CN1227192C - Heavy arenes lightening catalyst and preparing method thereof - Google Patents
Heavy arenes lightening catalyst and preparing method thereof Download PDFInfo
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- CN1227192C CN1227192C CNB021258422A CN02125842A CN1227192C CN 1227192 C CN1227192 C CN 1227192C CN B021258422 A CNB021258422 A CN B021258422A CN 02125842 A CN02125842 A CN 02125842A CN 1227192 C CN1227192 C CN 1227192C
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Abstract
The present invention relates to a catalyst for light aromatics of heavy aromatics, which comprises 0.01 to 2.0 wt% of metal in the VIII family and a composite carrier containing 30 to 70 wt% of ZSM-5 zeolite, 5 to 20 wt% mordenite and 10 to 65 wt% alumina. The catalyst is used for light aromatics of heavy aromatics. The present invention can increase the conversion rate of C9 aromatics and the output rate of benzene and xylene and decrease carbon deposit.
Description
Technical field
The present invention is a kind of heavy arenes lightening catalyst and preparation method thereof.Specifically, be the Catalysts and its preparation method of the heavy aromatic hydrocarbon light more than nine carbon atoms being produced benzene, toluene and dimethylbenzene (BTX) that is applicable to of a kind of silicon aluminate zeolite and noble metal component.
Background technology
Heavy aromatics refers generally to catalytic reforming, and disproportionation and isomerization reaction generate contained C in oil and the cracking of ethylene hydrogenated gasoline
9～C
16Single, double cycloalkyl aromatic hydrocarbons.The heavy aromatics resource is not rationally utilized for a long time, removes a small amount of as solvent and extraction C
9Or C
10Outside the monomer aromatic hydrocarbons, all mix in the fuel basically and use.Perfect day by day along with environmental regulation, the content of heavy aromatics will be subjected to strict restriction in the oil fuel.Therefore, how to effectively utilize the heavy aromatics resource and become an important research project.
At present, the main method of heavy aromatics lighting is to adopt pyrolysis method and catalytic dealkylation method to produce light aromatic hydrocarbons, and its main drawback is temperature of reaction and pressure height, and air speed is low, and the commercialization of technology is restricted.
The main reaction that heavy arenes catalytic dealkylation carries out lighting is the hydro-dealkylation reaction, mainly is to slough C
2Above alkyl.Its reaction expression is as follows:
According to above reaction expression as can be known: ethyl methyl benzene, diethylbenzene or dimethyl ethyl benzene etc. contained in the heavy arene can be sloughed ethyl, and depropylations such as n-proplbenzene, isopropyl benzene, methyl-propyl benzene generate benzene,toluene,xylene and ethane or propane; Condensed-nuclei aromaticss such as naphthalene system and methylnaphthalene system at first carry out the aromatic hydrogenation saturated reaction, and saturated then aromatic ring carries out the disconnected side chain reaction of open loop, finally generates benzene,toluene,xylene and ethane or propane.
In recent years, have many about carry out the report of heavy aromatics lighting research by catalytic dealkylation.USP4,341,622 disclose a kind of method of utilizing the heavy reformate to produce BTX.This method adopts that restricted index is 1～12, the zeolite of high silica alumina ratio, low acid activity is a catalyzer, and the heavy reformate is reacted under the condition of 800～1000 (427～540 ℃), the resultant fractionation by distillation is obtained benzene, toluene and dimethylbenzene (BTX) again.Also contain in this catalyzer and have the active VIII of hydrogenation/dehydrogenation family precious metal, preferred platinum, its zeolite silica alumina ratio of selecting for use is all higher, is generally more than 200, preferred 500～1600, 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 dimethylbenzene is not converted to other material in reaction process.
USP5,001,296 discloses a kind of method of arenes catalytic hydro-dealkylation.The catalyzer that uses in this method comprises metal component and the accessible raw material range broad of this catalyzer of MCM-22 zeolite that is selected from precious metal, nickel or the mixture between them, can process C
6～C
12Mononuclear aromatics is greater than the raw material of 50mol%, as for improving the high boiling point gasoline component that the light cycle quality is obtained.The MCM-22 zeolite of its use has advantages such as Heat stability is good and specific surface 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 catalyzer of Pt, can be at 600～900 (315～482 ℃), 200psig, liquid hourly space velocity 2.5, hydrogen cycle rate 2000 standard scales
3Under the reaction conditions of/barrel, with C
+ 9Aromaticity content is that the feedstock conversion of 96.8 moles of % is BTX.Its reactive behavior is with C
9 +Transformation efficiency is calculated as 21.0～82.0mol%, and the BTX selectivity reaches 63.8～79.8mol%.
Disclose a kind of heavy aromatic hydrocarbon light among the CN1117404A and produced the catalyzer of BTX.This catalyzer 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 %, 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) 500～1200 operational condition under, this catalyzer has higher activity and activity stability and lower hydrogen consumption.
USP5,990,031 disclose a kind of improvement zeolite catalyst takes off the active method of alkyl.This patent is carried out zeolite ammonium exchange, roasting earlier, carry out the ammonium exchange second time then, the zeolite of handling after ammonium exchanges with fluorine-containing salts solution is introduced fluorine again, the zeolite of introducing behind the fluorine also can further be introduced metal components such as nickel, and then with this zeolite mix with binding agent, moulding, roasting make catalyzer.For transalkylation process tail oil and heavy reformation liquid, this catalyzer has the higher alkyl activity of taking off, and demonstrates the good selectivity for benzene and monoalkyl aromatic hydrocarbons simultaneously.The zeolite that is suitable for carrying out with this method modification has mordenite, ZSM-5, ω-zeolite or beta-zeolite.
Summary of the invention
The purpose of this invention is to provide a kind of heavy arenes lightening catalyst, this catalyzer has higher C
9Aromatic hydrocarbons activity of conversion and activity stability, and have higher benzene and dimethylbenzene productive rate.
Another object of the present invention provides a kind of above-mentioned Preparation of catalysts method, and this method is easy and simple to handle and can reduce the zeolite loss.
Catalyzer of the present invention adopts the zeolite with two kinds of different apertures to prepare complex carrier, makes and contains the bigger mordenite in an amount of aperture in the carrier, thereby can make C
9 +Heavy arene reacts in bigger zeolite pore, thereby improves C
9 +The productive rate of the transformation efficiency of heavy arene and benzene and dimethylbenzene.In addition, the mordenite that contains in the carrier has stronger anti-carbon deposition ability, therefore makes activity of such catalysts stability increase.
Catalyzer provided by the invention adopts the method preparation of first moulding, back ion-exchange.This method is compared with the method for the first ion-exchange aftershaping of habitually practising in the art, can reduce the loss of ion exchange process mesolite, has improved the yield of zeolite, also can reduce the pollution of zeolite dust to environment simultaneously, shortens the filtration washing required time greatly.
Embodiment
Heavy arenes lightening catalyst provided by the invention comprises VIII family metal and the complex carrier of 0.01～2.0 heavy %, and described complex carrier comprises the ZSM-5 zeolite of 30～70 heavy %, the mordenite of 5～20 heavy % and the aluminum oxide of 10～65 heavy %.
Complex carrier provided by the invention comprises the zeolite in two kinds of different apertures, and a kind of is the ZSM-5 zeolite of mesopore, and a kind of is the mordenite of macropore, and all the other are the binding agent aluminum oxide.The content of ZSM-5 zeolite preferred 40～60 heavy %, mordenite content preferred 10～20 heavy % in the complex carrier, alumina content preferred 20～50 heavy %.
The metal active constituent of catalyzer of the present invention is selected from VIII family metal, preferred platinum or palladium, its content preferred 0.03～0.5 heavy %.Also can contain 0.01～0.5 heavy % rhenium or tin in the catalyzer, form two metal constituent element catalyzer, preferred rhenium or tin content are 0.01～0.3 heavy %.Also can contain the rhenium of 0.01～0.3 heavy % and the tin of 0.01～0.3 heavy % in the catalyzer simultaneously, form three metal constituent element catalyzer.
The silica alumina ratio of ZSM-5 zeolite in the described catalyzer, promptly the mol ratio of silicon oxide and aluminum oxide is 15～150, and is preferred 25～120, the silica alumina ratio of mordenite is 10～30, preferred 25～30.
The preferred gama-alumina of described aluminum oxide or η-aluminum oxide, gama-alumina or η-aluminum oxide that the high-purity hydrated aluminum oxide that preferably adopts the aluminum alkoxide hydrolysis to make prepares.
Preparation of catalysts method of the present invention comprises:
(1) sodium type ZSM-5 zeolite, mordenite and hydrated aluminum oxide are mixed by the butt weight ratio, pinch through mixing, moulding, roasting make complex carrier,
(2) with ammonium salt aqueous solution complex carrier is carried out ion-exchange, make the exchange capacity of the sodium ion in the carrier be at least 90%, washing then,
(3) compound of VIII family metal is made into carrier after steeping fluid floods above-mentioned ammonium exchange, dry, roasting.
(1) step of aforesaid method is the preparation of complex carrier, be that the ZSM-5 zeolite of sodium type and mordenite and hydrated aluminum oxide are mixed by predetermined proportion, add again mixed powder weight 25～60%, preferred 35～45%, concentration be the aqueous nitric acid of 1～5 heavy %, preferred 1.5～3.0 heavy % mix pinch, moulding, again with the shaping carrier drying, roasting in 450～650 ℃, preferred 500～600 ℃ air, roasting time 2～8 hours, preferred 3～6 hours.
Described method (2) step is the ammonium exchange, promptly with ammonium salt aqueous solution carrier is carried out the ammonium exchange, removes sodium ion wherein, and the exchange capacity of sodium is at least 90% in the carrier, preferred 90～95%.The temperature of carrying out ion-exchange is 15～120 ℃, preferred 85～100 ℃, used ammonium salt is ammonium chloride or ammonium nitrate, and the ammonium salt concentration of preparation is 0.1～0.8N, preferred 0.2～0.6N, during each ion-exchange preferred 1～6 hour, exchange number of times preferred one or secondary.After the ion-exchange carrier washing is not existed to there being negatively charged ion, can introduce the metal constituent element.
The inventive method (3) step is to introduce metal component with pickling process in carrier to make catalyzer.The steeping fluid of preparation should contain the soluble compound of required each metal component of catalyzer.When only containing VIII family metal in the catalyzer, with VIII family metallic compound preparation steeping fluid; When containing VIII family metal and rhenium or tin in the catalyzer, be mixed with steeping fluid with VIII family metallic compound and rhenium-containing or stanniferous compound; Contain VIII family metal, rhenium and Xi Shi in the catalyzer, then with VIII family metallic compound, contain rhenium compound and sn-containing compound is mixed with steeping fluid.Preferred VIII family metallic compound is Platinic chloride or Palladous chloride, and preferred sn-containing compound is a tin protochloride, and preferably containing rhenium compound is perrhenic acid.
The preferred room temperature of the temperature of described impregnated carrier, the liquid-solid volume ratio during dipping is 1～3, dipping time is 8～60 hours, preferred 12～36 hours.Carrier behind the impregnating metal should carry out drying and roasting, and maturing temperature is 400～600 ℃, preferred 450～550 ℃, and the time is 1～10 hour, preferred 3～6 hours.
High-purity hydrated aluminum oxide that the preparation complex carrier used preferred aluminum alkoxide hydrolysis of hydrated aluminum oxide makes is as according to disclosed by C in the CN85100218 patent
1～C
4High-purity hydrated aluminum oxide of making of low-carbon alkoxy aluminium hydrolysis.Described metal component Sn also can promptly adopt high-purity hydrated aluminum oxide of stanniferous 0.01～0.5 heavy % to prepare complex carrier by introduce carrier in advance when preparing hydrated aluminum oxide.
Catalyzer provided by the invention is applicable to that heavy aromatic hydrocarbon light produces benzene, toluene and dimethylbenzene.Described heavy arene is for containing C
+ 9The hydrocarbon feed of aromatic hydrocarbons.Heavy aromatic hydrocarbon light reaction needs carry out under hydro condition, and suitable condition is 350～450 ℃, 0.5～3.5MPa, feed weight air speed 1～5 o'clock
-1, hydrogen/hydrocarbon volume ratio 500～1200.Can obtain pure aromatic hydrocarbon product after reaction product recovery and the separation.
Further specify the present invention below by example, but the present invention is not limited to this.
Example 1～6
Prepare catalyzer of the present invention.
(1) preparation complex carrier
(dying of Shanghai seven factories produce with an amount of sodium type ZSM-5 zeolite, sodium content 0.4～0.6 heavy %), sodium type mordenite (sodium content 4.0～8.0 heavy %) mixes with the HP aluminium hydrate powder for preparing by the described method of CN85100218, add powder weight 40%, concentration and be 2% aqueous nitric acid mix pinch, extruded moulding, 110～120 ℃ of dryings 2 hours, 550 ℃ of roastings made complex carrier in 4 hours in the air.
(2) ammonium exchange
Get the above-mentioned complex carrier of 10 grams, at 90 ± 10 ℃ of NH that use 0.5N down
420 milliliters of Cl solution carried out ion-exchange 2 hours to carrier, filter, with deionized water wash to there not being Cl
-
(3) introduce the metal constituent element
The precursor of each metal component of predetermined amount is mixed with steeping fluid, it in room temperature, liquid-solid ratio the carrier after the above-mentioned ammonium ion exchange of dipping 24 hours under 2 the condition, filter, 110～120 ℃ of dryings 2 hours, 500 ℃ of roastings promptly got catalyzer in 4 hours in the air, and note is made catalyst A, B, C, D, E, F respectively.
In the aforesaid method, when containing two or more metal component in the catalyzer, adopt the required metal constituent element of leaching method introducing altogether.The used platinic compound that contains of preparation steeping fluid is a Platinic chloride, and its concentration is 2.86 mg/ml.Containing rhenium compound is perrhenic acid, and concentration is 11.8 mg/ml.Containing palladium compound is Palladous chloride, during use with dissolving with hydrochloric acid and be mixed with the solution that concentration is 1 heavy %.Sn-containing compound is a tin protochloride, during use with water dissolution and be mixed with the solution that concentration is 1 heavy %.
NaZSM-5 zeolite, sodium type mordenite and Al when table 1 has been listed each example catalyst metal component content and preparation carrier
2O
3Consumption.
Comparative Examples 1
Method by example 1 prepares comparative catalyst K, only mixes with the HP aluminium hydrate powder with the ZSM-5 zeolite when different is the preparation carrier, makes catalyzer K again after soaking method supporting Pt, Sn and Re altogether, and its each component concentration sees Table 1.
Example 7～8
Getting the SB aluminium hydrate powder that German condea company produces, is the SnCl of 10 mg/ml with concentration under the condition of room temperature, liquid-solid ratio 2
2Solution impregnation 15 hours, 110～120 ℃ of dryings make the aluminum oxide of stanniferous 0.48 heavy % after 2 hours.With this stanniferous aluminum oxide and ZSM-5 zeolite and mordenite 25: 60: 15 butt weight ratio mixing in accordance with regulations, by the method HNO of example 1
3Make stanniferous carrier after peptization, the moulding, carry out the ammonium exchange then, the Platinic chloride and the perrhenic acid that are respectively 2.86 mg/ml and 11.8 mg/ml with concentration are made into steeping fluid, in liquid/solid volume than being 2 ratio impregnated carrier 24 hours at room temperature, 110～120 ℃ of dryings 2 hours, 500 ℃ of roastings made catalyzer G and H in 4 hours in the air.Its component concentration zeolite character sees Table 2.
Example 9
Catalyst A～F of the present invention and comparative catalyst are estimated.
On 10 milliliters of reaction units, filling 5 gram catalyzer are with the C of reformation, disproportionation and isomerization by-product
+ 9Aromaticity content is that the heavy arenes of 97.95 heavy % are raw material, 400 ℃, when 1.0MPa, weight space velocity 2.0
-1, hydrogen/hydrocarbon volume ratio 1000 condition under catalyzer is carried out evaluation experimental, gained the results are shown in Table 3.
Used heavy arene raw material (heavy %) composed as follows: C
- 8Alkane and naphthenic hydrocarbon 0.47; C
8Aromatic hydrocarbons 1.58; C
9Aromatic hydrocarbons 21.42; C
10Aromatic hydrocarbons 44.73; C
11Aromatic hydrocarbons 13.80; C
+ 12Aromatic hydrocarbons 18.00.In the table 3
Example 10
Method by example 9 is estimated catalyzer G of the present invention and H, the results are shown in table 4.
By table 3, table 4 data as can be known, catalyzer provided by the invention is compared with the comparative catalyst, can obtain higher C
+ 9The growing amount of aromatics conversion rate and BTX.
Table 1
| Instance number | 1 | 2 | 3 | 4 | 5 | 6 | Contrast |
| The catalyzer numbering | A | B | C | D | E | F | K |
| ZSM-5 zeolite silica alumina ratio consumption, heavy % mordenite silica alumina ratio consumption, heavy % Al 2O 3The crystal formation consumption, heavy % metal content, heavy % Pt Pd Re Sn | 60 60 27 5 γ 35 0.05 - 0.10 0.12 | 60 60 27 10 γ 30 0.05 - 0.10 0.12 | 60 60 27 15 γ 25 - 0.05 0.15 0.05 | 60 60 27 20 γ 20 0.25 - - - | 60 40 27 20 γ 40 0.15 - - 0.12 | 120 60 27 20 γ 20 0.15 - 0.12 - | 60 60 - - γ 40 0.05 - 0.10 0.12 |
Table 2
| Instance number | 7 | 8 |
| The catalyzer numbering | G | H |
| ZSM-5 zeolite silica alumina ratio mordenite silica alumina ratio metal component content, heavy % Pt Sn Re | 60 11 0.05 0.12 0.10 | 60 17 0.05 0.12 0.10 |
Table 3
| The catalyzer numbering | A | B | C | D | E | F | K |
| Products distribution, heavy % C - 8Alkane and cycloalkanes benzene (B) toluene (T) dimethylbenzene (X) trimethylbenzene (TMB) other | 6.2 4.2 7.5 17.0 15.2 49.9 | 6.8 5.0 6.5 19.0 14.0 48.7 | 7.2 5.8 5.0 22.5 12.5 47.0 | 7.4 6.8 3.5 25.4 10.8 46.1 | 6.5 4.8 7.0 18.0 14.5 49.2 | 7.0 5.2 6.3 20.0 13.5 48.0 | 5.9 3.9 8.1 15.8 15.8 50.5 |
| C + 9Aromatics conversion rate, heavy % BTX growing amount, heavy % | 33.5 28.7 | 36.0 30.5 | 39.2 33.3 | 41.91 35.7 | 34.97 29.8 | 37.21 31.5 | 32.3 27.8 |
Table 4
| The catalyzer numbering | G | H |
| Products distribution, heavy % C - 8Alkane and cycloalkanes benzene (B) toluene (T) dimethylbenzene (X) trimethylbenzene (TMB) other | 6.1 4.1 7.9 16 2 15.6 50.1 | 6.6 4.6 7.5 17.0 15.0 49.3 |
| C + 9Aromatics conversion rate, heavy % BTX growing amount, heavy % | 32.9 28.2 | 34.35 29.1 |
Claims (11)
1, a kind of heavy arenes lightening catalyst comprises that 0.01～2.0 weighs platinum or palladium and the complex carrier of %, and described complex carrier comprises the ZSM-5 zeolite of 30～70 heavy %, the mordenite of 5～20 heavy % and the aluminum oxide of 10～65 heavy %.
2,, it is characterized in that comprising in the described complex carrier ZSM-5 zeolite of 40～60 heavy %, the mordenite of 10～20 heavy % and the aluminum oxide of 20～50 heavy % according to the described catalyzer of claim 1.
3,, it is characterized in that described aluminum oxide is gama-alumina or η-aluminum oxide according to claim 1 or 2 described catalyzer.
4, according to claim 1 or 2 described catalyzer, the silica alumina ratio mol ratio that it is characterized in that the ZSM-5 zeolite is 15～150, and the silica alumina ratio of mordenite is 10～30.
5,, it is characterized in that also containing in the described catalyzer rhenium or the tin of 0.01～0.5 heavy % according to claim 1 or 2 described catalyzer.
6,, it is characterized in that also containing in the described catalyzer rhenium of 0.01～0.3 heavy % and the tin of 0.01～0.3 heavy % according to claim 1 or 2 described catalyzer.
7, the described Preparation of catalysts method of a kind of claim 1 comprises:
(1) sodium type ZSM-5 zeolite, mordenite and hydrated aluminum oxide are mixed by the butt weight ratio, pinch through mixing, moulding, roasting make complex carrier,
(2) with ammonium salt aqueous solution complex carrier is carried out ion-exchange, make the sodium ion exchange capacity in the carrier be at least 90%, washing then,
(3) compound of platinum or palladium is made into carrier after steeping fluid floods above-mentioned ammonium exchange, dry, roasting.
8, in accordance with the method for claim 7, it is characterized in that described aluminum oxide is selected from high-purity hydrated aluminum oxide that the aluminum alkoxide hydrolysis makes, wherein contain the tin of 0.01～0.5 heavy %.
9, in accordance with the method for claim 8, it is characterized in that described aluminum oxide is selected from by C
1～C
4High-purity hydrated aluminum oxide of making of aluminum alkoxide hydrolysis.
10, in accordance with the method for claim 7, the compound that it is characterized in that (3) step described platinum or palladium is selected from Platinic chloride or Palladous chloride.
11, in accordance with the method for claim 10, it is characterized in that also containing in the described steeping fluid of (3) step the mixture of tin protochloride or perrhenic acid or tin protochloride and perrhenic acid.
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|---|---|---|---|
| CNB021258422A CN1227192C (en) | 2002-07-30 | 2002-07-30 | Heavy arenes lightening catalyst and preparing method thereof |
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|---|---|---|---|
| CNB021258422A CN1227192C (en) | 2002-07-30 | 2002-07-30 | Heavy arenes lightening catalyst and preparing method thereof |
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| CN1227192C true CN1227192C (en) | 2005-11-16 |
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100425343C (en) * | 2005-06-30 | 2008-10-15 | 中国石油化工股份有限公司 | Alkyl arene isomerizing catalyst and its usage |
| CN100460370C (en) * | 2006-01-11 | 2009-02-11 | 中国石油化工股份有限公司 | Method used for heavy arene light formation and alkyl transfer |
| CN101607207B (en) * | 2008-06-19 | 2011-06-22 | 中国石油天然气股份有限公司 | Heavy aromatic hydrocarbon light catalyst, preparation method and application thereof |
| CN102671696B (en) * | 2011-03-17 | 2014-10-01 | 中国石油化工股份有限公司 | Composite zeolite catalyst containing modified NU-85 zeolite and preparation method |
| CN106345463A (en) * | 2016-08-26 | 2017-01-25 | 山东恒信科技发展有限公司 | Catalyst for heavy aromatics hydrogenation dealkylation |
| CN106693988A (en) * | 2016-12-21 | 2017-05-24 | 山东玉皇化工有限公司 | Method for preparing Pd hydrogenation catalyst composite support |
| CN109395728B (en) * | 2017-08-18 | 2021-10-01 | 中国石油化工股份有限公司 | Catalyst for converting heavy aromatic hydrocarbon into light aromatic hydrocarbon |
| CN109395722B (en) * | 2017-08-18 | 2022-04-05 | 中国石油化工股份有限公司 | Polycyclic aromatic hydrocarbon lightening catalyst |
| EP3539652A1 (en) * | 2018-03-14 | 2019-09-18 | Saudi Arabian Oil Company | Method of heavy reformate conversion into btx over metal-impregnated zsm-5+mesoporous mordenite zeolite composite catalyst |
| CN110745928A (en) * | 2019-11-22 | 2020-02-04 | 武汉格林环源净化工程有限公司 | Chemical fiber sewage treatment agent and application method thereof |
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