chromium or nickel are as chloro-iridic acid.
The described compound that contains IVA family metal can be oxide, sulfide, halide, oxyhalogenation thing, sulfate, nitrate or the phosphate of described metal.Preferred germanium, tin or plumbous halide, nitrate, sulfate or phosphate.
In the described dipping process, in carrier, evenly disperse, preferably in maceration extract, add halide for making metal active constituent.The preferred hydrochloric acid of halide is so that Cl wherein
-With the absorption of competing of hydrogenation metal ion.
Halogen in the catalyst of the present invention can be introduced in catalyst preparation process, also can introduce in the catalyst use, as introducing catalyst by the mode of introducing halogen compounds in reaction raw materials.Preferred mode be the form of or organohalogen compounds inorganic with hydrochloric acid or other when dipping and the metal constituent element together introduce.
The moulding of described high-temperature inorganic oxide can be adopted conventional extruded moulding or drip the ball forming method.
The method of extruded moulding is with the high-temperature inorganic oxide of powdery or its precursor adds suitable quantity of water and peptizing agent is mixed pinches, and described peptizing agent is generally acid.Pinch even back gains extrusion, drying, roasting and promptly get the carrier of moulding mixing.
The method of dripping ball forming is: high-temperature inorganic oxide or its precursor of powdery are added suitable quantity of water, are 1.0～3.0 Gu make liquid/mass ratio.Stirring makes its pulp, adds acid then and carries out acidifying, adds when adding acid to account for high-temperature inorganic oxide or the urea of its precursor 20～40 quality % and an amount of hydrochloric acid, stirs 1 hour.The dosage of described hydrochloric acid is 0.5～9.5 quality % of high-temperature inorganic oxide.Optionally adding the kerosene that accounts for high-temperature inorganic oxide or its precursor 10～40 quality % then continues to stir 0.5～5.0 hour.Slurries are splashed into oil ammonia column make bead, wet bulb is 60～80 ℃ of dryings, preferred 2～12 hours of time, and again 120～130 ℃ of dryings, preferred 4～24 hours of time.With carrier after the drying in dry air in 450～750 ℃ of roastings, preferred 4～10 hours of roasting time, the gas the during roasting/preferred 700～1000:1 of agent volume ratio.
Peptizing agent described in the above-mentioned forming method or be used for the preferred nitric acid of acid, hydrochloric acid, acetate or the citric acid of acidifying slurries.The consumption of peptizing agent is preferably 0.5～6.0 quality % of high-temperature inorganic oxide or its precursor, and the sour consumption of acidifying slurries is counted 4～10 milliliters acid solution with per 100 gram acidifying raw materials.Preferred 1.0～6.0 volume % of the concentration of described peptizing agent or the used acid of acidifying slurries.
It is the process that dried catalyst is at high temperature handled with the water vapour that contains HCl that described water chlorine activation is handled.Preferred 450～700 ℃ of water chlorine activation temperature described in the inventive method, the H that feeds during activation
2Preferred 3～the 100:1 of the mol ratio of O and HCl, more preferably 5～40:1, preferred 2～200 hours of water chlorine activation time, more preferably 4～150 hours.
Catalyst after water chlorine handled reduces with reducibility gas and promptly obtains reduction catalyst.Described reducibility gas is selected from hydrogen or carbon monoxide, preferred hydrogen.Suitable reduction temperature is 250～600 ℃, H during reduction
2/ catalyst volume ratio is 150～2500:1, preferred 2～24 hours of recovery time.
Use catalyst of the present invention with C
9 +Aromatic hydrocarbons is converted into the method for light aromatics, comprises C
9 +Aromatic hydrocarbons and catalyst of the present invention in the presence of hydrogen, at 380～600 ℃, preferred 380～550 ℃, haptoreaction under the condition of 0.1～5.0MPa, preferred 0.5～2.5MPa.
Described C
9 +The liquid volume air speed that aromatic hydrocarbons contacts with catalyst is 1～100 hour
-1, preferred 1～15 hour
-1, hydrogen/hydrocarbon mol ratio is 0.1～20.0:1, preferred 0.1～15:1.
C of the present invention
9 +The heavy virtue gently can be naphtha catalytic reforming product liquid gained after separating, and also can be the heavy aromatics that cracking of ethylene technology produces, and can also be the heavy aromatics that other technology produces, wherein C9
+Arene content is not less than 70 quality %, preferably is not less than 85 quality %.Particularly, C9 of the present invention
+The C that contains 0.1～5.0 quality % during virtue is light
8Aromatic hydrocarbons, the C of 2.0～88 quality %
9Aromatic hydrocarbons, the C of 10～75 quality %
10Aromatic hydrocarbons, the C of 1.0～30 quality %
11 +Aromatic hydrocarbons, wherein gum level is not less than 20mg/100ml.Quantity of distillate by ASTM D2887 simulation distil gas chromatography determination is the boiling point of 99.5 quality %, and promptly final boiling point is not less than 280 ℃, preferably is not less than 320 ℃.
Below by example in detail the present invention, but the present invention is not limited to this.
Example 1
Prepare Ir-Sn bimetallic catalyst of the present invention.
(1) preparation gamma-aluminium oxide carrier.
Get the deionized water that 135 gram aluminium hydrate powders (condea company produces, trade mark SB) add 200 grams, stir and make its pulp.Adding volume ratios by the amounts of 7.5 milliliters in per 100 gram SB powder is the nitric acid of 1:1, adds 30 gram urea simultaneously and 10.0 gram concentration are the hydrochloric acid solution of 36.5 quality %, stirs 1 hour, adds 30 gram kerosene again and stirs a ball forming in oil ammonia column 1 hour.Wet bulb is to solidify 1 hour in the ammoniacal liquor of 6.0 quality % in concentration, filters then, spends deionised water 2～3 times, 60 ℃ of dryings 6 hours, 120 ℃ of dryings 10 hours, then in dry air with gas/solid volume of 700/1 than in 600 ℃ of roastings 4 hours, obtain gamma-aluminium oxide carrier.
(2) preparation catalyst
Get above-mentioned gamma-aluminium oxide carrier 100 grams, use SnCl
2With the mixed solution dipping of hydrochloric acid preparation, contain Sn 0.2 quality %, HCl 8.0 quality % (being that benchmark calculates all, down together) in the maceration extract with the butt gama-alumina, add deionized water, making liquid/solid volume ratio is 1.4.25 ℃ of dippings filtered after 24 hours, 120 ℃ of dryings 12 hours, and 500 ℃ is that blowing air was handled 4 hours under the condition of 1000:1 in gas/agent volume ratio, makes the aluminium oxide that contains Sn.
The mixed solution that the aluminium oxide of the above-mentioned Sn of containing is prepared with chloro-iridic acid and hydrochloric acid is the maceration extract dipping, contains Ir 2.4 quality %, HCl 1.0 quality % in the maceration extract, adds deionized water, and making liquid/solid volume ratio is 1.6.25 ℃ of dippings filtered after 24 hours, and 120 ℃ of dryings 12 hours are again in 550 ℃, H
2The O/HCl mol ratio is a water chlorine activation 6 hours under 20 the condition, 350 ℃, H
2/ catalyst volume obtains catalyst A than for using hydrogen reducing 4 hours under the condition of 250:1, and it is that each constituent content that benchmark calculates sees Table 1 with the butt gamma-aluminium oxide carrier.
Example 2
Method by example 1 prepares catalyst, and different is to contain Sn 0.1 quality % in the used maceration extract of dipping gamma-aluminium oxide carrier, and the active component content of the catalyst B that makes sees Table 1.
Example 3
Method by example 1 prepares catalyst, contains Ir 1.8 quality % in the used maceration extract of the aluminium oxide of different is dipping contains Sn, and the active component content of the catalyst C that makes sees Table 1.
Example 4
Method by example 1 prepares catalyst, contains Ir 1.2 quality % in the used maceration extract of the aluminium oxide of different is dipping contains Sn, and the active component content of the catalyst D that makes sees Table 1.
Example 5
Method by example 1 prepares catalyst, contains Ir 0.6 quality % in the used maceration extract of the aluminium oxide of different is dipping contains Sn, and the active component content of the catalyst E that makes sees Table 1.
Example 6
Method by example 1 prepares catalyst, contains Sn 0.1 quality % in the used maceration extract of different is dipping gamma-aluminium oxide carrier, and dipping contains in the used maceration extract of the aluminium oxide of Sn and contains Ir 1.8 quality %, and the active component content of the catalyst F that makes sees Table 1.
Example 7
Method by example 1 prepares catalyst, contains Sn 0.1 quality % in the used maceration extract of different is dipping gamma-aluminium oxide carrier, and dipping contains in the used maceration extract of the aluminium oxide of Sn and contains Ir 1.2 quality %, and the active component content of the catalyst G that makes sees Table 1.
Example 8
Method by example 1 prepares catalyst, contains Sn 0.1 quality % in the used maceration extract of different is dipping gamma-aluminium oxide carrier, and dipping contains in the used maceration extract of the aluminium oxide of Sn and contains Ir 0.6 quality %, and the active component content of the catalyst H that makes sees Table 1.
Example 9
Prepare Ir-Ge bimetallic catalyst of the present invention.
Get the gamma-aluminium oxide carrier of 100 grams, use GeO by the preparation of example 1 (1) one step process
2With chloro-iridic acid and hydrochloric acid liquid mixture prepared dipping, contain Ge 0.1 quality % in the maceration extract, contain Ir 1.8 quality %, HCl 2.0 quality %, add deionized water, making liquid/solid volume ratio is 1.4.25 ℃ of dippings filtered after 24 hours, and 120 ℃ of dryings 12 hours are again in 550 ℃, H
2The O/HCl mol ratio is a water chlorine activation 6 hours under 20 the condition, 350 ℃, H
2/ catalyst volume obtains catalyst I than using hydrogen reducing 4 hours under the condition of 250:1, and it is that each constituent content that benchmark calculates sees Table 1 with the butt gamma-aluminium oxide carrier.
Example 10
Method by example 9 prepares catalyst, and different is to contain Ge 0.05 quality % in the maceration extract, and the active component content of the catalyst J that makes sees Table 1.
Example 11
Method by example 9 prepares catalyst, and different is to contain Ir 1.2 quality % in the maceration extract, and the active component content of the catalyst K that makes sees Table 1.
Example 12
Method by example 9 prepares catalyst, and different is to contain Ir 1.2 quality %, Ge 0.05 quality % in the maceration extract, and the active component content of the catalyst L that makes sees Table 1.
Example 13
Prepare Ir-Pb bimetallic catalyst of the present invention.
Get the gamma-aluminium oxide carrier of 100 grams, with Pb (NO by the preparation of example 1 (1) one step process
3)
2, the preparation of chloro-iridic acid and hydrochloric acid the mixed solution dipping, contain Pb 0.05 quality % in the maceration extract, contain Ir 1.8 quality %, HCl 2.0 quality %, add deionized water, making liquid/solid volume ratio is 1.4,25 ℃ of dippings filtered after 24 hours, and 120 ℃ of dryings 12 hours are again in 550 ℃, H
2The O/HCl mol ratio is a water chlorine activation 6 hours under 20 the condition, 350 ℃, H
2/ catalyst volume obtains catalyst M than using hydrogen reducing 4 hours under the condition of 250:1, and it is that each constituent content that benchmark calculates sees Table 1 with the butt gamma-aluminium oxide carrier.
Example 14
Method by example 13 prepares catalyst, and different is to contain Ir 1.2 quality % during maceration extract is, the active component content of the catalyst n that makes sees Table 1.
Comparative Examples 1
The preparation active component is the catalyst of iridium.
Get gamma-aluminium oxide carrier 100 grams by the preparation of example 1 (1) one step process, mixed solution with chloro-iridic acid and hydrochloric acid preparation is the maceration extract dipping, contain Ir 1.5 quality %, HCl 1.0 quality % (being that benchmark calculates all) in the maceration extract with the butt gamma-aluminium oxide carrier, add deionized water, making liquid/solid volume ratio is 1.6.25 ℃ of dippings filtered after 24 hours, and 120 ℃ of dryings 12 hours are again in 550 ℃, H
2The O/HCl mol ratio is a water chlorine activation 6 hours under 20 the condition, 350 ℃, H
2Use hydrogen reducing 4 hours under the condition of/agent volume ratio 250:1, obtain comparative catalyst O, it is that each constituent content that benchmark calculates sees Table 1 with the butt gamma-aluminium oxide carrier.
Comparative Examples 2
Method by Comparative Examples 1 prepares catalyst, and different is to contain Ir 1.8 quality % in the maceration extract, and the active component content of the catalyst P that makes sees Table 1.
Comparative Examples 3
Method by Comparative Examples 1 prepares catalyst, and different is to contain Ir 1.2 quality % in the maceration extract, and the active component content of the catalyst Q that makes sees Table 1.
Comparative Examples 4
Method by Comparative Examples 1 prepares catalyst, and different is to contain Ir 0.6 quality % in the maceration extract, and the active component content of the catalyst R that makes sees Table 1.
Table 1
Example 15～28
Following example is estimated catalyst of the present invention and comparative catalyst's reactivity worth.
Two sections filling 20ml catalyst in continuous fixed bed reactor, each 10ml of last hypomere is with the C of reformation, disproportionation, isomerization by-product
9 +Aromatic hydrocarbons is raw material, and the raw material composition sees Table 2.500 ℃, 1.0MPa, liquid volume air speed 3 hours
-1, hydrogen/hydrocarbon mol ratio is to react under the condition of 5:1, wherein the reaction result of Ir-Sn catalyst sees Table 3, the reaction result of Ir-Ge (Pb) catalyst sees Table 4, wherein:
C
9 +Aromatics conversion rate=[1-(C in the product liquid
9 +Aromatic hydrocarbons mass percent * liquid is received)/feedstock oil in C
9 +The aromatic hydrocarbons mass percent] * 100%;
The light arenes selectivity=(C that light aromatic hydrocarbons molal quantity * liquid receipts/generation transforms in the liquid product
9 +The aromatic hydrocarbons molal quantity) * 100%.
Table 2
Table 3
Annotate: the triphen summation is the summation of benzene, toluene and dimethylbenzene (BTX)
Table 4
Comparative Examples 5
Preparing metal component by the method for CN1048425C is Pt-Re-Sn and the catalyst that contains ZSM-5.
The gamma oxidation aluminium powder that accounts for carrier quality 40% is at room temperature used scheduled volume SnCl
2Solution (Sn content account for butt carrier quality 0.35%) dipping 15 hours, liquid/solid volume the ratio of dipping is 2, behind the dipping with liquid in 110～120 ℃ of evaporates to dryness, the silica that adds carrier quality 60% is 120 ZSM-5, mix, adding accounts for powder quality 40%, concentration is mixed the pinching of aqueous solution of nitric acid of 2.0 quality %, extruded moulding, 110～120 ℃ of dryings 12 hours, 550 ℃ of roastings 4 hours, make the carrier that contains 40 quality % gama-aluminas and 60 quality %ZSM-5, each amounts of components sees Table 5 during the preparation carrier.
Get the above-mentioned carrier of 10 grams, at 90 ± 10 ℃ of NH that use 0.5N down
4Cl solution 20ml carried out ion-exchange 2 hours to carrier, filtered, washed 110～120 ℃ of dryings.At 25 ℃, liquid/solid volume than being under 2 the condition with containing chloroplatinic acid and perrhenic acid solution impregnation, the Re that makes the Pt, the 0.40 quality % that contain 0.20 quality % in the maceration extract is (all with respect to carrier, down together), dipping back solid was in 110～120 ℃ of dryings 12 hours, roasting is 4 hours in 500 ℃ of air, 500 ℃ of hydrogen reducings obtained catalyst S in 6 hours, and its metal component content with respect to carrier sees Table 5.
Comparative Examples 6
To prepare metal component be Pt and contain ZSM-5 and the catalyst of modenite complex carrier by the method for CN1472181A.
With an amount of silica is that to be 27 sodium type modenite mix with HP aluminium hydrate powder by the described method preparation of CN85100218 for 60 sodium type ZSM-5 zeolite, silica, add powder weight 40%, concentration be the aqueous solution of nitric acid of 2 quality % mix pinch, extruded moulding, 110～120 ℃ of dryings 2 hours, 550 ℃ of roastings obtained complex carrier in 4 hours in the air.Contain the ZSM-5 zeolite of 40 quality %, the modenite of 20 quality % and the gama-alumina of 40 quality % in the carrier, each amounts of components sees Table 5 during the preparation carrier.
Get the above-mentioned carrier of 10 grams, at 90 ± 10 ℃ of NH that use 0.5N down
4Cl solution 20ml carried out ion-exchange 2 hours to carrier, filtered, washed to there not being Cl
-
With the concentration of scheduled volume be the platinum acid chloride solution of 7.0mg/ml at 25 ℃, liquid/solid volume than being the carrier after the above-mentioned ammonium ion exchange of dipping 24 hours under 2 the condition, filter, 110～120 ℃ of dryings 2 hours, 550 ℃ of roastings are 4 hours in the air, 500 ℃ of hydrogen reducings obtained catalyst T in 6 hours, and Pt content sees Table 5 among the catalyst T.
Comparative Examples 7
To prepare metal component be Pt and contain ZSM-5 and the catalyst of β zeolite complex carrier by the method for CN1472182A.
With an amount of silica is that to be 25 sodium type β zeolite mix with HP aluminium hydrate powder by the described method preparation of CN85100218 for 60 sodium type ZSM-5 zeolite, silica, the aqueous solution of nitric acid that adds powder weight 40%, concentration and be 2 quality % mixes and pinches, extruded moulding, 110～120 ℃ of dryings 2 hours, 550 ℃ of roastings obtained complex carrier in 4 hours in the air.Contain the ZSM-5 zeolite of 60 quality %, the β zeolite of 20 quality % and the gama-alumina of 20 quality % in the carrier, each amounts of components sees Table 5 during the preparation carrier.
Get the above-mentioned carrier of 10 grams, at 90 ± 10 ℃ of NH that use 0.5N down
4Cl solution 20ml carried out ion-exchange 2 hours to carrier, filtered, and washing is to there not being Cl
-
With the concentration of scheduled volume be the platinum acid chloride solution of 7.0mg/ml at 25 ℃, liquid/solid volume than being the carrier after the above-mentioned ammonium ion exchange of dipping 24 hours under 2 the condition, filter, 110～120 ℃ of dryings 2 hours, 550 ℃ of roastings are 4 hours in the air, 500 ℃ of hydrogen reducings obtained catalyst U in 6 hours, and the Pt content among the catalyst U sees Table 5.
Comparative Examples 8
Carrier 100 grams of the modenite that contains 25 quality % aluminium oxide and 75 quality % by method and the feedstock production of CN200580009162 embodiment 1, extrusion is made the cylindrical vector that diameter is 0.16cm.Carrier at 565 ℃ with the steam calcination of 15 quality % 2 hours.
With the chloro-iridic acid of scheduled volume and the mixed solution of hydrochloric acid preparation is that maceration extract floods above-mentioned carrier, making liquid/solid volume ratio is 1.8, contain iridium 1.2 quality % in the maceration extract, chloride 1.6 quality %, 110～120 ℃ of dryings 12 hours, 550 ℃ of roastings are 4 hours in the air, and 500 ℃ of hydrogen reducings made catalyst V in 6 hours, and wherein Ir content sees Table 5.
Table 5
| The Comparative Examples numbering | 5 | 6 | 7 | 8 |
| The catalyst numbering | S | T | U | V |
| ZSM-5 zeolite silica consumption, quality % | 120 60 | 60 40 | 60 60 | |
| Modenite silica consumption, quality % | - - - | 27 20 | - - - | 30 75 |
| β zeolite silica consumption, quality % | - - - | - - - | 25 20 | |
| Content in the aluminium oxide crystalline phase carrier, quality % | - - - | γ 0 | γ 20 | γ 25 |
| Catalyst metal content, quality % Pt Re Sn Ir | 0.2 0.4 0.35 - | 0.25 - - - | 0.25 - - - | - - - 0.5 |
Example 29～36
Following example is estimated the reactivity worth of the catalyst of Comparative Examples preparation.
Two sections filling 20ml catalyst in continuous fixed bed reactor, each 10ml of last hypomere is with the C shown in the table 2
9 +Aromatic hydrocarbons was raw material, 500 ℃, 1.0MPa, liquid volume air speed 3 hours
-1, hydrogen/hydrocarbon mol ratio is to react under the condition of 5:1, the results are shown in Table 6.
Table 6
Example 37～42
Catalyst D of the present invention, M and comparative catalyst Q, P, S, V are carried out the lighting reaction by the method for example 15, and two sections average coke contents see Table 7 on 200 hours post catalyst reactions.As shown in Table 7, the carbon deposition quantity of catalyst of the present invention is low than the comparative catalyst.
Table 7
| Instance number | 37 | 38 | 39 | 40 | 41 | 42 |
| The catalyst numbering | D | M | P | Q | S | V |
| Catalyst carbon deposit, quality % | 0.98 | 1.13 | 1.52 | 1.36 | 2.6 | 2.2 |
Example 43
Prepare catalyst of the present invention.
Get gamma-aluminium oxide carrier 100 grams, use SnCl by the preparation of example 1 (1) one step process
2Mixed solution dipping with the hydrochloric acid configuration, containing Sn 0.25 quality %, HCl 8.0 quality % in the maceration extract (is that benchmark calculates with the butt gamma-aluminium oxide carrier all, down together), add deionized water, making liquid/solid volume ratio is 1.4,25 ℃ of dippings filtered after 24 hours, 120 ℃ of dryings 12 hours, and 500 ℃ is that blowing air was handled 4 hours under 1000/1 the condition in gas/agent volume ratio; The Sn aluminium oxide that contains that makes is the maceration extract dipping with the mixed solution of chromic nitrate and hydrochloric acid preparation, contains Cr 7.5 quality %, HCl 1.0 quality % in the maceration extract, adds deionized water, and making liquid/solid volume ratio is 2.5.25 ℃ of dippings filtered after 24 hours, and 120 ℃ of dryings 12 hours are again in 550 ℃, H
2The O/HCl mol ratio is a water chlorine activation 6 hours under 20 the condition, 350 ℃, H
2Use hydrogen reducing 4 hours under the condition of/agent volume ratio 250:1, obtain catalyst W, it is that each constituent content that benchmark calculates sees Table 8 with the butt gamma-aluminium oxide carrier.
Example 44
Method by example 43 prepares catalyst, different is, and will to contain the Sn aluminium oxide be the maceration extract dipping with the mixed solution of nickel nitrate and hydrochloric acid preparation, contain Ni 5.0 quality %, HCl 1.0 quality % in the maceration extract, obtain catalyst X behind processing of water chlorine and hydrogen reducing, it is that each constituent content that benchmark calculates sees Table 8 with the butt gamma-aluminium oxide carrier.
Comparative Examples 9
Method by example 43 prepares catalyst, different is the mixed solution dipping gamma-aluminium oxide carrier of preparing with chromic nitrate and hydrochloric acid, obtain catalyst Y behind water chlorine activation and hydrogen reducing, it is that each constituent content that benchmark calculates sees Table 8 with the butt gamma-aluminium oxide carrier.
Comparative Examples 10
Method by example 43 prepares catalyst, different is with the mixed solution of nickel nitrate and hydrochloric acid preparation is maceration extract dipping gamma-aluminium oxide carrier, contain Ni 5.0 quality %, HCl 1.0 quality % in the maceration extract, obtain catalyst Z behind dipping back solid drying, water chlorine activation and the hydrogen reducing, it is that each constituent content that benchmark calculates sees Table 8 with the butt gamma-aluminium oxide carrier.
Table 8
Example 45～48
Reactivity worth to the catalyst of example 42,43 and Comparative Examples 9,10 preparations is estimated.
Two sections filling 20ml catalyst in continuous fixed bed reactor, each 10ml of last hypomere is with the C shown in the table 2
9 +Aromatic hydrocarbons was raw material, 510 ℃, 1.5MPa, liquid volume air speed 2 hours
-1, hydrogen/hydrocarbon mol ratio is to react under the condition of 10:1, the results are shown in Table 9.
Table 9
Claims (13)
1, a kind of C
9 +Arenes lightening catalyst comprises the high-temperature inorganic oxide carrier and is the following component of content that benchmark calculates with the butt carrier:
Hydrogenation metal 0.01～10.0 quality %
IVA family metal 0.01～1.0 quality %
Halogen 0.1～5.0 quality %
Described hydrogenation metal chosen from Fe, cobalt, chromium, nickel or iridium.
2,, it is characterized in that each components contents is in the described catalyst according to the described catalyst of claim 1:
Hydrogenation metal 0.1～5.0 quality %
IVA family metal 0.05～0.5 quality %
Halogen 0.1～3.0 quality %
3, according to claim 1 or 2 described catalyst, it is characterized in that described hydrogenation metal is selected from iridium, chromium or nickel, IVA family metal is selected from tin or lead, and halogen is selected from chlorine, and the high-temperature inorganic oxide carrier is an aluminium oxide.
4,, it is characterized in that described aluminium oxide is a gama-alumina according to the described catalyst of claim 3.
5, the described Preparation of catalysts method of a kind of claim 1, comprise that with containing IVA family solution of metal compound be high-temperature inorganic oxide behind the maceration extract dip forming, again with hydrogenation metal compound solution dipping, carry out the water chlorine activation after the drying and handle after drying, the roasting.
6, the described Preparation of catalysts method of a kind of claim 1 comprises that with the solution that contains IVA family metallic compound and hydrogenation metal compound be high-temperature inorganic oxide behind the maceration extract dip forming, carries out the water chlorine activation after the drying and handles.
7,, it is characterized in that also containing in the described maceration extract halide according to claim 5 or 6 described methods.
8,, it is characterized in that described hydrogenation metal compound is selected from the chloracid of the chloride of iridium, chromium or nickel, nitrate, oxychlorination thing or described metal according to claim 5 or 6 described methods.
9,, it is characterized in that the described IVA of containing family metallic compound is selected from germanium, tin or plumbous halide, nitrate, sulfate or phosphate according to claim 5 or 6 described methods.
10,, it is characterized in that described water chlorine activation treatment temperature is 450～700 ℃, the H that feeds during activation according to claim 5 or 6 described methods
2The mol ratio of O and HCl is 3～100:1.
11, a kind of with C
9 +Aromatic hydrocarbons is converted into the method for light aromatics, comprises C
9 +The described catalyst of aromatic hydrocarbons and claim 1 in the presence of hydrogen, haptoreaction under 380～600 ℃, the condition of 0.1～5.0MPa.
12, in accordance with the method for claim 11, it is characterized in that described C
9 +The liquid volume air speed that aromatic hydrocarbons contacts with catalyst is 1～00 hour
-1, hydrogen/hydrocarbon mol ratio is 0.1～15.0:1.
13, in accordance with the method for claim 11, it is characterized in that described C
9 +The C that contains 0.1～5.0 quality % during virtue is light
8Aromatic hydrocarbons, the C of 2.0～88 quality %
9Aromatic hydrocarbons, the C of 10～75 quality %
10Aromatic hydrocarbons, the C of 1.0～30 quality %
11 +Aromatic hydrocarbons, wherein gum level is not less than 20mg/100ml.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101782311A CN101444732B (en) | 2007-11-28 | 2007-11-28 | C9 aromatic hydrocarbon lightening catalyst and lightening method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101782311A CN101444732B (en) | 2007-11-28 | 2007-11-28 | C9 aromatic hydrocarbon lightening catalyst and lightening method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101444732A true CN101444732A (en) | 2009-06-03 |
| CN101444732B CN101444732B (en) | 2012-05-23 |
Family
ID=40740791
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007101782311A Active CN101444732B (en) | 2007-11-28 | 2007-11-28 | C9 aromatic hydrocarbon lightening catalyst and lightening method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101444732B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102189002A (en) * | 2010-03-04 | 2011-09-21 | 中国石油化工股份有限公司 | Pseudo-boehmite and molecular sieve composition and carrier prepared from same |
| CN102205249A (en) * | 2010-03-31 | 2011-10-05 | 中国石油化工股份有限公司 | Catalytic de-waxing catalyst and its application |
| CN102205241A (en) * | 2010-03-31 | 2011-10-05 | 中国石油化工股份有限公司 | Aromatic hydrogenated saturated catalyst and application thereof |
| CN107759430A (en) * | 2016-08-23 | 2018-03-06 | 中国石油化工股份有限公司 | The compound bed process of heavy aromatics lighting increasing production of xylol |
-
2007
- 2007-11-28 CN CN2007101782311A patent/CN101444732B/en active Active
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102189002A (en) * | 2010-03-04 | 2011-09-21 | 中国石油化工股份有限公司 | Pseudo-boehmite and molecular sieve composition and carrier prepared from same |
| CN102189002B (en) * | 2010-03-04 | 2013-04-24 | 中国石油化工股份有限公司 | Pseudo-boehmite and molecular sieve composition and carrier prepared from same |
| CN102205249A (en) * | 2010-03-31 | 2011-10-05 | 中国石油化工股份有限公司 | Catalytic de-waxing catalyst and its application |
| CN102205241A (en) * | 2010-03-31 | 2011-10-05 | 中国石油化工股份有限公司 | Aromatic hydrogenated saturated catalyst and application thereof |
| CN102205249B (en) * | 2010-03-31 | 2013-06-05 | 中国石油化工股份有限公司 | Catalytic de-waxing catalyst |
| CN102205241B (en) * | 2010-03-31 | 2013-09-04 | 中国石油化工股份有限公司 | Aromatic hydrogenated saturated catalyst and application thereof |
| CN107759430A (en) * | 2016-08-23 | 2018-03-06 | 中国石油化工股份有限公司 | The compound bed process of heavy aromatics lighting increasing production of xylol |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101444732B (en) | 2012-05-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0884103B1 (en) | Catalyst based on high-silica zeolite and bismuth and its use for the conversion of aromatic hydrocarbons | |
| CN105642341B (en) | Supported amorphous catalyst of phosphatizing nickel and its preparation and application for light paraffins isomerization | |
| CN104399520B (en) | Catalyst for producing high-octane-number gasoline composition from heavy aromatic hydrocarbons and preparation method of catalyst | |
| CN102895995B (en) | Naphtha reforming catalyst and preparation method thereof | |
| CN107626343A (en) | A kind of one-step method from syngas prepares catalyst of light aromatics and preparation method and application | |
| CN101987969B (en) | Method for converting C9+ heavy arenes into light arenes | |
| CN100548480C (en) | A kind of hydro carbons Working liquids product modifying catalyst and method for modifying | |
| CN101444732B (en) | C9 aromatic hydrocarbon lightening catalyst and lightening method thereof | |
| CN103288578A (en) | Isomerization reaction method of C-8 aromatic hydrocarbon | |
| CN101357876B (en) | Method for conveying C<+>9 heavy aromatics to light aromatics | |
| CN102078819A (en) | Light hydrocarbon aromatization catalyst and preparation method thereof | |
| JP5291924B2 (en) | Method for isomerizing aromatic C8 compounds in the presence of a catalyst comprising modified EUO zeolite | |
| CN1048425C (en) | Catalyst and method for converting heavy arene into light one | |
| CN1227192C (en) | Heavy arenes lightening catalyst and preparing method thereof | |
| CN109465022B (en) | Catalyst suitable for aromatization of low-carbon hydrocarbons in Fischer-Tropsch synthetic oil and preparation and application thereof | |
| CN103551187B (en) | A kind of catalyst producing toluene and C8 aronmatic and its preparation method and application | |
| CN102895993B (en) | Sulfur-containing alkane aromatization catalyst, preparation method and applications thereof | |
| CN100425343C (en) | Alkyl arene isomerizing catalyst and its usage | |
| CN110075912A (en) | A kind of C10+Heavy arene hydrogenation takes off the catalyst and preparation method thereof that alkyl prepares low-carbon aromatic hydrocarbons | |
| JP3302553B2 (en) | Catalyst for converting heavy aromatics to light aromatics and method for converting the same | |
| CN103539619A (en) | Method for preparing arene from mixed C4 in aromatization mode | |
| CN104383961A (en) | Catalyst for hydrocracking heavy aromatics for producing high-purity BTX aromatics and preparing method of catalyst | |
| CN102397791B (en) | Catalyst for conversion of C9<+> heavy aromatic hydrocarbon to light aromatic hydrocarbon, preparation and application method | |
| US11660588B2 (en) | Catalyst for producing C8 aromatic hydrocarbon having reduced ethylbenzene content and preparation method therefor | |
| CN103831128A (en) | Modified nano molecular sieve hydrogenation aromatization catalyst and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |