CN102397791A - Catalyst for conversion of C9<+> heavy aromatic hydrocarbon to light aromatic hydrocarbon, preparation and application method - Google Patents
Catalyst for conversion of C9<+> heavy aromatic hydrocarbon to light aromatic hydrocarbon, preparation and application method Download PDFInfo
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Abstract
A catalyst for the conversion of C9<+> heavy aromatic hydrocarbon to light aromatic hydrocarbon contains a high-temperature resistant inorganic oxide carrier and active components. The active components, which are calculated with the carrier as the reference, comprise 0.1-1.0 wt% of Ir, 0.1-2.0 wt% of alkaline earth metal and 0.01-3.0 wt% of a halogen. The catalyst is prepared by a stepwise impregnation method. The alkaline earth metal is firstly introduced into the carrier, and Ir is then introduced; and finally chlorination activation and reduction are carried out to obtain the catalyst. Used for the conversion of C9<+> heavy aromatic hydrocarbon to light aromatic hydrocarbon, the catalyst provided by the invention has high C9<+> aromatic hydrocarbon conversion rate and BTX yield, and has good regrowth performance.
Description
Technical field
The present invention is a kind of C
9 +Heavy arenes lightening catalyst and preparation and application process, specifically, be a kind of be heavy arenes lightening catalyst and the preparation and the lightening method of active component with iridium.
Background technology
Heavy aromatics generally is meant catalytic reforming, and disproportionation and isomerization reaction generate contained C in oil and the cracking of ethylene hydrogasoline
9-C
16Single, double cycloalkyl aromatic hydrocarbons.For a long time, the heavy aromatics resource does not all 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 see that it all is worthless that heavy aromatics is directly acted as a fuel from the angle of economy and environmental protection.On the one hand, heavy aromatics can be converted into benzene, toluene and xylenes light aromatic hydrocarbons such as (BTX); On the other hand,, there has been report to think in recent years and can have alleviated the pollution that vehicle exhaust causes, and thought the T of gasoline through reducing doing of gasoline from environmental angle
90Should be lower than or between 132 ℃～177 ℃.Above-mentioned two aspect reasons all show: heavy aromatics further is converted into light aromatic hydrocarbons, from economy still be environmental angle all be favourable.
The main method of heavy aromatics lighting at present is pyrolysismethod and catalytic dealkylation method, and the main deficiency of prior art is reaction temperature and pressure height, and air speed is low, and the commercialization of technology is restricted.
The key reaction that the heavy aromatics catalytic dealkylation carries out lighting is the hydro-dealkylation reaction, and generally speaking, the aromatic hydrocarbons side chain is long more, in the hydro-dealkylation reaction, sloughs side chain more easily.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 employing restricted index is 1-12, high silica alumina ratio, low acid activity is a catalyst, and the heavy reformate is reacted under 427-540 ℃ condition, again the product separated is obtained benzene, toluene and xylenes.Contain in this catalyst and have the active VIII family noble metal of hydro-dealkylation, preferred platinum, the zeolite silica alumina ratio of selecting for use is higher, is generally more than 200, and is preferred 500～1600, and preferred zeolite is ZSM-5, ZSM-11, ZSM-12, ZSM-35, ZSM-38 etc.The purpose of selecting the high silica alumina ratio zeolite is to reduce the acidity of zeolite, so that xylenes 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 uses in this method comprises metal component and the MCM-22 zeolite that is selected from noble metal, nickel and the mixture between them, and the accessible raw material range broad of this catalyst can be processed C
6～C
12Mononuclear aromatics is greater than the raw material of 50mol%, as obtaining the higher boiling gasoline component for improving the light cycle quality.The MCM-22 zeolite of its use has advantages such as Heat stability is good and specific area be big.The Al of the MCM-22 zeolite that consists of 65 heavy % of its preparation, 35 heavy %
2O
3, 0.66 heavy % the catalyst of platinum, can be at 315～482 ℃, 200psig, liquid hourly space velocity (LHSV) 2.5, hydrogen cycle rate 2000 gauges
3Under the reaction condition of/barrel, 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 zeolite catalyst that improves takes off the active method of alkyl.This method is carried out a series of processing back with zeolite earlier and is introduced fluorine and metal constituent element, again through steps such as shaping and roastings.For transalkylation process tail oil and heavy reformate, this catalyst possesses the higher alkyl activity of taking off, and shows the good selectivity to benzene and monoalkyl aromatic hydrocarbons simultaneously.
CN1048425C discloses the catalyst that a kind of heavy aromatic hydrocarbon light is produced BTX.This catalyst is with the ZSM-5 zeolite of the heavy % of 30-70 and the γ of 30-70 weight %-or η-Al
2O
3Be carrier, the tin of the rhenium of the heavy % of load 0.1-0.5, the heavy % of 0.1-0.5, the palladium of the platinum of the heavy % of 0.05-0.3 or the heavy % of 0.2-0.8.At 350～450 ℃, 0.5～3.5MPa, weight space velocity 1～5 o'clock
-1, hydrogen/hydrocarbon volume ratio 500～1200 operating condition under, this catalyst has higher activity and activity stability and lower hydrogen consumption.
CN1082539C discloses a kind of heavy aromatic hydrocarbon light and has produced the catalyst of BTX and the separation method of lighting product.Said catalyst is made up of the VIII family noble metal of 0.05～0.3 heavy %, the zeolite with MOR structure of 20～59 heavy %, the MFI zeolite of 20～50 heavy % and the aluminium oxide of 20～40 heavy %.Heavy arene contacts with above-mentioned catalyst under 350～450 ℃, 0.5～3.5MPa condition, and gained lighting product can obtain Organic Ingredients such as BTX and mesitylene, pseudocumene, durol through fractionation.
CN1472181A, CN1472182A disclose a kind of VIII family noble metal that contains 0.01～2.0 heavy % separately; Carrier is the catalyst of complex carrier, and wherein the disclosed complex carrier of CN1472181A contains the ZSM-5 zeolite of the heavy % of 30-70, the modenite of the heavy % of 5-20 and the aluminium oxide of the heavy % of 10-65; And the disclosed complex carrier of CN1472182A contains the ZSM-5 zeolite of 30～70 heavy %, the β zeolite of 5～30 heavy % and the aluminium oxide of 10～65 heavy %.Compare with the catalyst that the carrier that only contains ZSM-5 zeolite and aluminium oxide makes, can not only improve C when the catalyst that above-mentioned complex carrier makes is used for the heavy aromatics lighting
9 +The conversion ratio of aromatic hydrocarbons can also improve the productive rate of benzene and xylenes simultaneously, and reduces carbon deposit.
CN200580009162 discloses a kind of transalkylation method; The catalyst carrier of using 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, when generating xylenes, also can to a certain degree reduce the 99.5wt% final boiling point (ASTM D2887 simulation distil gas chromatography determination) of feed stream.
CN200710119762.3 discloses a kind of C
9 +The method of heavy aromatic hydrocarbon light, the catalyst that uses comprise the high-temperature inorganic oxide carrier and are the halogen of 0.01～3.0 quality % and the iridium of 0.01～5.0 quality % with carrier as the content that benchmark calculates.This catalyst have fabulous reactivity worth, but regeneration is comparatively difficult with heavy ends lighting raising the output BTX in the reformed oil, and the activity and the selectivity of regeneration rear catalyst obviously descend.
Summary of the invention
The purpose of this invention is to provide a kind of C
9 +Heavy arenes lightening catalyst and preparation method, this catalyst has higher C
9 +Aromatics conversion rate and BTX productive rate, and regenerability is better.
C provided by the invention
9 +Heavy arenes lightening catalyst comprises the high-temperature inorganic oxide carrier and is the following active component of content that benchmark calculates with the carrier:
Ir 0.1～1.0 quality %,
Alkaline-earth metal 0.1～2.0 quality %,
Halogen 0.01～3.0 quality %.
Catalyst of the present invention adds alkaline earth metal component in main active component iridium, make the catalyst that makes after using inactivation, through burn, after water chlorine activation and the reduction, catalyst performance is recovered completely.Compare with containing the Ir single-metal reforming catalyst, catalyst of the present invention has the excellent reproducibility ability.
The specific embodiment
Catalyst of the present invention is carrier with the high-temperature inorganic oxide, through load active component iridium, and the alkaline-earth metal constituent element; The acid function of control content of halogen adjustment catalyst; Make it have suitable acidity, transform the generation light aromatics to promote the heavy arene in the reaction raw materials, and the ethylbenzene in the light aromatics is transformed as far as possible; Further increase the content of BTX in the upgraded product, the single-metal reforming catalyst that the regenerability of catalyst more only contains Ir has tangible improvement.
Catalyst preferred active ingredient content of the present invention is following:
Ir 0.1～0.6 quality %,
Alkaline-earth metal 0.1～1.5 quality %,
Halogen 0.1～2.0 quality %.
The preferred Mg of described alkaline-earth metal, Ca, Sr or Ba.The preferred chlorine of described halogen.
Described high-temperature inorganic oxide carrier should have uniform composition and under the service condition of hydrocarbon conversion process, have suitable refractoriness." 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 of 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-scandium oxide, preferred aluminium oxide.The crystalline phase of said aluminium oxide can be γ, η or θ, preferred γ phase
Described carrier can be any required shape, like sphere, sheet, ingot shape, bar shaped, powder, graininess etc., and preferred sphere or bar shaped.
Preparation of catalysts method provided by the invention comprises with the high-temperature inorganic oxide carrier after the solution impregnation moulding of alkaline including earth metal compound, dry, roasting, and then, carry out water chlorine activation, reduction after the drying with containing the iridic compound solution impregnation.
The moulding of said high-temperature inorganic oxide can be adopted conventional extruded moulding or drip ball forming.
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 said 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 process 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 during roasting/agent volume ratio preferred 700～1000: 1.
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 said peptizing agent or the used acid of acidifying slurries.
The compound of described alkaline including earth metal is oxide, chloride, nitrate or the acetate of alkaline-earth metal, preferably calcium chloride, strontium chloride, barium chloride, calcium nitrate, strontium nitrate, barium nitrate.During with the solution impregnating carrier of alkaline including earth metal compound, the liquid/solid volume of dipping is than preferred 1.0～3.0: 1, and preferred 20～40 ℃ of dipping temperature.Maceration extract can add an amount of inorganic monoacid, preferred hydrochloric acid of inorganic monoacid and nitric acid, and addition is 0.5～5.0%, preferred 1.0～2.5% of a butt carrier quality.Behind the dipping with solid in 100～200 ℃ of dryings 2～20 hours, preferred 4～16 hours, dry roasting.Sintering temperature is 450～700 ℃, and preferred 450～650 ℃, roasting time is 2～12 hours, preferred 4～8 hours.Roasting is carried out under the condition of bubbling air, and the gas volume that per hour feeds is 500～2500: 1 with the ratio of catalyst volume, and preferred 800～1500: 1.
In the inventive method, dipping is introduced the carrier of alkaline-earth metal, after drying, roasting, introduces iridium with containing the iridic compound solution impregnation again.The described iridic compound that contains is selected from chloro-iridic acid, ammonium chloroiridate, iridium chloride or yttrium oxide.Preferably contain halide described containing in the iridic compound solution, so that halogen ion wherein, like Cl
-With the absorption of competing of chloro-iridic acid ion, iridium is uniformly distributed in the carrier, the preferred hydrochloric acid of described halide.Liquid/solid volume during dipping is than preferred 1.0～3.0: 1, and preferred 20～40 ℃ of dipping temperature.Filter the dipping back, solid is carried out the water chlorine activation handle after 100～200 ℃ of dryings.
Carrier with behind the solution impregnation introducing alkaline-earth metal that contains the Ir compound promptly makes catalyst through drying, the processing of high-temperature water chlorine activation and reduction again.Halogen in the catalyst can be introduced in catalyst preparation process, also can in the catalyst use, introduce, as introducing catalyst through the mode of in reaction raw materials, introducing halogen compounds.Best mode be the form of or organohalogen compounds inorganic with hydrochloric acid or other when dipping and metal Ir together introduce.
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 the temperature of water chlorine activation, the H that feeds during activation
2The mol ratio of O and HCl preferred 3～100: 1, more preferably 5～60: 1, preferred 2～200 hours of water chlorine activation time, more preferably 4～100 hours.
Catalyst behind the water chlorine activation is promptly obtained reduction catalyst with the reducibility gas reduction.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 to carry out C
9 +The method of heavy aromatic hydrocarbon light comprises C
9 +Heavy arene and catalyst of the present invention in the presence of hydrogen, haptoreaction under 380～600 ℃, 0.1～5.0MPa condition.
Described C
9 +The liquid volume air speed that aromatic hydrocarbons contacts with catalyst is 1.0～100 hours
-1, preferred 1.0～15 hours
-1, hydrogen/hydrocarbon mol ratio is 0.1～15.0: 1.
C of the present invention
9 +Aromatic hydrocarbons 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, and generally requires C in the raw material
9 +Arene content is not less than 70 quality %, preferably is not less than 85 quality %.
Catalyst of the present invention is through the C of certain hour
9 +After the arene light formation reaction, the carbon deposited catalyst that obtains burns under certain condition, and after the catalyst process water chlorine activation after burning, the reduction, catalyst performance is recovered completely.The condition of burning is pressure 0.1～0.5MPa; The inlet temperature of beds is 350～700 ℃, and the gas that per hour feeds is 1500～6000: 1 with the ratio of catalyst volume, preferred 2500～4000: 1; Oxygen content is 0.3～1.5 volume % in the gas, preferred 0.4～1.0 volume %.
Pass through example in detail the present invention below, but the present invention is not limited to this.
Instance 1
Prepare catalyst of the present invention.
(1) preparation gamma-aluminium oxide carrier.
Get the deionized water that 100 gram aluminium hydrate powders (Condea company produces, trade mark SB) add 200 grams, stir and make its pulp.Adding volume ratio by the amount of 7.5 milliliters in per 100 gram SB powder is 1: 1 nitric acid, and the concentration that adds 30 gram urea and 10.0 grams simultaneously is the hydrochloric acid solution of 36.5 quality %, stirs 1 hour, adds 30 gram kerosene 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 the mixed solution of calcium chloride and hydrochloric acid preparation to flood, calcic 0.2 quality %, HCl 2.0 quality % (being that benchmark calculates all, down together) in the maceration extract with the butt gamma-aluminium oxide carrier as maceration extract; Add deionized water, making liquid/solid volume ratio is 1.2.25 ℃ of dippings rotated evaporate to dryness after 8 hours, and 120 ℃ of dryings 12 hours are roasting 6 hours in the air under 1200/1 the condition in 550 ℃, gas agent volume ratio again.
Carrier behind the dipping Ca that aforesaid way makes uses the mixed solution of chloro-iridic acid and hydrochloric acid preparation to flood as maceration extract, contains iridium 0.1 quality %, HCl 2.5 quality % in the maceration extract; Add deionized water; Making liquid/solid volume ratio is that 1.5,25 ℃ of dippings filtered in 8 hours, 120 ℃ of dryings 12 hours; Again in 500 ℃, H
2The O/HCl mol ratio is a water chlorine activation 6 hours under 50 the condition, 450 ℃, H
2With hydrogen reducing 4 hours, obtain catalyst A under 250: 1 the condition of/agent volume ratio, it is that benchmark activity calculated constituent content is seen table 1 with the butt gamma-aluminium oxide carrier.
Instance 2
Method by instance 1 prepares catalyst, and calcium content is 0.3 quality % in the maceration extract of different is (2) calcic that the step impregnated carrier uses, and contains that Ir content is 0.3 quality % in the maceration extract of chloro-iridic acid, and the active component content of the catalyst B that makes is seen table 1.
Instance 3
Method by instance 1 prepares catalyst, and calcium content is 0.5 quality % in the maceration extract of different is (2) calcic that the step impregnated carrier uses, and contains that Ir content is 0.5 quality % in the maceration extract of chloro-iridic acid, and the active component content of the catalyst C that makes is seen table 1.
Instance 4
Method by instance 1 prepares catalyst, and calcium content is 1.4 quality % in the maceration extract of different is (2) calcic that the step impregnated carrier uses, and contains that Ir content is 1.0 quality % in the maceration extract of chloro-iridic acid, and the active component content of the catalyst D that makes is seen table 1.
Instance 5
Method by instance 1 prepares catalyst, contains strontium 0.5 quality % in different is (2) the maceration extract that the step impregnated carrier uses, contains that Ir content is 0.5 quality % in the maceration extract of chloro-iridic acid, and the active component content of the catalyst E that makes is seen table 1.
Instance 6
Method by instance 1 prepares catalyst, and baric 0.5 quality % in different is (2) the maceration extract that the step impregnated carrier uses contains that Ir content is 0.5 quality % in the maceration extract of chloro-iridic acid, and the active component content of the catalyst F that makes is seen table 1.
Comparative Examples 1
Method by instance 1 prepares catalyst, and different is (2) step only to use the maceration extract impregnated carrier that contains chloro-iridic acid, and Ir content is 0.3 quality % in the maceration extract, and the active component content of the catalyst G that makes is seen table 2.
Comparative Examples 2
Method by instance 1 prepares catalyst, and different is (2) step only to use the maceration extract impregnated carrier that contains chloro-iridic acid, and Ir content is 0.5 quality % in the maceration extract, and the active component content of the catalyst H that makes is seen table 2.
Comparative Examples 3
Method by instance 1 prepares catalyst, and different is (2) step only to use the maceration extract impregnated carrier that contains chloro-iridic acid, and Ir content is 1.0 quality % in the maceration extract, and the active component content of the catalyst I that makes is seen table 2.
Instance 7～15
Following instance 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 raw material consists of: C
8Aromatic hydrocarbons 3.8 quality %, C
9Aromatic hydrocarbons 67.8 quality %, C
10Aromatic hydrocarbons 21.2 quality %, C
11 +Aromatic hydrocarbons 6.2 quality %.1.0MPa, liquid volume air speed 3 hours
-1, hydrogen/hydrocarbon mol ratio is to react under 5: 1 the condition; Adopt the 200th hour reactivity worth of online reaction to represent the evaluation initial performance of catalyst; The 1450th hour reactivity worth is represented the evaluation performance in latter stage of catalyst; Catalyst A～F reaction result is seen table 3, and catalyst G～I reaction result is seen table 4, under same reaction conditions, sees table 5 through 1500 hours post catalyst reaction A～average coke contents of I two sections.
The data computing formula is following:
C
9 +Aromatics conversion rate=[(C in the feedstock oil
9 +C in aromatic hydrocarbons-generation oil
9 +Aromatic hydrocarbons * liquid yield)/feedstock oil in C
9 +Aromatic hydrocarbons] * 100% (quality)
Aromatic ring loss=[aromatic ring total mole number in (in the feedstock oil in aromatic ring total mole number-generation oil aromatic ring total mole number * liquid yield)/feedstock oil] * 100% (mole)
Carbon deposit=(carbon deposit quality on the catalyst/catalyst nature matrix amount) * 100%
C wherein
9 +Aromatics conversion rate is represented activity of such catalysts, and selection of catalysts property is represented in the aromatic ring loss.
Table 1
Table 2
Table 3
Table 4
Table 5
| Instance number | 7 | 8 | 9 | 10 | 11 | 12 | 13 | 14 | 15 |
| The catalyst numbering | A | B | C | D | E | F | G | H | I |
| Catalyst carbon deposit, quality % | 3.2 | 3.8 | 4.1 | 4.8 | 4.2 | 4.2 | 4.0 | 4.3 | 5.0 |
Instance 16～23
The Pd/carbon catalyst that contains after the stability test in 1500 hours is regenerated according to following method.
At 0.2MPa; Oxygen content is 0.6 volume %, and gas volume is 3000/1 with the ratio of catalyst volume, and the beds inlet temperature is to burn 2 hours under 430 ℃ the condition; Temperature to 470 ℃ is burnt in adjustment subsequently; Keep this inlet temperature to burning end, burn and finish rear catalyst in 500 ℃, H
2The O/HCl mol ratio is a water chlorine activation 6 hours under 40 the condition, 450 ℃, H
2Under 250: 1 the condition of/agent volume ratio with hydrogen reducing 4 hours, the catalyst after obtaining regenerating.
Two sections filling 20ml catalyst in continuous fixed bed reactor, each 10ml of last hypomere is with the C of instance 7 described reformations, disproportionation, isomerization by-product
9 +Aromatic hydrocarbons is raw material.Use regenerated catalyst at 484 ℃, 1.0MPa, liquid volume air speed 3 hours
-1, hydrogen/hydrocarbon mol ratio is to react under 5: 1 the condition.Choose the reaction result of the 200th hour data of online reaction after as catalyst regeneration, evaluation result is seen table 6.
Can know by table 6; Bimetallic catalyst provided by the invention is through after regenerating; The BTX yield, liquid is received, and the aromatic ring loss is all suitable basically with the preceding fresh catalyst of regenerating; And the performance of single-metal reforming catalyst G, H, the I regeneration rear catalyst reactivity worth of comparing with fresh catalyst obviously descends, and the BTX yield reduces significantly.
Table 6
Claims (12)
1. C
9 +Heavy arenes lightening catalyst comprises the high-temperature inorganic oxide carrier and is the following active component of content that benchmark calculates with the carrier:
Ir 0.1～1.0 quality %,
Alkaline-earth metal 0.1～2.0 quality %,
Halogen 0.01～3.0 quality %.
2. according to the described catalyst of claim 1, it is characterized in that said catalyst activity constituent content is following:
Ir 0.1～0.6 quality %,
Alkaline-earth metal 0.1～1.5 quality %,
Halogen 0.1～2.0 quality %.
3. according to claim 1 or 2 described catalyst, it is characterized in that described alkaline-earth metal is Mg, Ca, Sr or Ba.
4. according to claim 1 or 2 described catalyst, it is characterized in that described halogen is a chlorine, the high-temperature inorganic oxide carrier is an aluminium oxide.
5. said Preparation of catalysts method of claim 1; Comprise with the high-temperature inorganic oxide carrier after the solution impregnation moulding of alkaline including earth metal compound; Dry, roasting, and then, carry out water chlorine activation, reduction after the drying with containing the iridic compound solution impregnation.
6. according to the described method of claim 5, the compound that it is characterized in that described alkaline including earth metal is oxide, chloride, nitrate or the acetate of alkaline-earth metal.
7. according to the described method of claim 5, it is characterized in that the described iridic compound that contains is selected from chloro-iridic acid, ammonium chloroiridate, iridium chloride or yttrium oxide.
8. according to the described method of claim 5, it is characterized in that containing in the iridic compound solution and contain halide.
9. according to the described method of claim 5, it is characterized in that sintering temperature is 450～700 ℃.
10. according to the described method of claim 5, it is characterized in that the temperature of water chlorine activation is 400～700 ℃, the H that feeds during activation
2The mol ratio of O and HCl is 3～100: 1.
11. C
9 +The method of heavy aromatic hydrocarbon light comprises C
9 +The described catalyst of heavy arene and claim 1 in the presence of hydrogen, haptoreaction under 380～600 ℃, 0.1～5.0MPa condition.
12., it is characterized in that described C according to the described method of claim 11
9 +The liquid volume air speed that aromatic hydrocarbons contacts with catalyst is 1～100 hour
-1, hydrogen/hydrocarbon mol ratio is 0.1～15.0: 1.
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| US3856661A (en) * | 1970-02-23 | 1974-12-24 | Inst Francais Du Petrole | Reforming using homogeneous platinum-iridium catalyst |
| US4968408A (en) * | 1989-07-03 | 1990-11-06 | Exxon Research & Engineering Company | Reforming using platinum agglomerated iridium catalysts |
| US6414209B1 (en) * | 1997-12-10 | 2002-07-02 | Mannesman Ag | Catalyst for converting paraffinic hydrocarbon into corresponding olefin |
| CN101664679A (en) * | 2009-11-17 | 2010-03-10 | 中国科学院大连化学物理研究所 | Coal bed gas deoxidation catalyst as well as preparation method and application thereof |
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