CN102397791B - 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
- Publication number
- CN102397791B CN102397791B CN201010276701.XA CN201010276701A CN102397791B CN 102397791 B CN102397791 B CN 102397791B CN 201010276701 A CN201010276701 A CN 201010276701A CN 102397791 B CN102397791 B CN 102397791B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- quality
- heavy
- earth metal
- carrier
- 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.)
- Active
Links
Landscapes
- Catalysts (AREA)
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 method specifically, are a kind of heavy arenes lightening catalyst and preparation and lightening methods taking iridium as active component.
Background technology
Heavy aromatics generally refers to catalytic reforming, and disproportionation and isomerization reaction generate contained C in oil and cracking of ethylene hydrogasoline
9-C
16single, double cycloalkyl aromatic hydrocarbons.For a long time, Heavy Aromatic Hydrocarbons does not all obtain rationally, utilizes fully, is used as solvent and extracts C except a small amount of
9, C
10outside monomer aromatic hydrocarbons, generally all directly mix gasoline pool as fuel.But, from the angle of economy and environmental protection, be directly no matter all worthless as fuel using heavy aromatics.On the one hand, heavy aromatics can be converted into the light aromatic hydrocarbons such as benzene, toluene and dimethylbenzene (BTX); On the other hand, from environmental angle, there is in recent years report to think and can alleviate by reducing doing of gasoline the pollution that vehicle exhaust causes, and thought the T of gasoline
90should lower than or between 132 DEG C～177 DEG C.Above-mentioned two reasons all show: heavy aromatics is further converted to light aromatic hydrocarbons, from economy or environmental angle is all favourable.
The main method of at present heavy aromatics lighting is pyrolysismethod and catalytic dealkylation method, the main deficiency of prior art be reaction temperature and pressure high, air speed is low, and the commercialization of technology is restricted.
The key reaction that heavy aromatics catalytic dealkylation carries out lighting is hydro-dealkylation reaction, and generally speaking, aromatic hydrocarbons side chain is longer, more easily in hydro-dealkylation reaction, sloughs side chain.Thereby contained ethyl methyl benzene, diethylbenzene or dimethyl ethyl benzene in heavy arene, n-proplbenzene, isopropylbenzene, methyl-propyl benzene etc. comparatively easily reacts, and generates benzene,toluene,xylene etc.
USP4,341,622 disclose a kind of method of utilizing heavy reformate to produce BTX.The zeolite that this method employing restricted index is 1-12, high silica alumina ratio, low acid activity is catalyst, heavy reformate is reacted under the condition of 427-540 DEG C, then product separated is obtained to benzene, toluene and dimethylbenzene.In this catalyst, contain the VIII family noble metal with hydro-dealkylation activity, preferably platinum, the Zeolite of selecting is higher, is generally more than 200, preferably 500～1600, preferred zeolite is ZSM-5, ZSM-11, ZSM-12, ZSM-35, ZSM-38 etc.The object of selecting 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 using in the method comprises the metal component and the MCM-22 zeolite that are selected from noble metal, nickel and the mixture between them, and the accessible raw material range of this catalyst is wider, can process C
6～C
12mononuclear aromatics is greater than the raw material of 50mol%, as obtained higher boiling gasoline component for improving light cycle quality.The MCM-22 zeolite of its use has Heat stability is good and the advantage such as specific area is large.What it was prepared consists of the MCM-22 zeolite of 65 heavy %, the Al of 35 heavy %
2o
3, 0.66 heavy % the catalyst of platinum, can be at 315～482 DEG C, 200psig, liquid hourly space velocity (LHSV) 2.5, hydrogen cycle rate 2000 gauges
3under the reaction condition of/barrel, by 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 BTX selectively reaches 63.8～79.8mol%.
USP5,990,031 disclose a kind of method of improving the de-alkyl activity of zeolite catalyst.This method first carries out zeolite introducing fluorine and metal constituent element after a series of processing, then through steps such as shaping and roastings.For transalkylation process tail oil and heavy reformate, this catalyst possesses higher de-alkyl activity, shows the good selectivity to benzene and monoalkyl aromatic hydrocarbons simultaneously.
CN1048425C discloses the catalyst of a kind of heavy aromatic hydrocarbon light production BTX.This catalyst is with the ZSM-5 zeolite of the heavy % of 30-70 and the γ of the heavy % of 30-70-or η-Al
2o
3for 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 DEG C, 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.Described catalyst is made up of the VIII family noble metal of 0.05～0.3 heavy %, the zeolite with MOR structure, the MFI zeolite of 20～50 heavy % and the aluminium oxide of 20～40 heavy % of 20～59 heavy %.Heavy arene contacts with above-mentioned catalyst under 350～450 DEG C, 0.5～3.5MPa condition, and gained lighting product can obtain the 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 is containing ZSM-5 zeolite, the modenite of the heavy % of 5-20 and the aluminium oxide of the heavy % of 10-65 of the heavy % of 30-70; And the disclosed complex carrier of CN1472182A is containing ZSM-5 zeolite, the β zeolite of 5～30 heavy % and the aluminium oxide of 10～65 heavy % of 30～70 heavy %.Compare with the catalyst that only carrier containing ZSM-5 zeolite and aluminium oxide makes, the catalyst that above-mentioned complex carrier makes can not only improve C during for heavy aromatics lighting
9 +the conversion ratio of aromatic hydrocarbons, can also improve the productive rate of benzene and dimethylbenzene, and reduce carbon deposit simultaneously.
CN200580009162 discloses a kind of transalkylation method, the catalyst carrier 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 processing the feed stream containing high boiling substance, also can to a certain degree reduce the 99.5wt% final boiling point (ASTM D2887 simulation distil gas chromatography determination) of feed stream in generating dimethylbenzene.
CN200710119762.3 discloses a kind of C
9 +the method of heavy aromatic hydrocarbon light, the catalyst of use comprises that high-temperature inorganic oxide carrier and the content taking carrier as benchmark are the halogen of 0.01～3.0 quality % and the iridium of 0.01～5.0 quality %.This catalyst, by heavy constituent lighting volume increase BTX in reformed oil, has fabulous reactivity worth, but comparatively difficulty of regeneration, the activity and selectivity of regeneration rear catalyst obviously declines.
Summary of the invention
The object 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 high-temperature inorganic oxide carrier and the following active component of the content taking carrier as benchmark:
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, in main active component iridium, adds alkaline earth metal component, and the catalyst that makes is being used after inactivation, and through burning, after water chlorine activation and reduction, catalyst performance is recovered completely.Compare with containing Ir single-metal reforming catalyst, catalyst of the present invention has fabulous regenerability.
Detailed description of the invention
Catalyst of the present invention is taking high-temperature inorganic oxide as carrier, by load active component iridium, alkaline-earth metal constituent element, control content of halogen and adjust the acid function of catalyst, make it have suitable acidity, to promote the heavy arene in reaction raw materials to transform generation light aromatics, and the ethylbenzene in light aromatics is transformed as far as possible, the content that further increases BTX in upgraded product, the regenerability of catalyst more only has obvious improvement containing the single-metal reforming catalyst of Ir.
The preferred active component content of catalyst of the present invention is as follows:
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." composition uniformly " refers to that high-temperature inorganic oxide is that intrinsic component not stratified, its composition does not have concentration gradient and complete uniformity on composition.Therefore,, if carrier is the mixture of two or more refractory materials, 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, preferential oxidation aluminium.The crystalline phase of described aluminium oxide can be γ, η or θ, preferably γ phase
Described carrier can be any required shape, as spherical, sheet, ingot shape, bar shaped, powder, graininess etc., and preferably spherical or bar shaped.
The preparation method of catalyst 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 with containing iridic compound solution impregnation, after being dried, carry out water chlorine activation, reduction.
The moulding of described high-temperature inorganic oxide can adopt conventional extruded moulding or drip ball forming.
The method of extruded moulding is that the high-temperature inorganic oxide of powdery or its precursor are added to suitable quantity of water and peptizing agent kneading, and described peptizing agent is generally acid.By kneading evenly after gains extrusion, the carrier that dry, roasting obtains moulding.
The method of dripping ball forming is: the high-temperature inorganic oxide of powdery or its precursor are added to suitable quantity of water, are 1.0～3.0 Gu make liquid/mass ratio.Stirring makes its pulp, and then acid adding is carried out acidifying, adds and account for high-temperature inorganic oxide or the urea of its precursor 20～40 quality % and appropriate hydrochloric acid when acid adding, stirs 1 hour.The dosage of described hydrochloric acid is 0.5～9.5 quality % of high-temperature inorganic oxide.Then optionally add the kerosene that accounts for high-temperature inorganic oxide or its precursor 10～40 quality % to continue to stir 0.5～5.0 hour.Slurries are splashed into oil ammonia column and make bead, wet bulb is dried at 60～80 DEG C, preferably 2～12 hours time, then be dried preferably 4～24 hours time at 120～130 DEG C.After being dried carrier in dry air in 450～750 DEG C of roastings, roasting time preferably 4～10 hours, gas/agent volume ratio when roasting preferably 700～1000: 1.
Peptizing agent described in above-mentioned forming method or for the preferred nitric acid of acid, hydrochloric acid, acetic acid 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 the acid solution of 4～10 milliliters with every 100 grams of acidifying raw materials.The concentration of described peptizing agent or the acid used of acidifying slurries is 1.0～6.0 volume % preferably.
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, Gu the liquid/volume ratio of dipping preferably 1.0～3.0: 1, preferably 20～40 DEG C of dipping temperatures.Maceration extract can add appropriate inorganic monoacid, the preferred hydrochloric acid of inorganic monoacid and nitric acid, and addition is 0.5～5.0% of butt carrier quality, preferably 1.0～2.5%.After dipping by solid in 100～200 DEG C dry 2～20 hours, preferably 4～16 hours, dry roasting.Sintering temperature is 450～700 DEG C, and preferably 450～650 DEG C, roasting time is 2～12 hours, preferably 4～8 hours.Roasting is carried out under the condition that passes into air, and the gas volume passing into per hour is 500～2500: 1 with the ratio of catalyst volume, and preferably 800～1500: 1.
In the inventive method, dipping is introduced the carrier of alkaline-earth metal, after drying, roasting, then with introducing iridium containing iridic compound solution impregnation.Described is selected from chloro-iridic acid, ammonium chloroiridate, iridium chloride or yttrium oxide containing iridic compound.Described preferably contains halide containing in iridic compound solution, so that halogen ion wherein, as Cl
-with the absorption of competing of chloro-iridic acid ion, iridium is uniformly distributed in carrier, the preferred hydrochloric acid of described halide.Gu liquid/volume ratio when dipping preferably 1.0～3.0: 1, preferably 20～40 DEG C of dipping temperatures.After dipping, filter, solid is carried out to the processing of water chlorine activation in 100～200 DEG C after dry.
With the carrier after the solution impregnation introducing alkaline-earth metal containing Ir compound, more drying, the processing of high-temperature water chlorine activation and reduction make catalyst.Halogen in catalyst can be introduced in catalyst preparation process, also can in catalyst use procedure, introduce, as introduced catalyst by the mode of introducing halogen compounds in reaction raw materials.Best mode be with the form of hydrochloric acid or other inorganic or organohalogen compounds when the dipping and metal Ir together introduce.
Described water chlorine activation processing is at high temperature by the process of processing containing the water vapour of HCl by dried catalyst.Preferably 450～700 DEG C of the temperature of water chlorine activation, the H passing into when activation
2the mol ratio of O and HCl preferably 3～100: 1, more preferably 5～60: 1, preferably 2～200 hours water chlorine activation time, more preferably 4～100 hours.
Catalyst after water chlorine activation is obtained to reduction catalyst with reducibility gas reduction.Described reducibility gas is selected from hydrogen or carbon monoxide, preferably hydrogen.Suitable reduction temperature is 250～600 DEG C, H when reduction
2/ catalyst volume ratio is 150～2500: 1, preferably 2～24 hours 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 under hydrogen exists, haptoreaction under 380～600 DEG C, 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, preferably 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 can be also the heavy aromatics that cracking of ethylene technique produces, and can also be the heavy aromatics that other technique produces, C in General Requirements raw material
9 +arene content is not less than 70 quality %, is preferably not less than 85 quality %.
Catalyst of the present invention is through the C of certain hour
9 +after arene light formation reaction, the carbon deposited catalyst obtaining burns under certain condition, and the catalyst after burning is after water chlorine activation, reduction, and catalyst performance is recovered completely.The condition of burning is pressure 0.1～0.5MPa, the inlet temperature of beds is 350～700 DEG C, and the gas passing into per hour is 1500～6000: 1 with the ratio of catalyst volume, preferably 2500～4000: 1, in gas, oxygen content is 0.3～1.5 volume %, preferably 0.4～1.0 volume %.
Below by example in detail the present invention, but the present invention is not limited to this.
Example 1
Prepare catalyst of the present invention.
(1) prepare gamma-aluminium oxide carrier.
Get 100 grams of aluminium hydrate powders (Condea company produce, trade mark SB) and add the deionized water of 200 grams, stir and make its pulp.Adding volume ratio by the amount of 7.5 milliliters, every 100 grams of SB powder is the nitric acid of 1: 1, and add the concentration of 30 grams of urea and 10.0 grams is the hydrochloric acid solution of 36.5 quality % simultaneously, stirs 1 hour, adds 30 grams of kerosene to stir 1 hour, drips ball forming in oil ammonia column.Wet bulb is to solidify 1 hour in the ammoniacal liquor of 6.0 quality % in concentration, then filters, with deionized water washing 2～3 times, 60 DEG C are dried 6 hours, 120 DEG C dry 10 hours, then in dry air with the gas/solid volume ratio of 700: 1 in 600 DEG C of roastings 4 hours, obtain gamma-aluminium oxide carrier.
(2) Kaolinite Preparation of Catalyst
Get 100 grams of above-mentioned gamma-aluminium oxide carriers, be that maceration extract floods with the mixed solution that calcium chloride and hydrochloric acid are prepared, in maceration extract, calcic 0.2 quality %, HCl 2.0 quality % are (all taking butt gamma-aluminium oxide carrier as benchmark, lower same), adding deionized water, is 1.2 Gu make liquid/volume ratio.25 DEG C of dippings rotated evaporate to dryness after 8 hours, 120 DEG C dry 12 hours, then roasting 6 hours in air under the condition that 550 DEG C, gas agent volume ratio are 1200/1.
Carrier after the dipping Ca that aforesaid way makes, be that maceration extract floods with the mixed solution that chloro-iridic acid and hydrochloric acid are prepared, in maceration extract, contain iridium 0.1 quality %, HCl 2.5 quality %, add deionized water, Gu making liquid/volume ratio is that 1.5,25 DEG C of dippings filter for 8 hours, 120 DEG C are dried 12 hours, again in 500 DEG C, H
2o/HCl mol ratio is 50 Water Under chlorine activation 6 hours, 450 DEG C, H
2under/agent volume ratio the condition of 250: 1, use hydrogen reducing 4 hours, obtain catalyst A, its active component content taking butt gamma-aluminium oxide carrier as benchmark is in table 1.
Example 2
Press the method Kaolinite Preparation of Catalyst of example 1, in the maceration extract of different the is calcic that (2) step impregnated carrier uses, calcium content is 0.3 quality %, be 0.3 quality % containing Ir content in the maceration extract of chloro-iridic acid, the active component content of the catalyst B making is in table 1.
Example 3
Press the method Kaolinite Preparation of Catalyst of example 1, in the maceration extract of different the is calcic that (2) step impregnated carrier uses, calcium content is 0.5 quality %, be 0.5 quality % containing Ir content in the maceration extract of chloro-iridic acid, the active component content of the catalyst C making is in table 1.
Example 4
Press the method Kaolinite Preparation of Catalyst of example 1, in the maceration extract of different the is calcic that (2) step impregnated carrier uses, calcium content is 1.4 quality %, be 1.0 quality % containing Ir content in the maceration extract of chloro-iridic acid, the active component content of the catalyst D making is in table 1.
Example 5
Pressing the method Kaolinite Preparation of Catalyst of example 1,, containing strontium 0.5 quality %, is 0.5 quality % containing Ir content in the maceration extract of chloro-iridic acid in different is maceration extract that (2) step impregnated carrier uses, and the active component content of the catalyst E making is in table 1.
Example 6
Press the method Kaolinite Preparation of Catalyst of example 1, baric 0.5 quality % in different is maceration extract that (2) step impregnated carrier uses, is 0.5 quality % containing Ir content in the maceration extract of chloro-iridic acid, and the active component content of the catalyst F making is in table 1.
Comparative example 1
Press the method Kaolinite Preparation of Catalyst of example 1, different is that (2) step is only used the maceration extract impregnated carrier containing chloro-iridic acid, and in maceration extract, Ir content is 0.3 quality %, and the active component content of the catalyst G making is in table 2.
Comparative example 2
Press the method Kaolinite Preparation of Catalyst of example 1, different is that (2) step is only used the maceration extract impregnated carrier containing chloro-iridic acid, and in maceration extract, Ir content is 0.5 quality %, and the active component content of the catalyst H making is in table 2.
Comparative example 3
Press the method Kaolinite Preparation of Catalyst of example 1, different is that (2) step is only used the maceration extract impregnated carrier containing chloro-iridic acid, and in maceration extract, Ir content is 1.0 quality %, and the active component content of the catalyst I making is in table 2.
Example 7～15
Following instance is evaluated catalyst of the present invention and comparative catalyst's reactivity worth.
Two sections of filling 20ml catalyst in continuous fixed bed reactor, the each 10ml of upper-lower section, reforming, the C of 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, react under hydrogen/hydrocarbon mol ratio condition that is 5: 1, adopt the online reaction reactivity worth of the 200th hour to represent the evaluation initial performance of catalyst, the reactivity worth of the 1450th hour represents the evaluation performance in latter stage of catalyst, catalyst A～F reaction result is in table 3, catalyst G～I reaction result is in table 4, under same reaction conditions through 1500 hours average coke contents of post catalyst reaction A～I two sections in table 5.
Data processing computing formula is as follows:
C
9 +aromatics conversion rate=[(C in feedstock oil
9 +c in aromatic hydrocarbons-generation oil
9 +aromatic hydrocarbons × liquid yield) C in/feedstock oil
9 +aromatic hydrocarbons] × 100% (quality)
Aromatic ring loss=[aromatic ring total mole number in (in 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/catalyst nature culture amount on catalyst) × 100%
Wherein C
9 +aromatics conversion rate represents the activity of catalyst, and aromatic ring loss represents the selective of catalyst.
Table 1
Table 2
Table 3
Table 4
Table 5
| Instance number | 7 | 8 | 9 | 10 | 11 | 12 | 13 | 14 | 15 |
| 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 |
Example 16～23
By regenerating as follows containing Pd/carbon catalyst after stability test in 1500 hours.
At 0.2MPa, oxygen content is 0.6 volume %, gas volume is 3000/1 with the ratio of catalyst volume, beds inlet temperature is to burn 2 hours under the condition of 430 DEG C, adjust and burn temperature to 470 DEG C subsequently, keep this inlet temperature to burning end, burn and finish rear catalyst in 500 DEG C, H
2o/HCl mol ratio is 40 Water Under chlorine activation 6 hours, 450 DEG C, H
2under/agent volume ratio the condition of 250: 1, use hydrogen reducing 4 hours, obtain the catalyst after regeneration.
Two sections of filling 20ml catalyst in continuous fixed bed reactor, the each 10ml of upper-lower section, with the C of the reformation described in example 7, disproportionation, isomerization by-product
9 +aromatic hydrocarbons is raw material.Use regenerated catalyst at 484 DEG C, 1.0MPa, liquid volume air speed 3 hours
-1, react under hydrogen/hydrocarbon mol ratio condition that is 5: 1.Choose the reaction result of the online reaction data of the 200th hour after as catalyst regeneration, evaluation result is in table 6.
As shown in Table 6, bimetallic catalyst provided by the invention is after regeneration, BTX yield, liquid is received, aromatic ring loss all with regeneration before fresh catalyst substantially suitable, and the performance of single-metal reforming catalyst G, H, the I regeneration rear catalyst reactivity worth of comparing with fresh catalyst obviously declines, BTX yield significantly reduces.
Table 6
Claims (12)
1. a C
9 +heavy arenes lightening catalyst, is made up of high-temperature inorganic oxide carrier and the following active component of the content taking carrier as benchmark:
Ir 0.1～1.0 quality %,
Alkaline-earth metal 0.1～2.0 quality %,
Halogen 0.01～3.0 quality %.
2. according to catalyst claimed in claim 1, it is characterized in that described catalyst activity constituent content is as follows:
Ir 0.1～0.6 quality %,
Alkaline-earth metal 0.1～1.5 quality %,
Halogen 0.1～2.0 quality %.
3. according to the catalyst described in claim 1 or 2, it is characterized in that described alkaline-earth metal is Mg, Ca, Sr or Ba.
4. according to the catalyst described in claim 1 or 2, it is characterized in that described halogen is chlorine, high-temperature inorganic oxide carrier is aluminium oxide.
5. the preparation method of catalyst described in a 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 with containing iridic compound solution impregnation, after being dried, carry out water chlorine activation, reduction.
6. in accordance with the method for claim 5, it is characterized in that oxide, chloride, nitrate or the acetate that the compound of described alkaline including earth metal is alkaline-earth metal.
7. in accordance with the method for 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. in accordance with the method for claim 5, it is characterized in that containing halide containing in iridic compound solution.
9. in accordance with the method for claim 5, it is characterized in that sintering temperature is 450～700 DEG C.
10. in accordance with the method for claim 5, it is characterized in that the temperature of water chlorine activation is 400～700 DEG C, the H passing into when activation
2the mol ratio of O and HCl is 3～100: 1.
11. 1 kinds of C
9 +the method of heavy aromatic hydrocarbon light, comprises C
9 +heavy arene and catalyst claimed in claim 1 under hydrogen exists, haptoreaction under 380～600 DEG C, 0.1～5.0MPa condition.
12. in accordance with the method for claim 11, it is characterized in that described C
9 +the liquid volume air speed that heavy arene contacts with catalyst is 1～100 hour
-1, hydrogen/hydrocarbon mol ratio is 0.1～15.0: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010276701.XA CN102397791B (en) | 2010-09-09 | 2010-09-09 | Catalyst for conversion of C9<+> heavy aromatic hydrocarbon to light aromatic hydrocarbon, preparation and application method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010276701.XA CN102397791B (en) | 2010-09-09 | 2010-09-09 | Catalyst for conversion of C9<+> heavy aromatic hydrocarbon to light aromatic hydrocarbon, preparation and application method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102397791A CN102397791A (en) | 2012-04-04 |
| CN102397791B true CN102397791B (en) | 2014-07-02 |
Family
ID=45880673
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010276701.XA Active CN102397791B (en) | 2010-09-09 | 2010-09-09 | Catalyst for conversion of C9<+> heavy aromatic hydrocarbon to light aromatic hydrocarbon, preparation and application method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102397791B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2010
- 2010-09-09 CN CN201010276701.XA patent/CN102397791B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102397791A (en) | 2012-04-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101172250B (en) | Light hydrocarbon aromatization catalyst and its preparing process | |
| CN103121906B (en) | Method for preparing mononuclear aromatics by using polycyclic aromatic hydrocarbon | |
| CN104399520B (en) | Catalyst for producing high-octane-number gasoline composition from heavy aromatic hydrocarbons and preparation method of catalyst | |
| CN101987969B (en) | Method for converting C9+ heavy arenes into light arenes | |
| CN107206365A (en) | For converting methanol into the method for being suitable as gasoline or mixed material | |
| CN100548480C (en) | A kind of hydro carbons Working liquids product modifying catalyst and method for modifying | |
| CN102909058B (en) | Catalyst containing modified EUO type molecular sieve, and preparation method and application thereof | |
| CN102078819A (en) | Light hydrocarbon aromatization catalyst and preparation method thereof | |
| CN101444732B (en) | C9 aromatic hydrocarbon lightening catalyst and lightening method thereof | |
| JP5291924B2 (en) | Method for isomerizing aromatic C8 compounds in the presence of a catalyst comprising modified EUO zeolite | |
| CN101357876B (en) | Method for conveying C<+>9 heavy aromatics to light aromatics | |
| JPH10180101A (en) | Dehydrogenation catalyst | |
| CN1191331C (en) | Dual-function reforming catalyst containing Pt and Sn and its preparing process | |
| CN102397791B (en) | Catalyst for conversion of C9<+> heavy aromatic hydrocarbon to light aromatic hydrocarbon, preparation and application method | |
| US11648544B2 (en) | Catalyst for converting alkylaromatic hydrocarbon and preparation method thereof | |
| CN102895993B (en) | Sulfur-containing alkane aromatization catalyst, preparation method and applications thereof | |
| CN102909057B (en) | Catalyst comprising EUO type zeolite, preparation method and applications thereof | |
| JPS60146835A (en) | Preparation of olefin | |
| CN106975515A (en) | A kind of base metal heavy aromatics lightening catalyst and preparation method thereof | |
| CN104148066B (en) | A kind of multimetal reforming catalyst and preparation and application thereof | |
| CN104383961A (en) | Catalyst for hydrocracking heavy aromatics for producing high-purity BTX aromatics and preparing method of catalyst | |
| US20230249166A1 (en) | Catalyst for Producing C8 Aromatic Hydrocarbon Having Reduced Ethylbenzene Content and Preparation Method Therefor | |
| CN112657539A (en) | Selective hydrocracking catalyst for polycyclic aromatic hydrocarbon and preparation method and application thereof | |
| CN114433217B (en) | Benzene and synthesis gas alkylation catalyst and preparation method and application thereof | |
| CN112023978B (en) | Xylene isomerization catalyst and preparation method and application 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 |